US 20200365862A1 IN ( 19 ) United States ( 12 ) Patent Application Publication ( 10 ) Pub . No .: US 2020/0365862 A1 ROUMI et al . ( 43 ) Pub . Date : Nov. 19 , 2020
( 54 ) MEMBRANES FOR ELECTROCHEMICAL 18 , 2013 , provisional application No. 61 / 938,794 , CELLS filed on Feb. 12 , 2014 , provisional application No. 61 / 985,204 , filed on Apr. 28 , 2014 , provisional appli ( 71 ) Applicant: CALIFORNIA INSTITUTE OF cation No. 62 / 024,104 , filed on Jul . 14 , 2014 . TECHNOLOGY , Pasadena, CA ( US ) Publication Classification ( 72 ) Inventors : Farshid ROUMI , Pasadena, CA (US ); Jamshid ROUMI , Pasadena , CA ( US ) ( 51 ) Int . CI . HOIM 2/16 ( 2006.01) ( 73 ) Assignee : CALIFORNIA INSTITUTE OF HOIM 10/0565 (2006.01 TECHNOLOGY, Pasadena , CA ( US ) HOIM 10/0562 ( 2006.01 ) HOIM 10/48 ( 2006.01 ) ( 21 ) Appl . No .: 16 /890,326 HOIM 10/052 ( 2006.01 ) HOIM 10/42 ( 2006.01 ) (22 ) Filed : Jun . 2 , 2020 (52 ) U.S. CI. CPC HOIM 2/1686 ( 2013.01 ) ; HOIM 10/0565 Related U.S. Application Data ( 2013.01 ) ; HOTM 10/0562 ( 2013.01 ) ; HOLM ( 63 ) Continuation of application No. 14 / 680,997 , filed on 10/48 ( 2013.01 ) ; HOIM 2300/0071 ( 2013.01 ) ; Apr. 7 , 2015 , now Pat . No. 10,714,724 , which is a HOLM 10/052 ( 2013.01 ) ; HOTM 10/4235 continuation - in -part of application No. 14 / 546,953 , ( 2013.01 ) ; HOIM 2300/0085 ( 2013.01 ) ; HOIM filed on Nov. 18 , 2014 , now abandoned , said appli 2300/0082 ( 2013.01 ) ; HOIM 2/1673 ( 2013.01 ) cation No. 14 / 680,997 is a continuation - in -part of application No. PCT /US14 / 66200, filed on Nov. 18 , ( 57 ) ABSTRACT 2014 . Ionically conducting composite membranes are provided ( 60 ) Provisional application No. 61 / 976,281 , filed on Apr. which include a solid - state ionically conducting material 7 , 2014 , provisional application No. 61 / 905,678 , filed The ionically conducting composite membranes may be on Nov. 18 , 2013 , provisional application No. 61/938 , used in electrochemical cells . The solid - state ionically con 794 , filed on Feb. 12 , 2014 , provisional application ducting material may be an electrochemically active mate No. 61/9 5,204 , filed on Apr. 28 , 2014 , provisional rial. In some electrochemical the solid - state ionically application No. 62 / 024,104 , filed on Jul. 14 , 2014 , conducting material may be in electronic communication provisional application No. 61 / 905,678 , filed on Nov. with an external tab . Patent Application Publication Nov. 19 , 2020 Sheet 1 of 34 US 2020/0365862 A1
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MEMBRANES FOR ELECTROCHEMICAL covery and integration of new materials for battery compo CELLS nents . Lithium battery technology, for example , continues to rapidly develop , at least in part, due to the discovery of novel CROSS REFERENCE TO RELATED electrode and electrolyte materials for these systems . The APPLICATION element lithium has a unique combination of properties that make it attractive for use in an electrochemical cell . First , it [ 0001 ] The present application is a continuation applica is the lightest metal in the periodic table having an atomic tion of U.S. patent application Ser . No. 14 / 680,997 filed Apr. mass of 6.94 AMU . Second , lithium has a very low elec 7 , 2015 , which claims the benefit of priority from U.S. trochemical oxidation / reduction potential ( i.e. , -3.045 V vs. Provisional Application No. 61 / 976,281 , filed Apr. 7 , 2014 NHE ( normal hydrogen reference electrode ) ). This unique and is a continuation - in -part application U.S. patent appli combination of properties enables lithium based electro cation Ser . No. 14 / 546,953 , filed Nov. 18 , 2014 , which chemical cells to have very high specific capacities . State of claims the benefit of priority to U.S. Provisional Application the art lithium ion secondary batteries provide excellent No. 61 / 905,678 , filed Nov. 18 , 2013 ; U.S. Provisional Appli charge -discharge characteristics, and thus , have also been cation No. 61 / 938,794 , filed Feb. 12 , 2014 ; U.S. Provisional widely adopted as power sources in portable electronic Application No. 61 / 985,204 , filed Apr. 28 , 2014 and U.S. devices, such as cellular telephones and portable computers. Provisional Application No. 62 / 024,104 , filed Jul . 14 , 2014 U.S. Pat . Nos . 6,852,446 , 6,306,540 , 6,489,055 , and all of which are incorporated herein by reference in their “ Lithium Batteries Science and Technology ” edited by Gho entireties . lam - Abbas Nazri and Gianfranceo Pistoia , Kluer Academic Publishers, 2004 , which are hereby incorporated by refer STATEMENT REGARDING FEDERALLY ence in their entireties, are directed to lithium and lithium SPONSORED RESEARCH OR DEVELOPMENT ion battery systems . [ 0002 ] Not applicable. [ 0006 ] Advances in electrode materials, electrolyte com positions and device geometries continue to support the BACKGROUND further development of Li based electrochemical systems. [ 0003 ] Over the last few decades revolutionary advances For example, U.S. Patent Application Publication US2012 / have been made in electrochemical storage and conversion 0077095 , published on Mar. 29 , 2012 , and International devices expanding the capabilities of these systems in a Patent Application publication WO 2012/034042 , published variety of fields including portable electronic devices , air on Mar. 15 , 2012 , disclose three - dimensional electrode array and space craft technologies, passenger vehicles and bio structures for electrochemical systems including lithium medical instrumentation . Current state of the art electro batteries . chemical storage and conversion devices have designs and [ 0007 ] As will be generally recognized from the forego performance attributes that are specifically engineered to ing , a need currently exists for electrochemical systems, provide compatibility with a diverse range of application such as lithium based or alkaline based batteries, flow requirements and operating environments . For example , batteries , supercapacitors and fuel cells, exhibiting electro advanced electrochemical storage systems have been devel chemical properties useful for a range of applications. Spe oped spanning the range from high energy density batteries cifically, lithium electrochemical systems capable of good exhibiting very low self - discharge rates and high discharge electrochemical performance and high versatility for both reliability for implanted medical devices to inexpensive, primary and secondary lithium based batteries are needed . light weight rechargeable batteries providing long runtimes for a wide range of portable electronic devices to high SUMMARY capacity batteries for military and aerospace applications [ 0008 ] In an aspect , the invention provides an ionically capable of providing extremely high discharge rates over conducting composite membrane which includes a solid short time periods. state ionically conducting material. The membranes pro [ 0004 ] Despite the development and widespread adoption vided by the present invention can be used in electrochemi of this diverse suite of advanced electrochemical storage and cal cells . Use of a solid - state ionically conducting material conversion systems , significant pressure continues to stimu in the composite membrane can seal one portion of the cell late research to expand the functionality of these systems, from another. For example, use of such an ionically con thereby enabling an even wider range of device applications. ductive membrane can allow use of an aqueous electrolyte Large growth in the demand for high power portable elec in contact with one electrode and a non - aqueous electrolyte tronic products , for example , has created enormous interest in contact with another electrolyte . In other aspects , the in developing safe, light weight primary and secondary invention provides electrochemical cells including the ioni batteries providing higher energy densities. In addition , the cally conducting composite membranes and methods for demand for miniaturization in the field of consumer elec using the electrochemical cells . In embodiments, the elec tronics and instrumentation continues to stimulate research trochemical cell is a Li - ion or Na - ion cell into novel design and material strategies for reducing the [ 0009 ] Solid - state ionically conducting materials conven sizes , masses and form factors of high performance batter tionally used as electrolytes include gelled polymers, solvent ies . Further, continued development in the fields of electric free polymers, inorganic crystalline compounds and inor vehicles and aerospace engineering has also created a need ganic glasses . In an embodiment, solid - state ionically con for mechanically robust, high reliability, high energy density ducting materials include materials which include materials and high power density batteries capable of good device whose ionic conductivity is electronically “ activated ” , such performance in a useful range of operating environments . as by application of voltage or current . In embodiments, the [ 0005 ] Many recent advances in electrochemical storage applied current or voltage can be direct or alternating ( e.g. and conversion technology are directly attributable to dis a sinusoidal voltage ) . In an embodiment, such a material has US 2020/0365862 A1 Nov. 19 , 2020 2 a significantly greater ionic conductivity in the “ activated ” positive electrode and the negative electrode , the composite state ; use of such a material can provide gating functionality . membrane comprising a layer comprising a solid - state ioni [ 0010 ] In a further embodiment, solid - state ionically con cally conductive material . In an embodiment, the cell further ducting materials suitable for use in the composite mem comprises at least one liquid electrolyte disposed between branes disclosed herein include materials conventionally the composite membrane and each of the positive and the used as active materials in electrochemical cells . Such a negative electrodes and the composite membrane comprises material may be “ activated ” by application of a voltage a porous or perforated electronically insulating separator varying between the charge - discharge voltage of the elec layer disposed between the layer comprising the solid - state trolyte . In an embodiment, such a solid - state ionically con ionically conductive material and each of the positive and ductive material is an oxide material , such as lithium titanate the negative electrode . In an embodiment, the positive or titanium dioxide . In another embodiment, the solid - state electrode comprises a positive electrode active material and ionically conductive material is a semiconductor, such as a first current collector in electronic communication with the silicon . In another embodiment, the solid - state ionically positive electrode active material , the first current collection conductive material is a conventional carbonaceous anode further comprising a first external connection tab , a negative material such as graphite, modified graphite, and non electrode comprising a negative electrode active material graphitic carbons. In a further embodiment, one or more of and a second current collector in electronic communication these materials conventionally used as electrochemically with the negative electrode active material, the second active materials is used in combination with one or more current collector further comprising a second external con conventional solid electrolyte materials . Benefits of such nection tab and the ionically conductive solid - state material cells include , but are not limited to higher mechanical being in electronic communication with a third external flexibility of the cell during manufacturing and operation , connection tab . In an embodiment, the solid - state ionically ease of manufacturing, allowing different materials with conductive material is electronically “ activatable ” so that better thermal and mechanical stability to be used , slow application of a voltage between the third external tab and down of the migration of active materials between the any of the electrodes produces a significant increase in the electrodes and lower impedance between the electrodes and ionic conductivity of the material. the membrane which results in faster rates and longer cycle [ 0015 ] In an embodiment, the invention provides an elec life . In some embodiments where the electronchemically trochemical cell comprising: active materials are in electrical communication with an [ 0016 ] a positive electrode comprising a positive elec external tabl, active material additives may be released to the trode active material and a first current collector in cell when needed . electronic communication with the positive electrode [ 0011 ] In embodiments, the solid - state ionically conduc active material, the first current collection further com tive material is in the form of a free standing layer, a coating prising a first external connection tab ; layer, or included in a support or frame of an electronically [ 0017 ] a negative electrode comprising a negative elec conducting or electronically insulating material ( e.g. a mate trode active material and a second current collector in rial which does not conduct electrons through the thickness electronic communication with the negative electrode of the support ). Supported solid electrolyte material may be active material, the second current collector further in the form of bulk pieces , particles or fibers . Particles or comprising a second external connection tab ; fibers of solid electrolyte material may be combined with [ 0018 ] a composite membrane disposed between the other materials such binders and / or conductive particles or positive electrode and the negative electrode ; the com fibers. The support or frame may provide high mechanical posite membrane being ionically conductive and com strength to the layer including the solid - state ionically prising conductive material. In an embodiment, the composite mem [ 0019 ] an ionically conductive solid - state material in brane has a shear modulus from 1 GPa - 3 GPa , a tensile electronic communication with a third external con strength of 100-300 MPa and a rupture strength of 900 to nection tab ; 1100 gr. [ 0020 ] a first ionically conductive separator posi [ 0012 ] The ionic conductivity of the composite membrane tioned between the positive electrode and the com may be greater than 1 mS / cm In an embodiment, for posite membrane; and example, the composite membrane in the presence of an [ 0021 ] a second ionically conductive separator posi appropriate electrolyte provides a net ionic resistance from tioned between the negative electrode and the com the positive electrode to the negative electrode selected over posite membrane; and the range of 0.5 ohm cm² to 25 ohm cm², and preferably for [ 0022 ] one or more electrolytes positioned between said some applications less than 5 ohm cm². positive electrode and said negative electrode ; said one [ 0013 ] In an additional aspect , the solid - state ionically or more electrolytes capable of conducting ionic charge conductive material is in electronic communication with an carriers. external connection tab . The external connection tab may [ 0023 ] In a further embodiment, the composite membrane also be referred to as an external tab . In an embodiment, the further comprises a third current collector in electronic external connection tab used to modify the performance of communication with ionically conductive solid - state mate the cell by applying a voltage or current between the external rial, the third current collector being porous or perforated connection tab and either the external connection tab of one [ 0024 ] In an aspect , the disclosure provides an electro of the electrodes or of an additional electronically conduc chemical cell comprising a positive electrode , a negative tive layer in the composite separator electrode and a composite membrane disposed between the [ 0014 ] In an aspect , the disclosure provides an electro positive electrode and the negative electrode, the composite chemical cell comprising a positive electrode, a negative membrane comprising a layer comprising a solid - state ioni electrode and a composite membrane disposed between the cally conductive material . In an embodiment, the solid - state US 2020/0365862 A1 Nov. 19 , 2020 3 ionically conductive material is material conventionally [ 0047 ] In an embodiment, the invention provides an elec used as an active material in a positive or negative electrode trochemical cell comprising: material. In an embodiment, the cell further comprises at [ 0048 ] a positive electrode comprising a positive elec least one liquid electrolyte disposed between the composite trode active material and a first current collector in membrane and each of the positive and the negative elec electronic communication with the positive electrode trodes and the composite membrane comprises a porous or active material, the first current collection further com perforated electronically insulating separator layer disposed prising a first external connection tab ; between the layer comprising the solid - state ionically con [ 0049 ] a negative electrode comprising a negative elec ductive material and each of the positive and the negative trode active material and a second current collector in electrode. electronic communication with the negative electrode [ 0025 ] In an embodiment, the invention provides an elec active material, the second current collector further trochemical cell comprising: comprising a second external connection tab ; [ 0026 ] a positive electrode ; [ 0050 ] a composite membrane disposed between the [ 0027 ] a negative electrode ; positive electrode and the negative electrode; the com [ 0028 ] a composite membrane layer comprising posite membrane being ionically conductive and com ( 0029 ] a layer comprising an ionically conductive prising and electrochemically active solid - state material ; [ 0051 ] an ionically conductive solid - state material in [ 0030 ] a first ionically conductive porous separator electronic communication with a third external con positioned between the positive electrode and the nection tab ; membrane layer ; [ 0052 ] a first ionically conductive separator posi [ 0031 ] a second ionically conductive porous separa tioned between the positive electrode and the com tor positioned between the negative electrode and the posite membrane; and membrane layer ; and [ 0053 ] a second ionically conductive separator posi [ 0032 ] one or more electrolytes positioned between said tioned between the negative electrode and the com positive electrode and said negative electrode; said one posite membrane; and or more electrolytes capable of conducting ionic charge [ 0054 ] one or more electrolytes positioned between said carriers . In an embodiment, the porous separators are positive electrode and said negative electrode ; said one electronically insulating. or more electrolytes capable of conducting ionic charge [ 0033 ] In a further embodiment, the invention provides an carriers . In an embodiment, the separator is electroni electrochemical cell comprising: cally insulating [ 0034 ] a positive electrode; [ 0055 ] In a further embodiment, the invention provides an [ 0035 ] a negative electrode; electrochemical cell comprising: [ 0036 ] a composite membrane layer positioned between [ 0056 ] a positive electrode comprising a positive elec the said electrodes comprising trode active material and a first current collector in [ 0037 ] at least one porous separator layer; electronic communication with the positive electrode active material, the first current collection further com [ 0038 ] at least one ionically conductive and electro prising a first external connection tab ; chemically active solid - state material, and [ 0057 ] a negative electrode comprising a negative elec one or more electrolytes positioned between said positive trode active material and a second current collector in electrode and said negative electrode; said one or more electronic communication with the negative electrode electrolytes capable of conducting ionic charge carriers active material, the second current collector further [ 0039 ] In an additional embodiment, the invention pro comprising a second external connection tab ; vides an electrochemical cell comprising : [ 0058 ] a composite membrane disposed between the [ 0040 ] a positive electrode ; positive electrode and the negative electrode ; and com [ 0041 ] a negative electrode ; prising [ 0042 ] a composite porous separator layer positioned [ 0059 ] an ionically and electronically conductive between the said electrodes comprising layer; [ 0043 ] at least one ionically conductive and electro [ 0060 ] at least one electronically insulating porous chemically active solid - state material, and layer positioned between the said electronically con [ 0044 ] at least one solid - state binder material; and ductive porous layer and an electrode . [ 0045 ] one or more electrolytes positioned between said [ 0061 ] one or more electrolytes positioned between said positive electrode and said negative electrode; said one positive electrode and said negative electrode ; said one or more electrolytes capable of conducting ionic charge or more electrolytes capable of conducting ionic charge carriers. carriers . [ 0046 ] In a further embodiment, the active layer further [ 0062 ] In an embodiment, the disclosure provides an elec comprises a tab which allows connection of the layer trochemical cell comprising: a positive electrode; a negative comprising the ionically conductive and electrochemically electrode; one or more electrolytes positioned between said active solid - state material to another electrode or to a source positive electrode and said negative electrode; said one or of current or voltage . In an embodiment, an active layer acts more electrolytes capable of conducting ionic charge carri as an auxiliary electrode when an external tab is in electronic ers ; and a composite membrane comprising at least two communication with the active layer. In an addition embodi electronically insulating and ionically conductive layers ; ment, the active layer further comprises electronically and said membrane positioned between said positive electrode ionically conductive layer in electronic contact with the and said negative electrode such that said ionic charge electrochemically active material of the layer. carriers are able to be transported between said positive US 2020/0365862 A1 Nov. 19 , 2020 4 electrode and said negative electrode but not electronic formed of an electronically conducting material at least charge carriers . In an embodiment, at least one of the partially coated with an electronically insulating mate electronically insulating and ionically conductive layers rial; comprises a solid electrolyte . [ 0071 ] a second membrane layer being positioned [ 0063 ] In some aspects , the invention provides composite proximate to the other of the positive and the negative membranes and membrane systems for use in an electro electrode and proximate to the first membrane layer, the chemical cell and electrochemical cells comprising these second membrane layer comprising a plurality of pores , membrane systems . In an embodiment, the composite mem the pores of the second membrane layer not overlap brane comprises a first membrane layer comprising a solid ping the apertures of the first membrane layer and the or gel electrolyte disposed within the apertures of a support pores comprising a liquid electrolyte ; structure and a second membrane layer comprising a plu [ 0072 ] wherein each of the first and second membrane rality of pores , the pores of the second membrane layer layer is ionically conductive and at least one of the first being offset from the apertures of the first membrane layer. and second membrane layers is electronically insulat FIG . 1 illustrates an exemplary first membrane layer 20 ing . including a support structure 22 and apertures 24. FIG . 2 [ 0073 ] In an additional embodiment, the invention pro illustrates an exemplary second membrane layer 30 com vides an electrochemical cell comprising: prising pores 34 ; when these two layers are placed in [ 0074 ] a positive electrode ; contact, the pores of the second layer are offset from the [ 0075 ] a negative electrode ; apertures of the first membrane layer. In an embodiment the [ 0076 ] a membrane layer being positioned proximate to first membrane layer is a high mechanical strength layer . In an electrode , the membrane layer comprising a support a further embodiment only one high mechanical strength structure comprising a plurality of apertures and a solid layer is present in the membrane system and that high or gel electrolyte disposed within the apertures of the mechanical strength layer is the first membrane layer. In an support structures, wherein the support structure is embodiment, the second membrane layer may be a porous or formed of an electronically insulating material or is perforated polymeric separator. In the embodiment, the size formed of an electronically conducting material at least of the apertures of the first membrane layer are greater than partially coated with an electronically insulating mate the size of the pores of the second membrane layer, as rial; schematically illustrated in FIGS . 1 and 2. In embodiments , wherein the membrane layer is ionically conductive and at the ratio of the size of the apertures to the size of the pores least one side of the said membrane is electronically insu is from 5 : 1 to 100 : 1 , from 5 : 1 to 20 : 1 , from 25 : 1 to 100 : 1 or lating from 25 : 1 to 50 : 1 . In embodiments , the aperture size is from [ 0077 ] In embodiments, the ionically conductive material 5 nm to 2 mm , 10 nm to 1 mm , from 1 mm to 10 mm , or from or electrolyte is a single material or a combination of 500 um to 1 mm and the pore size is from 5 nm to 2 mm , materials . For example, in an embodiment, the ionically 10 nm to 1 mm , from 100 um to 500 um or from 10 um to conductive material is a glass electrolyte or a ceramic 50 um . electrolyte . A polymer electrolyte comprising a polymer [ 0064 ] In a further embodiment, the second membrane host , a solvent and an alkali metal salt provides an example layer further comprises an electronically conductive coating of an electronically conductive material which can be on one side of the layer. In an embodiment, the electronically viewed as a combination of a materials . In a further embodi conductive coating is on the electrode side of the layer. In an ment, the ionically conductive material is a composite further embodiment an external tab is connected to this material such as a combination of particles or fibers of an electronically conducting layer ; in this embodiment the ionically conductive material combined with another mate electronically conductive coating may be on either side of rial such as a polymer, a carbonaceous material or a metallic the membrane. material. [ 0065 ] In an embodiment, the first membrane layer is [ 0078 ] In an embodiment, a solid electrolyte is selected disposed proximate to the positive electrode and a liquid from the group consisting of polymer electrolytes , glass electrolyte is provided proximate to the negative electrode. electrolytes and ceramic electrolytes. In an embodiment, the In an embodiment, the liquid electrolyte at least partially fills solid electrolyte is a oxide or sulfide glass electrolyte . In an the pores of the second membrane layer. In a further embodiment, the oxide glass electrolyte is selected from embodiment, a second electrolyte is provided between the LVSO and LIPON . In a further embodiment, the electrolyte positive electrode and the first membrane layer. is a crystalline ceramic electrolyte . in an embodiment, the [ 0066 ] In an embodiment, the solid electrolyte is provided crystalline ceramic electrolyte is a NASICON type electro within a layer inside the apertures and the thickness of the lyte , a LISICON type electrolyte or a perovskite electrolyte . layer is from 0.01 mm to 0.5 mm or from 5 um to 20 um . [ 0079 ] In an embodiment, the material ( s) for the solid [ 0067 ] In an embodiment, the invention provides an elec electrolyte or electronically and ionically conductive mate trochemical cell comprising: rial are selected from the group consisting of carbon , lithium [ 0068 ] a positive electrode; titanate , Li , O2 , Li , 0 , titanium disulfide, iron phosphate, [ 0069 ] a negative electrode ; SiO2 , V2O5 , lithium iron phosphate, MnO2, Al2O3, TiO2, [ 0070 ] a first membrane layer being positioned proxi LiPF , LizP, LizN , LINO3 , LiC104 , LiOH , PEO , P205 , mate to one of the positive electrode and the negative LIPON , LISICON , ThioLISICO , Ionic Liquids, Al , Cu , Ti, electrode, the first membrane layer comprising a sup Stainless Steel , Iron, Ni , graphene oxide , PEDOT- PSS , and port structure comprising a plurality of apertures and a combinations thereof . solid or gel electrolyte disposed within the apertures of [ 0080 ] In additional aspects of the invention methods for the support structures, wherein the support structure operating electrochemical cells are provided , the methods formed of an electronically insulating material or is relating to any of the electrochemical cells provided herein . US 2020/0365862 A1 Nov. 19 , 2020 5
In an embodiment, the invention provides a method of batteries of ZnZnO in Zinc batteries ). 2 ) Cathode ( e.g. operating an electrochemical cell , the method comprising NMC , Sulfur, Air , LCO or LFP in Li - ion batteries or the steps of: providing said electrochemical cell as described Graphite, NiOOH or Ag - Ago in Zinc batteries. 3 ) Separator herein and charging, discharging or charging and discharg layer ( s ), e.g. microporous or nonwoven PE , PP, PVDF , ing the electrochemical cell , thereby inducing a surface polyester or polyim ides . 4 ) Perforated or porous conductive charge on the surface of the electronically conductive layer. layer, e.g. , Ni , Ti , stainless steel , Cu or Al . 5 ) Solid Elec trolyte layer in a frame, e.g. , LISICON in an aluminum BRIEF DESCRIPTION OF THE DRAWINGS Polyester frame [ 0081 ] FIG . 1. Schematic illustration of layer one of an [ 0088 ] FIG . 8. Schematic illustration of an additional cell exemplary membrane, a first pattern of LISICON disks with five types of element 1 ) Anode ( e.g. Li metal in Li - ion ( dark gray ) fills the holes in a metallic matrix ( light gray ). batteries of ZnZnO in Zinc batteries ). 2 ) Cathode ( e.g. Each solid electrolyte disk can be about 10 mm . After NMC , Sulfur, Air, LCO or LFP in Li - ion batteries or baking, at several hundreds of degrees Celsius , a polymer Graphite, NiOOH or Ag - Ago in Zinc batteries . 3 ) Separator coating is applied on the metallic part. The design of the first layers, e.g. perforated PE , PP, PVDF , polyester or polyim layer overcomes the brittleness, large thickness and expen ides with pattern A. 4 ) Perforated or porous conductive sive cost of ceramic - based solid electrolytes. layer, e.g. , Ni , Ti , stainless steel , Cu or Al . 5 ) Solid Elec [ 0082 ] FIG . 2. Schematic illustration of layer two of an trolyte layer in a frame with pattern B , e.g. , LISICON in an exemplary membrane, a second pattern of holes , each about aluminum -Polyester frame. 0.2 mm , is such that the holes of the second layer are aligned [ 0089 ] FIG . 9. Schematic illustration of a further cell with such that they have no overlap with the solid electrolyte five types of element 1 ) Anode ( e.g. Li metal in Li -ion filled holes of the first layer, offset design . The design of the batteries of Zn — ZnO in Zinc batteries ). 2 ) Cathode ( e.g. second layer limits the size of the largest short, which NMC , Sulfur, Air, LCO or LFP in Li - ion batteries or reduces the chance of a catastrophic failure . The offset Graphite, NiOOH or Ag - Ago in Zinc batteries. 3 ) Separator property of the two - layer design enforces a unique tortuosity layers, e.g. perforated PE , PP , PVDF , polyester or polyim such that the applied mechanical pressure may result in ides with pattern A. 4 ) Perforated or porous conductive layer stopping the growth of dendrites by kinetic frustration . with pattern B , e.g. , Ni , Ti , stainless steel , Cu or Al . 5 ) Solid [ 0083 ] FIG . 3. Schematic illustration of two layers A and Electrolyte layer in a frame, 4 , with pattern B , e.g. , LISI B of an exemplary membrane A ) Placed next to the cathode CON in an aluminum -Polyester frame . layer: Layer one , metal frame with polymer coating ( 0.007 [ 0090 ] FIG . 10. Schematic illustration of another cell with mm aluminum , stainless steel or copper and 2x0.003 mm five types of element 1 ) Anode ( e.g. Li metal in Li - ion polyimide or polyester ) with about 80 % porosity filled with batteries of Zn — ZnO in Zinc batteries ). 2 ) Cathode ( e.g. solid electrolyte ( LISICON ) . B ) Placed next to the lithium NMC , Sulfur, Air, LCO or LFP in Li - ion batteries or layer : Layer two , 0.010 mm thick aluminized polymer Graphite , NiOOH or Ag - Ago in Zinc batteries . 3 ) Separator ( polyimide or polyester) with about 10 % porosity filled with layers, e.g. microporous or nonwoven PE , PP, PVDF , poly nonwoven or micro - porous separator and aqueous electro ester or polyim ides . 4 ) Perforated or porous conductive lyte . The two layers can be attached by a 0.002 mm porous layer, e.g. , Ni , Ti, stainless steel , Cu or Al . 5 ) Solid Elec PVDF , 80 % opening. trolyte layer in a frame, 4 , e.g. , LISICON in an aluminum [ 0084 ] FIG . 4. Schematic illustration of a cell with four Polyester frame types of element: 1 ) Anode ( e.g. Li metal in Li - ion batteries [ 0091 ] FIG . 11. Schematic illustration of an additional Zn - ZnO in Zinc batteries ). 2 ) Cathode ( e.g. NMC , further cell with five types of element 1 ) Anode ( e.g. Li Sulfur, Air, LCO or LFP in Li - ion batteries or Graphite , metal in Li - ion batteries of Zn — ZnO in Zinc batteries ). 2 ) NiOOH or Ag - AgO in Zinc batteries ). 3 ) Separator layers , Cathode ( e.g. NMC , Sulfur, Air, LCO or LFP in Li - ion e.g. , microporous or nonwoven PE , PP, PVDF, polyester or batteries or Graphite , NiOOH or Ag - Ago in Zinc batteries . polyim ides . 4 ) Perforated or porous conductive layer, e.g. , 3 ) Separator layers, e.g. microporous or nonwoven PE , PP, Ni , Ti, stainless steel , Cu or Al . PVDF , polyester or polyimides . 4 ) Perforated or porous [ 0085 ] FIG . 5. Schematic illustration of another cell with conductive layer, e.g. , Ni , Ti , stainless steel , Cu or Al . 5 ) four types of element 1 ) Anode ( e.g. Li metal in Li - ion Solid Electrolyte layer in a frame, 4 ; e.g. , LISICON in an batteries of Zn — ZnO in Zinc batteries ). 2 ) Cathode ( e.g. aluminum - Polyester frame. NMC , Sulfur, Air, LCO or LFP in Li - ion batteries or [ 0092 ] FIG . 12 : Coating weights of polymer electrolyte Graphite, NiOOH or Ag - Ago in Zinc batteries . 3 ) Separator layers, e.g. microporous or nonwoven PE , PP, PVDF , poly coated per unit area of substrate, see Example 3 . ester or polyim ides . 4 ) Perforated or porous conductive [ 0093 ] FIGS . 13A and 13B : Scanning Electron Micro layer, e.g. , Ni , Ti, stainless steel , Cu or Al . scope ( SEM ) image of Kapton substrate coated with PEO [ 0086 ] FIG . 6. Schematic illustration of a cell with five polymer. FIG . 13A : Top view . FIG . 13B : Cross section . types of element 1 ) Anode ( e.g. Li metal in Li - ion batteries [ 0094 ] FIGS . 13C , 13D and 13E : Additional SEM images of Zn — ZnO in Zinc batteries ). 2 ) Cathode ( e.g. NMC , of coated Kapton substrates: FIG . 13C : Kapton + PEO , FIG . Sulfur, Air, LCO or LFP in Li - ion batteries or Graphite , 13D : Kapton + PEO : LiC104/ 90 : 10 . FIG . 13E : Kapton + PEO : NiOOH or Ag - Ago in Zinc batteries . 3 ) Separator layer ( s ) , LiC104 / 50 :50 . e.g. microporous or nonwoven PE , PP , PVDF , polyester or [ 0095 ] FIGS . 13F , 13G and 13H show SEM images of polyim ides . 4 ) Perforated or porous conductive layer, e.g. , coated Al substrates . FIG . 13F shows an Al substrate coated Ni , Ti , stainless steel , Cu or Al . 5 ) Solid Electrolyte layer, with PEO , FIG . 13G shows Al + PEO : LiC104 / 90 : 10 , FIG . e.g. , LISICON . 13H shows Al + PEO : LiC104 / 50 : 50 . [ 0087 ] FIG . 7. Schematic illustration of another a cell with [ 0096 ] FIG . 14A - 14D : FIG . 14A : Kapton + PEO ; FIG . five types of element 1 ) Anode ( e.g. Li metal in Li - ion 14B : Kapton + PEO : LiC104 / 90 : 10 ; US 2020/0365862 A1 Nov. 19 , 2020 6
[ 0097 ] FIG . 14C : Kapton + PEO : LiClo_70 : 30 ; FIG . 14D : [ 0115 ] Referring to the drawings, like numerals indicate Kapton + PEO : LiC10./50:50. like elements and the same number appearing in more than [ 0098 ] FIG . 14E - 14H : FIG . 14E : Al + PEO ; FIG . 14F : one drawing refers to the same element. In addition , here Al + PEO : LiC104/ 90 : 10 ; FIG . 14G : Al + PEO : LiC10_/ 70 : 30 ; inafter, the following definitions apply : FIG . 14H : Al + PEO : LiC104/ 50 : 50 . [ 0116 ] The term “ electrochemical cell ” refers to devices [ 0099 ] FIG . 15 : Average open circuit voltage ( OCV ) mea and / or device components that convert chemical energy into surements of the LCO half coin cells of Example 3 . electrical energy or electrical energy into chemical energy. [ 0100 ] FIG . 16 : Illustration of the measurement elements Electrochemical cells have two or more electrodes ( e.g. , used positive and negative electrodes ) and an electrolyte , wherein [ 0101 ] FIGS . 17A - 17C : Results obtained from circuit electrode reactions occurring at the electrode surfaces result simulation of the Nyquist plot . Displays the summary of in charge transfer processes . Electrochemical cells include, results obtained from relationship between coin cells with but are not limited to , primary batteries, secondary batteries different polymer coated electrolyte and 17A : ohmic resis and electrolysis systems. In certain embodiments , the term tance , 17B : double - layer capacitance, and 17C : polarization electrochemical cell includes fuel cells , supercapacitors, resistance capacitors, flow batteries, metal - air batteries and semi - solid [ 0102 ] FIG . 18 : The overlaid Nyquist plots of the data batteries . General cell and / or battery construction is known shown in FIGS . 16A - 16C . in the art, see e.g. , U.S. Pat . Nos . 6,489,055 , 4,052,539 , [ 0103 ] FIG . 19 : First cycle charge capacity, discharge 6,306,540 , Seel and Dahn J. Electrochem . Soc . 147 ( 3 ) capacity and percent retention of the coin cells with different 892-898 ( 2000 ) . polymer separator of Example 3 . [ 0117 ] The term “ capacity ” is a characteristic of an elec [ 0104 ] FIGS . 20A - 20B : shows the cycle life of the cell in trochemical cell that refers to the total amount of electrical Example 3. First cycle with PEO : 90 : 10 configuration coated charge an electrochemical cell , such as a battery, is able to on Kapton and Al mesh . FIG . 20A . Charge cycle . FIG . 20B . hold . Capacity is typically expressed in units of ampere Discharge cycle . hours . The term “ specific capacity ” refers to the capacity [ 0105 ] FIG . 21 Coating weights of PVDF based slurry output of an electrochemical cell , such as a battery, per unit coated separators in Example 4 . weight. Specific capacity is typically expressed in units of [ 0106 ] FIG . 22A - 22F : Microscope images of substrates ampere -hours kg coated with PVDF base slurries: FIG . 22A : Kapton® coated [ 0118 ] The term “ discharge rate ” refers to the current at with PVDF and LTO slurry . FIG . 22B : Kapton coated with which an electrochemical cell is discharged . Discharge rate PVDF , LTO , and CF slurry. FIG . 22C : Kapton coated with can be expressed in units of ampere . Alternatively, discharge PVDF , and graphite slurry. FIG . 22D : Al mesh coated with rate can be normalized to the rated capacity of the electro PVDF and LTO slurry. FIG . 22E : Al mesh coated with chemical cell , and expressed as C / ( X t ) , wherein C is the PVDF , LTO and CF slurry. FIG . 22F : Al mesh coated with capacity of the electrochemical cell , X is a variable and t is PVDF , and graphite slurry . a specified unit of time , as used herein , equal to 1 hour. [ 0107 ] FIG . 23 : SEM image of Al mesh coated with [ 0119 ] “ Current density ” refers to the current flowing per PVDF . unit electrode area . [ 0108 ] FIGS . 24A and 24B : SEM image of Al ( FIG . 24A ) [ 0120 ] Electrode refers to an electrical conductor where mesh and Kapton ( FIG . 24B ) coated with PVDF and graph ions and electrons are exchanged with electrolyte and an ite slurry . outer circuit . “ Positive electrode ” and “ cathode ” are used [ 0109 ] FIG . 25 Average open circuit voltage ( OCV ) mea synonymously in the present description and refer to the surements of the LCO half coin cells in Example 4 . electrode having the higher electrode potential in an elec [ 0110 ] FIGS . 26A - 26C summarize the results obtained trochemical cell ( i.e. higher than the negative electrode ). from circuit simulation of the Nyquist plot . Displayed is the “ Negative electrode ” and “ anode” are used synonymously in summary of results in the relationship between coin cells the present description and refer to the electrode having the with different polymer coated electrolyte and FIG . 26A : lower electrode potential in an electrochemical cell ( i.e. ohmic resistance, FIG . 26B : double - layer capacitance , and lower than the positive electrode ). Cathodic reduction refers FIG . 26C : polarization resistance to a gain of electron ( s ) of a chemical species , and anodic [ 0111 ] FIG . 27 Nyquist plot corresponding to FIGS . 26A oxidation refers to the loss of electron ( s ) of a chemical 26C . species . Positive electrodes and negative electrodes of the [ 0112 ] FIG . 28 : First cycle charge capacity, discharge present electrochemical cell may further comprise a con ductive diluent, such as acetylene black , carbon black , capacity, and percent retention of the coin cells with Kapton powdered graphite, coke , carbon fiber, graphene, and metal and Al mesh coated with PVDF and graphite slurry . lic powder, and / or may further comprises a binder, such as [ 0113 ] FIGS . 29A - 29B : Cycle life of cells with Kapton a polymer binder . Useful binders for positive electrodes in and Al mesh substrate coated with PVDF and graphite some embodiments comprise a fluoropolymer such as poly slurry. FIG . 29A : charge cycle . FIG . 29B : discharge cycle . vinylidene fluoride ( PVDF ) . Positive and negative elec trodes of the present invention may be provided in a range DETAILED DESCRIPTION of useful configurations and form factors as known in the art [ 0114 ] In general the terms and phrases used herein have of electrochemistry and battery science, including thin elec their art -recognized meaning, which can be found by refer trode designs , such as thin film electrode configurations. ence to standard texts , journal references and contexts Electrodes are manufactured as disclosed herein and as known to those skilled in the art . The following definitions known in the art, including as disclosed in , for example, U.S. are provided to clarify their specific use in the context of the Pat . Nos . 4,052,539 , 6,306,540 , and 6,852,446 . For some invention . embodiments, the electrode is typically fabricated by depos US 2020/0365862 A1 Nov. 19 , 2020 7 iting a slurry of the electrode material, an electronically mal steady state with one another. In some embodiments, conductive inert material, the binder, and a liquid carrier on elements in thermal communication with one another are the electrode current collector, and then evaporating the separated from each other by a thermally conductive mate carrier to leave a coherent mass in electrical contact with the rial or intermediate thermally conductive material or device current collector. component. In some embodiments, elements in thermal [ 0121 ] “ Electrode potential ” refers to a voltage , usually communication with one another are separated by a distance measured against a reference electrode , due to the presence of 1 um or less . In some embodiments, elements in thermal within or in contact with the electrode of chemical species communication with one another are provided in physical at different oxidation ( valence ) states . contact . [ 0122 ] “ Electrolyte ” refers to an ionic conductor which [ 0129 ] “ Chemically resistant” refers a property of compo can be in the solid state , the liquid state (most common ) or nents , such as layers, of separators and electrochemical more rarely a gas ( e.g. , plasma ) . systems of the invention wherein there is no significant [ 0123 ] “ Standard electrode potential” ( E ° ) refers to the chemical or electrochemical reactions with the cell active electrode potential when concentrations of solutes are 1M , materials , such as electrodes and electrolytes. In certain the gas pressures are 1 atm and the temperature is 25 degrees embodiments, chemically resistant also refers to a property Celsius . As used herein standard electrode potentials are wherein the tensile retention and elongation retention is at measured relative to a standard hydrogen electrode . least 90 % in the working environment of an electrochemical [ 0124 ] “ Active material” refers to the material in an elec system , such as an electrochemical cell . trode that takes part in electrochemical reactions which store [ 0130 ] “ Thermally stable ” refers a property of compo and / or deliver energy in an electrochemical cell . nents , such as layers, of separators and electrochemical [ 0125 ] “ Cation ” refers to a positively charged ion , and systems of the invention wherein there is no significant " anion ” refers to a negatively charged ion . chemical or electrochemical reactions due to normal and [ 0126 ] “ Electrical contact , ” “ electrical communication ” , operational thermal behavior of the cell . In certain embodi " electronic contact ” and “ electronic communication ” refer ments, thermally stable also refers to materials wherein the to the arrangement of one or more objects such that an melting point is more than 100 Celsius , and preferably for electric current efficiently flows from one object to another . some embodiments more than 300 Celsius , and optionally For example, in some embodiments , two objects having an the coefficient of thermal expansion is less than 50 ppm / electrical resistance between them less than 100 are consid Celsius . In an embodiment, thermally stable refers to a ered in electrical communication with one another. An property of a component of the separator system such that it electrical contact can also refer to a component of a device may perform in a rechargeable electrochemical cell without or object used for establishing electrical communication undergoing a change size or shape with the temperature that with external devices or circuits , for example an electrical significantly degrades the performance of the electrochemi interconnection . " Electrical communication ” also refers to cal cell . the ability of two or more materials and /or structures that are [ 0131 ] “ Porosity ” refers to the amount of a material or capable of transferring charge between them , such as in the component that corresponds to pores , such as apertures, form of the transfer of electrons. In some embodiments, channels, voids , etc. Porosity may be expressed as the components in electrical communication are in direct elec percentage of the volume of a material, structure or device trical communication wherein an electronic signal or charge component, such as a high mechanical strength layer, that carrier is directly transferred from one component to corresponds to pores, such as apertures, channels, voids , another. In some embodiments , comp nts in electrical etc. , relative to the total volume occupied by the material, communication are in indirect electrical communication structure or device component. wherein an electronic signal or charge carrier is indirectly [ 0132 ] High mechanical strength ” refers to a property of transferred from one component to another via one or more components of separator systems of the invention , such as intermediate structures , such as circuit elements, separating first, second, third and fourth high mechanical strength the components . layers, having a mechanical strength sufficient to prevent [ 0127 ] " Electrical conductivity " or " electrically conduc physical contact of opposite electrodes, sufficient to prevent tive” refers to transfer of charges which can be ionic ( ions ) short circuiting due to external objects within the cell , such or electronic ( electrons ). “ Electronic conductivity ” or “ elec as metallic particles from fabrication , and sufficient to tronically conductive” refers to transfer of charges which are prevent short circuiting due to growth of dendrites between electronic (electrons ). “ Ionic conductivity ” or “ ionically positive and negative electrodes of an electrochemical cell , conductive ” refers to transport of ionic charge carriers . for example, during charge and discharge cycles of a sec [ 0128 ] “ Thermal contact ” and “ thermal communication " ondary electrochemical cell . In an embodiment, for are used synonymously and refer to an orientation or posi example, a high mechanical strength layer has a mechanical tion of elements or materials, such as a current collector or strength sufficient to prevent piercing due to external objects heat transfer rod and a heat sink or a heat source , such that in the cell , such as metallic particles from the fabrication, there is more efficient transfer of heat between the two and shorts due to the growth of dendrites between elec elements than if they were thermally isolated or thermally trodes. In an embodiment, for example, a high mechanical insulated . Elements or materials may be considered in strength layer has a mechanical strength sufficient to prevent thermal communication or contact if heat is transported shorting between the positive electrode and the negative between them more quickly than if they were thermally electrode of an electrochemical cell due to external objects isolated or thermally insulated . Two elements in thermal in the cell such as metallic particles from the fabrication and communication or contact may reach thermal equilibrium or shorts due to the growth of dendrites between electrodes. In thermal steady state and in some embodiments may be an embodiment, for example, a high mechanical strength considered to be constantly at thermal equilibrium or ther layer is characterized by a Young's modulus greater than or US 2020/0365862 A1 Nov. 19 , 2020 8 equal to 500 MPa , and optionally for some applications a connection tab ; in an embodiment the external connection Young's modulus greater than or equal to 1 GPa , and tab is integral with the current collector . In an embodiment, optionally for some applications a Young's modulus greater the current collector is an electronically conductive material than or equal to 10 GPa , and optionally for some applica such as a metal. tions a Young's modulus greater than or equal to 100 GPa . [ 0138 ] Positive Electrode In an embodiment, for example, a high mechanical strength [ 0139 ] In embodiments where the cell is a lithium ion cell , layer is characterized by a yield strength greater than or the active material of the positive electrode is NMC ( lithium equal to 5 MPa , and optionally for some applications a yield nickel -manganese - cobalt oxide ) , sulfur, sulfur - carbon , car strength greater than or equal to 50 MPa , and optionally for bon - air, LCO ( lithium cobalt oxide , LiCo02 ) or LFP some applications a yield strength greater than or equal to ( lithium iron phosphate, LiFePO4 ) . In a further embodiment, 100 MPa , and optionally for some applications a yield active materials suitable for use in the positive electrode of strength greater than or equal to 500 MPa . In an embodi a lithium - ion cell include , but are not limited to Lithium ment, for example , a high mechanical strength layer is Cobalt ( LiCo02 ) , Lithium Manganese Oxide ( LiMnO4 ) , characterized by a propagating tear strength greater than or Lithium Iron Phosphate ( LiFePO4 ) , Lithium Nickel Cobalt equal to 0.005 N , and optionally for some applications a Aluminum Oxide ( LiNi..8C00.15Alo.o502 ) and Lithium propagating tear strength greater than or equal to 0.05 N , a Nickel manganese Cobalt Oxide ( LiNi..33Mno.33C00.3302) . propagating tear strength greater than or equal to 0.5 N , a Alternate materials include titanium disulfide ( TIS ) . propagating tear strength greater than or equal to 1 N. In an [ 0140 ] In embodiments where the cell is a zinc battery , the embodiment, for example, a high mechanical strength layer cathode material is graphite, NiOOH , Ag , or Ago . In an is characterized by an initiating tear strength greater than or embodiment, the positive electrode comprises an active equal to 10 N , and optionally for some applications an material in electronic communication with a current collec initiating tear strength greater than or equal to 100 N. In an tor . In an embodiment, the current collector comprises an embodiment, for example , a high mechanical strength layer external connection tab ; in an embodiment the external is characterized by a tensile strength greater than or equal to connection tab is integral with the current collector. In an 50 MPa , and optionally for some applications a tensile embodiment, the current collector is an electronically con strength greater than or equal to 100 MPa , and optionally for ductive material such as a metal. some applications a tensile strength greater than or equal to [ 0141 ] In embodiment, the positive electrode may be an 500 MPa , and optionally for some applications a tensile oxygen electrode or an air electrode. During discharge of the strength greater than or equal to 1 GPa . In an embodiment, cell , hydroxide ions are generated through dissociation of for example, a high mechanical strength layer is character oxygen and water at the surface of the oxygen or air ized by an impact strength greater than or equal to 10 N cm , electrode . During recharging of the cell , water dissociates to and optionally for some applications to an impact strength hydroxide and oxygen at the air or oxygen electrode. U.S. greater than or equal to 50 N cm , and optionally for some Pat. No. 6,221,523 is hereby incorporated by reference for applications to an impact strength greater than or equal to its description of oxygen and air electrodes and catalyst 100 N cm , and optionally for some applications to an impact deposition methods. strength greater than or equal to 500 N cm . [ 0142 ] Catalysts suitable for use with the positive elec [ 0133 ] Electrochemical Cell . trode include metals , metal alloys , metal oxides and metal [ 0134 ] In an embodiment, the electrochemical cell is a complexes. In an embodiment, a single catalyst is suitable secondary ( rechargeable ) electrochemical cell . In another for both reduction of oxygen ( during discharge) and evolu embodiment, the electrochemical cell is a primary electro tion of oxygen ( during charging ). Such a catalyst may be chemical cell . In embodiments, the electrochemical cell is a termed a bifunctional catalyst. Bifunctional catalysts known primary battery , a secondary battery , a fuel cell or a flow to the art include noble metal thin films, perovskites, and a battery, lithium battery, a lithium ion battery, a zinc spinel oxides . Perovskite - type oxides include transition anode -based battery , a nickel cathode - based battery , a semi metal oxides represented by the general composition for solid battery or a lead - acid - based battery. In additional mula ABO3 . One class of perovskite - type oxide is LaC003 , embodiments , the electrochemical cell is a Li - S , Li- Air , partial substitution products in which La is partially substi Li — LiFePO4 , or Zn - Ni electrochemical cell . In further tuted by one or more of Ca , Sr or Ba , partial substitution embodiments the cell is Mg based or Na based . products in which Co is partially substituted by one or more [ 0135 ] Negative Electrode Mn, Ni , Cu , Fe , Ir, and substitution products in which both [ 0136 ] In an embodiment where the cell is a lithium ion La and Co are partially substituted . cell , the active material of the negative electrode is lithium [ 0143 ] Electrolyte metal , a lithium alloy , silicon , a silicon alloy , silicon - graph [ 0144 ] In embodiments, the electrolyte is a liquid electro ite or graphite. In a further embodiment, active materials lyte , gel electrolyte, polymer electrolyte or ceramic electro suitable for use in the negative electrode of a lithium - ion cell lyte . In embodiments, the electrolyte is aqueous or nonaque include , but are not limited to carbonaceous material, ous . When the electrochemical cell is a lithium ion battery , lithium titanate ( LTO ) and titanium dioxide ( TiO2 ) . Carbo the electrolyte is preferably nonaqueous. In an embodiment, naceous materials include , but are not limited to natural the electrolyte comprises one or more lithium salts dissolved graphite, highly ordered pyrolytic graphite ( HOPG ) , Meso in a nonaqueous solvent. Carbon Microbeads ( MCMB ) and carbon fiber. [ 0145 ] Solid Electrolyte [ 0137 ] In an embodiment where the cell is a zinc cell , the [ 0146 ] In an embodiment, the solid electrolyte can be a anode material is Zn metal , ZnO or Zn - ZnO . In an embodi free standing layer or a coating layer. In another embodi ment, the negative electrode comprises an active material in ment, the solid electrolyte is in the form of particles or fibers electronic communication with a current collector. In an filling the holes -pores of an electronically insulating layer or embodiment, the current collector comprises an external the electronically conductive layer. In an embodiment, a US 2020/0365862 A1 Nov. 19 , 2020 9 layer is provided comprising at least a porous layer of of a voltage or current between the electronically conducting electronically conductive material and at least a group of layer and one of the electrodes results in gain and release of fibers or particles filling the pores or holes of the porous ions by the fibers or particles, such that ionic charge carriers layer. A variety of solid electrolytes are known to the art and are able to be transported between said positive electrode include , but are not limited to LISICON ( Lithium super and said negative electrode through the pores or holes of the ionic conductor, Li2 +2 Zn --Ge04 ) , PEO ( polyethylene electronically conducting layer. For example, a pulse or oxide ) , NASICON , and LIPON . sinusoidal voltage between 1 and 2.5 V may be applied [ 0147 ] Optionally, the first ionically conductive and elec between a graphite anode and a layer comprising LiTiO2 tronically insulating material comprises a solid electrolyte , a fibers inside a copper matrix in a Li - ion cell with a cathode gel electrolyte , a polymer electrolyte, LISICON , NASI such as air or sulfur. CON , PEO , LiGeP $ 12 , LIPON , PVDF, LizN , LizP, Lil , [ 0151 ] In an embodiment, the solid - state ionically con LiBr , LiCl, LiF , oxide perovskite, Laos, Lio . Ti03, thio ducting material is provided in the form of pellets inserted LISICON , Liz 25 Geo.25P0.75S4, glass ceramics , Li - P3S11 , in the frame such as a metallic frame. In an embodiment, the glassy materials , LiSSiSz, - Li3PO4, lithium nitride, pellets are bonded to the frame through solid state methods. polyethylene oxide , Doped LizN , LiSSiS , , -Li3PO4 , In a further embodiment, binders ( such as polymeric bind LIPON , Li14Zn ( Ge04 ) 4 , Li - beta - alumina , Liz.Si ... P.4049 ers ) and / or cements such as ( silica , alumina or iron oxide ) . Li ,SP , S3 , PEO - LiC104 , LiN ( CF SO2 ) / ( CH CHO ) , Additional surface coatings may be applied to overcome NaPON , ZrO2, Nafion , PEDOT : PSS , SiO2 , PVC , glass fiber interfacial resistance between the supported solid - state ioni mat , alumina, silica glass , ceramics, glass - ceramics, water cally conducting material and the electrode . stable polymers, glassy metal ion conductors, amorphous [ 0152 ] In another embodiment, the solid - state ionically metal ion conductors, ceramic active metal ion conductors, conductive material is provided as a composite of particles glass - ceramic active metal ion conductors, an ion conduct of the ionically conductive material with binder. As ing ceramic , an ion conducting solid solution , an ion con examples , the amount of binder is from 5 % to 35 % , ducting glass , a solid lithium ion conductor or any combi 5 % -25 % , 5 % -20 % , 5 % -15 % or 5 % -10 % ( wt % ). In a further nation of these . embodiment, electronically conductive particles may be [ 0148 ] In an embodiment, the solid electrolyte is a poly included in the composite . As an example, the amount of mer electrolyte. In an embodiment, polymer electrolyte is a electronically conductive particles is from 5 wt % to 10 wt polyelectrolyte comprising ionic groups. In an embodiment, % . In an additional embodiment, particles of an electroni the polyelectrolyte is an ionomer. In an embodiment, an cally insulating material such as alumina are included in the ionomer is a copolymer comprising nonionic repeat units composite . For example , the amount of alumina is from 5 wt and ion containing repeat units . In an embodiment, the ionic % to 15 wt % . The composite material may form a porous groups located upon nonpolar backbone chains . In an layer ; in embodiments the amount of porosity is from embodiment, the amount of ionic groups is 1 mol % to 15 20-60- % or from 40-60 % ( vol % ) . The solid - state ionically mol % . In an embodiment, the polymer electrolyte com conductive material may comprise an conventional solid prises a polymer complexed with an alkali metal salt . electrolyte , an electrochemically active ion - conductive Polymer electrolytes known to the art include , but are not material or a combination thereof. In an embodiment, the limited to , poly ( ethylene) oxide ( PEO ) , poly ( acrylonitrile ) amount of electrochemically active ion - conductive material ( PAN ), poly (methyl methacrylate ) ( PMMA ), poly ( vi in this mixture is from 5 % to 20 % or 5 % to 10 % (wt % ) . nylidene fluoride) (PVDF ) and poly ( vinylidene fluoride [ 0153 ] Insulator hexafluoro propylene ) ( PVDF - HFP ) . Lithium salts used in [ 0154 ] In embodiments, the electronically insulating layer for forming complexes include LiBr, Lil , LiCl , LiSCN , comprises a polymer, an oxide , a glass or a combination of LiC104, LiCF SO3 , LiBF4 and LiAsF . these . In embodiments , the electronically insulating is non [ 0149 ] In an embodiment, the solid electrolyte is a gelled woven or a woven . In an embodiment, the insulating layer or wet polymer. The gelled polymer may further comprise an is polymeric such as microporous or nonwoven PE , PP, organic liquid solvent and an alkali metal salt . The polymer PVDF , polyester or polyimide . In a further embodiment the host may comprise polyethylene ) oxide ( PEO ), polyacry insulating layer is an oxide such as aluminum oxide . In an lonitrile ) ( PAN ), poly (methyl methacrylate ) ( PMMA ), poly embodiment, said electronically insulating comprises a coat ( vinylidene fluoride ) ( PVDF ) and poly ( vinylidene fluoride ing provided on at least one side of said electronically hexafluoro propylene ) (PVDF -HFP ). Solvents include , but conductive layer. As an example , an aluminum oxide layer are not limited to ethylene carbonate, propylene carbonate , is provided on an aluminum layer. In an embodiment, the dimethyl formamide , diethyl phthalate , diethyl carbonate , electronically insulating comprises one or more perforated methyletyl carbonate, dimethyl carbonate, y - butyrolactone , or porous layers each independently having a porosity glycol sulfite and alkyl phthalates. greater than or equal to 30 % , from 30 % to 80 % or from 50 % [ 0150 ] In a further embodiment, the solid - state ionically to 75 % . In an embodiment, one or more perforated or porous conductive material is supported by a frame or porous layers each independently have a thickness selected over the support. In an embodiment , the frame or support is made of range of 20 nm to 1 mm , 0.005 mm to 1 mm , from 1 um to an electronically insulating material or of an electronically 500 um or from 5 um to 100 um . In an embodiment, the conducting material surface coated with an electronically separator comprises a first insulating layer having a plurality insulating material. In an embodiment, the support is porous of apertures arranged in a first pattern and a second insu or perforated and the holes or pores at least partially filled by lating layer having a plurality of apertures arranged in a particles or fibers of the solid - state ionically conductive second pattern ; wherein said second pattern has an off - set material. Suitable active materials include , but are not alignment relative to said first pattern such that an overlap of limited to , traditional electrode active materials such as said apertures of said first insulating layer and said apertures LiTiO2 , silicon or graphite. In an embodiment, application of said second insulating layer along axes extending per US 2020/0365862 A1 Nov. 19 , 2020 10 pendicularly from said first insulating layer to said second optionally all of, electronically insulating layers and the insulating layer is less than or equal to 20 % In an embodi electronically conducting layers each independently have an ment, there is no overlap of the apertures . average thickness selected over the range 10 nm to 2 um or [ 0155 ] Ionically Conductive Layer selected over the range 2 um to 50 um . ( 0156 ] In an embodiment, for example, a layer permeable [ 0161 ] Electronically Conductive Layer to ionic charge carriers has an ionic resistance less than or [ 0162 ] In embodiments, said electronically conductive equal to 20 ohm - cm², and preferably for some embodiments layer comprises a chemically resistant material, a heat less than or equal to 2 ohm - cm ?, and preferably for some resistant material, a mechanically resistant material or any embodiments less than or equal to 1 ohm - cm ?. combination of these . In an embodiment, the conductive [ 0157 ] In an embodiment, the electronically and ionically layer comprises a metal, alloy , carbon or a conductive conducting material or a material to be included in an a polymer. In an embodiment, the electronically conductive combination to produce an electronically and ionically con layer comprises a metal foil, a metallic thin film , an elec ducting material mixture is selected from the group consist tronically conductive polymer, a carbonaceous material or a ing of carbon , lithium titanate, Li202 , Li20 , titanium disul composite material of any of these . In an embodiment, the fide, iron phosphate, SiO2 , V205 , lithium iron phosphate , metal or alloy is selected from Al , Cu , Ti , Ni , Fe , stainless MnO , A1,0z, TiO , LIPF . , Li P, LizN , LINO3, LiCiO4, LiF , steel , Sn , Si , Au, Pt , Ag , Mn , Pb and their alloys and LiOH , poly ( ethylene oxide ) ( PEO ) , P2O5 , LIPON , LISI Zircalloy , Hastalloy , and superalloys. In an embodiment, the CON , ThioLISICO , an ionic liquid , Al , Cu , Ti , Stainless electronically conductive layer comprises a metal selected Steel , Iron , Ni , Poly ( 3,4 - ethylenedioxythiophene ) -poly ( sty from the group consisting of Al , Ti , Cu , stainless steel , Ni , renesulfonate ) ( PEDOT- PSS ), graphene oxide and combi Fe , or any alloys or composites thereof. In an embodiment, nations thereof. In a further embodiment, an electrolyte the carbonaceous material is selected from conductive car material or a material to be included in a combination to bon , super - P , carbon black and activated carbon . In an produce an electrolyte wherein the materials for the said embodiment, the electronically conducting polymer is electronically and ionically conductive material are selected selected from the linear - backbone “ polymer blacks ” ( poly from the group consisting of carbon , lithium titanate , Li202 , acetylene, polypyrrole, and polyaniline) and their copoly Li , o , titanium disulfide, iron phosphate, SiO2 , V , 05 , mers , poly ( p - phenylene vinylene ) ( PPV ) and its soluble lithium iron phosphate, MnO2, Al2O3 , TiO2, LiPF . , LizP , derivatives and poly ( 3 - alkylthiophenes. In an embodiment, LizN , LINO3 , LiC104 , LiOH , PEO , P2O5 , LIPON , LISI the electronically conducting layer does not react chemically CON , ThioLISICO , an ionic liquids, Al , Cu , Ti , Stainless or electrochemically with the electrolyte. In an embodiment, Steel , Iron, Ni , graphene oxide , PEDOT- PSS , and combi electronically conductive layer comprises a metal reactive nations thereof. with an active material of the negative or positive electrode . [ 0158 ] Optionally , an ionically conductive and electroni In an embodiment, the electronically conductive layer com cally insulating material has an ionic conductivity greater prises a metal selected from the group consisting of Al and than or equal to 10-5 S / cm , greater than or equal to 10-4 Sn . In embodiments , the thickness of the electronically S / cm , greater than or equal to 10-4 S / cm , greater than or conductive layer is greater than zero and less than 1 mm , equal to 10-3 S / cm , greater than or equal to 10-2 S / cm , greater than zero and less than 0.1 mm , from 0.001 mm to greater than or equal to 10-1 S / cm , greater than or equal to 1 mm , from 0.005 mm to 1 mm , from 0.005 mm to 0.5 mm , 10 S / cm , selected from the range of 10-7 S / cm to 100 S / cm , from 0.01 mm to 0.1 mm , from 0.075 mm to 0.2 mm or from selected from the range of 10-5 S / cm to 10 S / cm , selected of 25 nm to 0.5 mm . In an embodiment, the composite from the range of 10-3 S / cm to 1 S / cm . Optionally, the first separator further comprises one or more additional electroni ionically conductive and electronically insulating material cally conductive layers . has an ionic conductivity selected from the range of 10-7 [ 0163 ] Fabrication of composite membranes may include S / cm to 100 S / cm at an operating temperature of the cell . bonding of different membrane layers. In an embodiment, a [ 0159 ] Optionally, the above -mentioned first ionically polymeric binder is used . conductive and electronically insulating material has an [ 0164 ] The invention may be further understood by the average porosity less than 1 % . Preferably, the first ionically following non - limiting examples . conductive and electronically insulating material is non porous . Optionally, the first ionically conductive and elec Example 1 : Novel Membranes tronically insulating material has an average porosity [ 0165 ] 1 ) " a Unique Hybrid Membrane for Protecting selected from the range of 0 % to 5 % . Optionally, the first Lithium Metal Anode or Zinc Anode ” ionically conductive and electronically insulating material is [ 0166 ] An exemplary hybrid membrane is a novel com substantially free of pinholes, cracks, holes or any combi posite electrolyte composed of liquid , polymer and ceramic nation of these . Optionally, the first ionically conductive and electrolytes, designed in a special format. The hybrid mem electronically insulating material is substantially free of brane has high conductivity (more than 1 mS / cm ) , mechani defects . Optionally, the first ionically conductive and elec cal strength ( shear modulus = 2 GPa ; tensile strength = 200 tronically insulating material is doped . MPa ; rupture strength = 1000 gr ) and flexibility. The mem ( 0160 ] In an embodiment, the electronically insulating brane is low cost ( $ 1 / sq . m ) and can easily be produced in layers and the electronically conducting layers each inde large quantities ( rolls of 100 m long , 6 cm width and 0.025 pendently have an average thickness selected over the range mm thickness ). Using non - aqueous electrolyte near the 25 nm to 1 mm , optionally for some applications selected anode and aqueous electrolyte near the cathode allows using over the range 25 nm to 15 um , and optionally for some high capacity air and sulfur cathodes with lithium metal applications selected over the range of 1 um to 100 um , and anode. The membrane is chemically inert, does not react optionally for some applications selected over the range of with lithium metal , electrolytes , air or moisture , and sepa 5 um to 1 mm . In an embodiment, for example , any of, and rates the anolyte and catholyte environments. A schematic US 2020/0365862 A1 Nov. 19 , 2020 11 figure and the mechanism of the performance of the hybrid effort is focused on a unique class of advanced membranes membrane are shown in FIGS . 1-2 . The hybrid design with non - expensive , efficient and scalable manufacturing. resolves the high cost , fragility and high resistivity of solid [ 0173 ] To overcome the challenges of dendrite formation electrolytes without compensating the safety. Lithium elec and lithium contamination during recharging lithium metal troplating , including dendrite growth , is further controlled anode several interesting approaches have been suggested. by a ) providing high mechanical pressure on the surface of Several research groups, such as Balsara at LBNL have been the lithium metal , b ) manipulating the electric field by using working on polymer based electrolytes with the goal of a conductive layer inside the membrane . It is expected that stopping the dendrite formation or growth . Many different the novel hybrid electrolyte in conjunction with using state electrolytes (Doron Aurbach and Jeff Dahn pioneering work of the art electrolyte and additives can enable the next in 90's ) and additives, such as LiNO3 , have been tested to generation of high energy batteries with double the energy control the reactions between lithium metal and the electro at half the cost . lyte . Finally , PolyPlus has been using LISICON solid elec [ 0167 ] Placed next to the cathode layer: Layer one , metal trolyte to prevent the contamination of lithium metal in frame with polymer coating ( 0.007 mm aluminum , stainless lithium sulfur and lithium air cells . However, these efforts steel or copper and 2x0.003 mm polyimide or polyester ) have not been sufficient yet . Polymer electrolytes with high with about 80 % porosity filled with solid electrolyte ( e.g. , mechanical strength have low conductivity and adhesive LISICON ) . A first pattern of LISICON disks fills the holes ness at room temperature . Additives and different electro in a metallic matrix . Each solid electrolyte disk can be about lytes have not been successful beyond any coincells , as they 10 mm . After baking, at several hundreds of degrees Celsius , still need the mechanical pressure on the lithium sulfur. a polymer coating is applied on the metallic part. The design Ceramic electrolytes are still too thick , expensive and rigid . of the first layer overcomes the brittleness, large thickness Thus, still there is a critical need for more advanced mem and expensive cost of ceramic -based solid electrolytes, such branes that can help in protecting the lithium surface in as Ohara's. advanced lithium metal battery cells , larger than a few mAh . [ 0168 ] Placed next to the lithium layer : Layer two , 0.010 mm thick aluminized polymer ( polyimide or polyester ) with TABLE 1 about 10 % porosity filled with nonwoven or micro - porous Conduc Deform Protecting separator and aqueous electrolyte . A second pattern of holes , Membrane type tivity Cost ability Scability lithium each about 0.2 mm , is such that the holes of the second layer Aqueous Good Low High Excellent No are aligned such that they have no overlap with the solid electrolyte electrolyte filled holes of the first layer, Offset design. with separator [ 0169 ] The design of the first layer overcomes the brittle Polymer Poor Low Average Good No ness , large thickness and expensive cost of ceramic - based Electrolyte Ceramic Good Very Very Very Yes solid electrolytes, such as Ohara's. The design of the second Electrolyte High Poor poor layer limits the size of the largest short, which reduces the Hybrid Good Low High Good Yes chance of a catastrophic failure . Membrane [ 0170 ] The offset property of the two -layer design ( this work ) enforces a unique tortuosity such that the applied mechani cal pressure may result in stopping the growth of dendrites [ 0174 ] C - Layer Frame Fabrication Development by kinetic frustration . [ 0175 ] The frame of the C layer holds the ceramic elec [ 0171 ] A key element of our unique innovation is a double trolyte ( e.g. , LISICON ) pellets in place during the manu layer perforated polymer film designing the tortuosity of the facturing and operation. Metallic frames will be used to separator the way a composite material is made . Based on overcome the high temperature (more than 500 ° C. ) and the concept of “ offset ” widely used in the science of optics , milling needed to process the ceramic electrolyte. At the end we place two identical perforated layers in a complementary of the process , a thin electronically insulating layer will be pattern that prevents any light from passing from a side to coated on the metallic part. Thermal deformation of the the other side of the layers without going through at least one metallic frame can overcome the challenge of adherence of of the layers. Further, to provide low resistivity required for the pellets to the metallic frame. As an example, nickel , high power applications , layers of high mechanical strength aluminum and stainless steel can be used . and layers of low ionic resistance are placed next to each [ 0176 ] C - Layer Pellets Fabrication Development other as a layered composite. Our unique method allows [ 0177 ] We can use the guidelines and methods from recent fabrication of mechanically - thermally strong separators literature on ceramic electrolyte research to fabricate the from almost any materials , such as PEEK , Kapton , Polyes ceramic pellets. The process is very challenging and the ters , PET, polysulfone or even ceramics. dimensions of the pellets and process conditions play impor [ 0172 ] Protecting lithium metal anode is a critical step in tant roles in the quality of the product. We try to avoid the developing and improving the next generation of energy pinhole formation and cracks by optimizing the size of the storage technologies, since they represent the most critical pellets and the metallic frame structure . component needed to enable widespread commercialization [ 0178 ] Composite C - Layer Fabrication Development of PEVs . In this example , we are suggesting a unique hybrid [ 0179 ] Bonding the metallic frame to the ceramic pellets membrane for protecting lithium metal anode in advanced can be challenging. Solid state methods will be used as the high energy batteries, such as in lithium - sulfur and lithium first bonding method , such as a ) Powder blending and air batteries . The proposed membrane is a unique hybrid consolidation ( powder metallurgy ): Powdered metal and membrane with excellent conductivity, stability and flex discontinuous reinforcement are mixed and then bonded ibility that is needed for enabling lithium metal battery cells , through a process of compaction , degassing, and thermo with up to 500 Wh /Kg , 1000 Wh / L and 1000 cycles . Our mechanical treatment ( possibly via hot isostatic pressing US 2020/0365862 A1 Nov. 19 , 2020 12
( HIP ) or extrusion ), and b ) Foil diffusion bonding: Layers of [ 0190 ] Compressible Seal Development metal foil are sandwiched with long fibers, and then pressed [ 0191 ] The objective of this element is to implement a through to form a matrix . compressible seal that can ensure enough compressive pres [ 0180 ] Insulating polymer coating ( a few micrometers ) sure on the lithium surface even in a fully discharged cell . will be performed on the metallic frame as the final step . Smooth electroplating of lithium ions requires applying [ 0181 ] In case the bonding between the metallic frame and enough pressure on the lithium anode surface. As the high the ceramic pellets gets lose during fabrication or operation specific energy design limits us to spring - less formats, we and thermal treating ( difference in thermal coefficient of use a compressible housing for lithium anode . metals and ceramics ) being insufficient, we will use binders [ 0192 ] 2 ) A novel flexible and inexpensive composite such as PVDF polymer in NMP and cement ( SiO2 , A1203 , polymer -solid electrolyte electrolyte that has very high ionic Fe2O3 and CaO ) in water . This process has similarities with conductivity ( ceramic powders, such as TiO2 or lithium making reinforced concrete in structural engineering . As we titanate bounded by polymers ( about 10 % weight) such as will use non - aqueous with the cathodes in this testing , the pvdf or Polyethylene oxide ) . it allows making Li - air and interfacial resistance between the cathode and the C - layer Li – S batteries with energy densities 2-4x higher than state may be high . Surface treatment such as PVDF and SiO2 of the art . Traditional methods make ceramic electrolytes coating can be used to overcome the problem . without any binders , hence there are limitations on the size [ 0182 ] A - Layer Fabrication of the film ; it has to be thick to avoid pinholes but this makes [ 0183 ] Metalized polymer films will be perforated in a the, brittle . Also the dimensions (surface area ) are limited to periodic format, 0.1 mm diameter holes , by laser cutting, about 10 cmx10 cm . In our novel method , we can make lithography or micro punching and the least expensive ceramic - polymer electrolytes as thin as 20 micrometers and method will be implemented . Handling 200 cm long of 0.01 with high surface area , such as 2 mx6 cm . further, our solid mm films can be challenging , especially if the film wrinkles , electrolyte is flexible and can be used in traditional batteries which can cause the perforation challenging . Especial engi such as 18650 manufacturing. neering instruments will be designed to address this chal [ 0193 ] 3 ) Spar ( e.g. two perforated layers having a misfit lenge . between alignment of apertures) with different openings on [ 0184 ] The objective is to measure the effect of A - layer on each side : 20 % on the Li and 80 % on the Cathode . LTO , the performance of lithium metal anode cells . Especially the Li2O2 , Titanium disulfide, FePO4 and solid electrolytes effectiveness of controlling lithium electroplating by a ) deposited on nonwoven separator or in the holes of Spar . designed tortuosity b ) manipulating the electrical field , due [ 0194 ] 4 ) Coating the surface of the electrolyte /separator to the embedded conductive core layer will be investigated with filled holes ” particles with a hydrophobic skin , e.g. , [ 0185 ) Two of our suggested mechanisms to control the polydopamine , allows Li + transport while stabilizing the lithium metal dendrite forming and growth are a ) Manipu electrolyte particles in an aqueous electrolyte . lating the electric field inside the cell by using an inner [ 0195 ] 5 ) The stable surfaces of Li2O2 are half -metallic , metallic layer in the membrane that generates surface despite the fact that Li2O2 is a bulk insulator. A composite charges on its surface due to the charges on the lithium polymer gel containing a large volume fraction of an inor anode film . b ) Applying mechanical pressure on most of the ganic oxide and an organic liquid electrolyte immobilized in lithium metal surface which has been proven to enhance the a polymer can give a flexible , thin membrane with a au 10-3 electroplating of lithium . The surface of the perforated Scm , may assist in blocking dendrites from a Li anode or polymer may be treated , for example by PVDF and SiO2 soluble redox couples in a liquid cathode . In contrast, the coating , such that the interface resistance between the stable surfaces of Li20 are insulating and nonmagnetic . The lithium anode and the membrane be minimized . distinct surface properties of these compounds may explain ( 0186 ] Hybrid Membrane Fabrication Development observations of electrochemical reversibility for systems in [ 0187 ] Fabrication of the final product, hybrid membrane, which Li2O2 is the discharge product and the irreversibility requires the bonding between the A - layer and C - layer. The of systems that discharge to Li20 . Moreover, the presence of bonding should be very rigid so that we can implement our conductive surface pathways in Li ,O2 could offset capacity “ designed tortuosity ” mechanism to stop the growth of limitations expected to arise from limited electron transport lithium dendrite . Attention will be given to the bonding through the bulk solid electrolyte such as LTO , Li2O2 , TiS2 , between the C -layer and A - layer and also minimizing the FePO4 , or for Fuel cells , where the inside the electrolyte is bulk and interfacial resistance of the membrane . The bond electronically conductive ( such as Al or Ni or Tin layer in the ing should prevent any direct contact between the ceramic middle ) but it is electronically disconnected from the elec pellets and lithium , as most high conductivity ceramic trodes. Aluminized Mylar show how one can make it . In fact electrolytes react with lithium metal . As an example, we can in fuel cells and Na - S batteries or Molten salt batteries or use PVDF and SiO2 ( e.g. , dissolved in acetone at 40 ° C. ) as molten batteries they use high temperature , here I suggest the binder between the layers, which will allow enough using electronic conductivity + cell electric field ( my experi wetting of the C - layer by the anolyte and preserves the ments : middle of the cell is 1/2 of the total voltage ! ) " offset " between the layers . [ 0196 ] 6 ) Coating on separator or filing the holes in Spar [ 0188 ] The design used the " designed tortuosity " in block amphiphilic polymers — polymers composed of hydrophilic ing the dendrite and improving the electroplating of lithium . (water - loving ) and hydrophobic (water -hating ) parts — in [ 0189 ] The perfect separation between lithium metal modifying the interface between sulfur and the hollow anolyte from the cathode -catholyte is essential in some cells . carbon nanofiber, they used polyvinylpyrrolidone ( PVP ). Impermeable polymer housing for the cathode - catholyte can Also Lithium stearate coatings can be used . [Guangyuan be used such that only the hybrid membrane remains uncov Zheng, Qianfan Zhang, Judy J. Cha , Yuan Yang, Weiyang Li , ered . We may need to inject the catholyte by a syringe and Zhi Wei Seh , and Yi Cui ( 2013 ) Amphiphilic Surface then close the hole by heat sealing Modification of Hollow Carbon Nanofibers for Improved US 2020/0365862 A1 Nov. 19 , 2020 13
Cycle Life of Lithium Sulfur Batteries. Nano Letters doi : 50 % porosity coating of 90 % lithium titanate, 5 % carbon 10.1021/ n1304795g ]. In addition to Tio , on sulfur, Tis , black and 5 % PVDF binder on silicon anode in a li - ion cell . coatings can be formed on sulfur. B ) a 5 micrometer, 50 % porosity coating of 90 % lithium iron [ 0197 ] 7 ) Solid electrolytes for lithium batteries. E.g. , phosphate, 5 % carbon black and 5 % PVDF binder on sulfur LTO + 5 % binder as a solid electrolyte film . In an embodi cathode in a li - ion cell . C ) a 5 micrometer, 50 % porosity ment, this electrolyte gets lithium from one side and release coating of 90 % TiO2, 5 % carbon black and 5 % PVDF binder it to the other side ( due to chemical gradient and electric on silicon anode in a li - ion cell . D ) a 5 micrometer, 50 % gradient forces ). porosity coating of 85 % lithium titanate , 10 % Al2O3 and 5 % PVDF binder on sulfur cathode in a li - ion cell . The elec Example 2 : Hybrid Membranes trolytes can be liquid such as commercial PC - EC - DMC with [ 0198 ] In all types of batteries, such as li - ion , alkaline and 1 M LiPF 6, or can be solid such as LIPON , LISICON or lead - acid , the separator used with the liquid electrolyte is PEO with LiPF . based on electronically insulating and ionically insulating [ 0200 ] The inventors have also found that ceramic - glass polymers such as polyethylene ( PE ) and polypropylene and polymer electrolytes fortified with conventional active ( PP ) . Polymer electrolytes such as PEO have been tried in materials with different charge - discharge voltages vs Li + / Li , li - ion cells without liquid electrolyte and without a PE - PP such as conventional anode and cathode active materials in separator, but their ionic conductivity is too low . Polymer li - ion cells , can effectively resolve the manufacturing chal electrolytes such as PEO have been tried in Li - ion cells with lenges of solid electrolytes, such as low flexibility and liquid electrolyte and without a PE - PP separator, but their pinholes. Some examples are A ) a li - ion solid electrolyte structural stability is too low and there is no benefit in using with 85 % LISICON powder, 5 % lithium titanate and 10 % them . Ceramic - glass based electrolytes such as LIPON and PVDF binder, in NMP solvent made with a slurry process . LISICON have been tried in li - ion cells with and without B ) a li - ion solid electrolyte with 70 % LISICON , 15 % TiO2 , liquid electrolyte and without a PE - PP separator, but their 5 % lithium iron phosphate , 5 % carbon black and 5 % PVDF ionic conductivity is too low , and their cost is too high . binder, in NMP solvent made with a slurry process ; In this [ 0199 ] In Li - ion cell with liquid electrolyte, membranes case , due to the presence of the electronically conductive made of conventional active materials with different charge carbon black , a liquid electrolyte and separator or a non discharge voltages vs Li + / Li can effectively replace the electronic conductive porous coating is needed between the PE - PP separators and decrease the cost of the cell , while membrane and at least on electrode. C ) a li - ion solid increasing its performance and manufacturing speed . The electrolyte with 70 % PEO with LiPF6 salet, 15 % LISICON , cost of separators now is about $ 2 per sqm , but the cost of 5 % lithium titanate , 5 % A1203 and 5 % PVDF binder . D ) a the membrane suggested in this invention is $ 0.2 per sqm ; li - ion solid electrolyte with 65 % LISICON , 10 % MnO2, 5 % further the interface impedance between the PE - PP separa PEO with LiFP6 , 5 % A1203 , 5 % TiO2 , 5 % lithium titanate tors is much higher than that of the membrane suggested and 5 % PVDF binder . The electrolytes can be liquid such as here and electrodes, which increases the rate and cycle life ; commercial PC - EC - DMC with 1 M LiPF6 , or can be solid it further may prevent any catastrophic failure such as fire such as LIPON , LISICON or PEO with LiPF6 . A metallic due to the high thermal stability of the disclosed membrane . frame, such as aluminum copper , titanium , iron or stainless The active material can be initially lithiated or not . steel , can be used to provide both electronic conductive Examples of the materials are TiO2 , TiS2, lithium titanate , network in the membrane and structural stability; however graphite , LiFePO4 . An example is a 50 % porous layer, 10 the membrane should not connect the anode and cathode micrometers thick made of 90 % TiO2 mixed with 10 % electronically, for example one interface of the membrane binder such as PVDF . Al2O3 can also be added for lower and an electrode needs an electronically insulating layer. interface resistance on the electrode - electrolyte interface, an example is a 50 % porous layer, 10 micrometers thick made Example 3 : PEO /LICIO4 Polymer Electrolyte of 80 % lithium titanate mixed with 10 % binder such as Coated Seperatores PVDF and 10 % Al2O3 . In some embodiments this mem [ 0201 ] Kapton ( K ) separator and aluminum (Al ) mesh was brane can have several layers in which at least one of the coated with various combinations of poly ( ethylene ) oxide layers may have high electronic conductivity . An example is ( PEO ) and lithium perchlorate ( LiC102) polymer electrolyte a 50 % porous layer, 10 micrometers thick made of 80 % solutions. The description and concentrations of PEO coated lithium titanate mixed with 10 % binder such as PVDF and separators are shown in Table 2 below . Separators that were 10 % A1203 with a thin , a few micrometers or less , carbon coated with a 50:50 weight percent mixture of PEO : LiC104 coating on at least one side of it . Another example is a 50 % polymer electrolyte have the highest coating weigh and porous layer, 10 micrometers thick made of 80 % lithium separators coated with 5 % solid PEO in H2O have the lowest titanate mixed with 10 % binder such as PVDF and 10 % coating weight Al2O3 as the first layer and a 50 % porous layer, 10 microm eters thick made of 80 % lithium titanate mixed with 5 % TABLE 2 carbon black and 5 % binder such as PVDF and 10 % Al2O3 as the second layer. The electrolyte can be conventional Separator PEO li - ion electrolyte such as mix of organic solvents ( for Combination Polymer, LiC104 , example , PC , DMC , EC ) and a lithium salt ( for example , ( PEO : LICIO ) Substrate wt % wt % K + PEO Kapton 100 0 LiPF6 or LiC104 ) . The electrodes can be any li - ion elec K + PEO (90:10 ) Kapton 90 10 trodes such as lithium , silicon or graphite anode materials K + PEO ( 70:30 ) Kapton 70 30 and LiFePO4 , LiC002 , Sulfur or Air cathode . In some K + PEO - 50 : 50 Kapton 50 50 embodiments, the membrane can be a coating on at least one Al + PEO Al mesh 100 0 of the electrodes . Several examples are A ) a 5 micrometer, US 2020/0365862 A1 Nov. 19 , 2020 14
TABLE 2 - continued [ 0207 ] In general, the relationship between R1 , R2 and Q1 are inversely proportional and this trend can be seen from Separator PEO the data . The increase in R1 or R2 indicates internal resis Combination Polymer , LiC104 , tance increases inside of the cell . In this case all the coin ( PEO : LICIO ) Substrate wt % wt % cells were made the same way, with the only component that Al + PEO - 90 : 10 Al mesh 90 10 is variable is the different polymer electrolytes coated on Al + PEO - 70 : 30 Al mesh 70 30 different substrates. Therefore, the internal resistance can be Al + PEO - 50 : 50 Al mesh 50 50 attributed to the different polymer electrolytes on the sub strates . It is difficult to conclude from the data which [ 0202 ] Displayed in FIG . 13A is the SEM image of Kapton polymer electrolyte coated separator is the best without coated with PEO polymer at 89x magnification showing further investigation into optimized coating parameters, but uniform distribution of the polymer electrolyte coating . FIG . generally, cells with Al mesh as a substrate show lower RA , 13B displays a cross section of the same separator. It is R2 and higher Q1 in comparison to other cells . This could difficult to distinguish the difference between substrate and be due to conductivity of the Al mesh . The overlaid Nyquist the polymer electrolyte layers for polymer electrolyte thick plots of the data shown in FIGS . 17A - 17C are displayed in ness calculation . Better sample preparation for cross section FIG . 18. In the legend for FIG . 18 , the identifier Al- 50-50 imaging can done in the future , possibly using liquid nitro PEO -4_03_GBS_C01.mpr : -Im ( z ) vs. Re ( Z ) has been gen to fracture the sample more cleanly or to make use of a abbreviated as Al - 50-50 - PEO ; the identifier A1-90-10 -PEO diamond blade cutting surface . The SEM images reveal that 3_02_GBS_C01.mpr: -Im ( z ) vs. Re ( Z ) has been abbreviated the pores of the separator are not filled . Viscosity adjustment as Al - 90-10 - PEO ; the identifier 90-10 - PEO - 1_02_GBS_ of the solution concentrations along with controlling the C01.mpr: -Im ( z ) vs. Re ( Z ) has been abbreviated as 90-10 drying conditions would likely produce a fully filled film . PEO ; the identifier Al - 50-50 -PEO -4_03_GBS_C01.mpr : FIGS . 13C , 13D and 13E : shows additional SEM images of < Ew e > vs. Re ( Z ) has been abbreviated as Al - 50-50 - PEO coated Kapton substrates: FIG . 13C : Kapton + PEO , FIG . Ew e vs. Re ( Z ) ; the identifier Al- PEO -5_03_GBS_C01.mpr : 13D : Kapton + PEO : LiC104 / 90 : 10 . FIG . 13E : Kapton + PEO : -Im ( z ) vs. Re ( Z ) has been abbreviated as A1 - PEO ; the LiC104/ 50 : 50 . FIGS . 13F , 136 and 13H show SEM images identifier Celgard - 3_03_GBS_C01.mpr: -Im ( z ) vs. Re ( Z ) # of coated Al substrates . FIG . 13F shows an Al substrate has been abbreviated as Celgard ; the identifier Al- 70-30 coated with PEO , FIG . 13G shows an Al + PEO : LiC104 / 90 : PEO - 1_02_GBS_C01.mpr: < Ew e > vs. Re ( Z ) has been 10 , FIG . 13D shows Al + PEO : LiC104 / 50 : 50 . abbreviated as A1-70-30 - PEO Ew e vs. Re ( Z ) ; the identifier [ 0203 ] Microscope images of different polymer coated K -50-50 -PEO -4_02_GBS_C01.mpr : -Im ( z ) vs. Re ( Z ) has separators are displayed in FIGS . 14A - 14D and FIGS . been abbreviated as K - 50-50 - PEO ; the identifier A1-70-30 14E - 14H . FIG . 14A : Kapton + PEO ; FIG . 14B : Kapton + PEO - 1_02_GBS_C01.mpr: -Im ( z ) vs. Re ( Z ) has been PEO : LiC104 / 90 : 10 ; FIG . 14C : Kapton + PEO : LiClO4/ 70 : abbreviated as A1-70-30 - PEO and the identifier K -70-30 30 ; FIG . 14D : Kapton + PEO : LiC102/ 50 :50 . FIG . 14E : PEO - 3_02_GBS_C01.mpr: -Im ( z ) vs. Re ( Z ) has been Al + PEO ; FIG . 14F : Al + PEO : LiC104 / 90 : 10 ; FIG . 14G : abbreviated as K - 70-30 - PEO . Al + PEO : LiC10./70:30 ; FIG . 14H : A1 + PEO : LiCiO2/ 50 : 50 . [ 0208 ] Results of 1st cycle electrochemical data is dis [ 0204 ] Half cells in coin cell format with polymer elec played in FIG . 19 below . trolyte coated separators displayed in Table 1 , lithium cobalt [ 0209 ] FIG . 19 shows the first cycle charge capacity , oxide ( LCO ) cathodes, Li anode , and DMC / 1M LiC104 discharge capacity and percent retention of the coin cells electrolyte were prepared in a glovebox . with different polymer separators . The charge capacity indi [ 0205 ] FIG . 15 above shows the average OCV measure ments of these LCO half coin cells . The fraction next to the cated by the left hand column and the discharge capacity name of the cell at the bottom of the bar graph represents the indicated by the right hand column are plotted on the Y1 axis number of working cells yielded over the total number of ( left side) and the percent retention of the charge capacity cells made . This figure displays the average OCV of those indicated by the curve is plotted on Y2 axis ( right side ) . yielded cells in Volts ). In general, cells with Al mesh [ 0210 ] The cells were charged at C / 10 to 4.2V and dis substrate displayed the highest failure rate . It is possible that charged at a rate of C / 10 to 2.5 V. The designed capacity for the Al mesh , which is thicker and more rigid than Kapton is the cells were 6 mAh and on an average 5 mAh were shorting some of the cells when pressed into the coin cell extracted . Generally, cells with Kapton separator performed format . better then cells with Al mesh . Cells with Kapton coated [ 0206 ] After OCV measurements, the internal ohmic resis with PEO showed the best results . Cells with Kapton: PEO : tance measurements were taken for the individual coin cells . 90:10 type of polymer separator were selected for further FIG . 16 shows the definition of the measurement elements cycling used . FIGS . 17A - 17C summarizes the results obtained from [ 0211 ] Shown in FIG . 20A is the charge capacity cycle life circuit simulation of the Nyquist plot . Displayed in FIG . comparison of cells with PEO : 90:10 configuration of poly 17A is the relationship between coin cells with different mer electrolyte coated on Kapton and Al mesh against polymer coated electrolyte and R1 , which is defined as the control cell . Control cells display higher capacity through 4 electrolyte or ohmic resistance. ( See FIG . 16 ) . Displayed in cycles . No difference is observed between polymer electro FIG . 17B is the relationship between coin cells with different lytes coted on Kapton or Al mesh . Shown in FIG . 19B is the polymer coated electrolyte and Q1 , which is defined as the discharge capacity cycle life comparison of cell with PEO : double - layer capacitance. Finally , displayed in FIG . 17C is 90:10 configuration of polymer electrolyte coated on Kapton the relationship between coin cells with different polymer and Al mesh against the control cell . Polymer electrolyte coated electrolyte and R2 , which is the polarization resis coated in Al had slightly higher discharge capacity than tance . polymer coated on Kapton . At this time in the experiment, US 2020/0365862 A1 Nov. 19 , 2020 15 more cycle data is needed to draw a firm conclusion that this thickness calculations but the overall thickness is approxi performs better than the control cell however. mately 20 microns. Fracturing of the samples using liquid [ 0212 ] FIG . 20A - 20B : shows the cycle life of cells . First nitrogen for end on analysis or cutting with a diamond blade cycle with PEO : 90 : 10 configuration coated on Kapton and should provide more exact dimensional details in the future Al mesh . FIG . 20A . Charge cycle . FIG . 20B . Discharge should that be needed . cycle . [ 0219 ] Half cells in coin cell format were prepared in a glovebox using these PVDF polymer based slurry coated Example 4 : PVDF Polymer Base Slurry Coated on separators, LCO cathodes, Li anodes, and two different Supports electrolytes ( EC / DMC with 1M LIPF6 and DMC with 1M [ 0213 ] Kapton ( K ) separator and aluminum ( Al) mesh LiPF ). were coated with various combinations of slurry made of [ 0220 ] FIG . 25 shows average open circuit voltage ( OCV ) Polyvinylidene fluoride ( PVDF ) , Lithium - titanate ( LTO ), measurements of the LCO half coin cells made with PVDF Carbon Filler ( CF ) and Graphite ( G ) . The descriptions and base slurries . The fraction next to the name of the cell concentrations of these PVDF based slurry coated separators represents the number of working cells yielded over the total are displayed in Table 3 below . number of cells attempted . The figure displays the average OCV in volts of the working cells . Overall, all the cells had TABLE 3 low OCV and the yields of functioning coin cells were relatively low . This was attributed to use of two different PVDF types of electrolyte. Coin cell mechanics, cathode electrode Separator Binder Active Conductive Formulation Amount Taterial Filler ( punched edges ), quality of Li and crimper also can con Name Substrate wt % wt % wt % tribute to bad yield . K + PVDF Kapton 100 0 0 [ 0221 ] After OCV measurements were taken , the internal K + PVDF + LTO Kapton 30 60 10 ohmic resistance measurements were recorded for indi K + PVDF + LTO + Kapton 35 65 0 vidual coin cells . FIGS . 26A - 26C summarize the results CF obtained from circuit simulation of the Nyquist plot . Dis K + PVDF + G Kapton 35 65 0 AL + PVDF Al mesh 100 0 0 played in FIG . 26A is the relationship between coin cells AL + PVDF + LTO Al mesh 30 60 10 with different polymer coated electrolytes and R1 , which is AL + PVDF + LTO + Al mesh 35 65 0 defined as the electrolyte or ohmic resistance . ( See FIG . 16 ) . CF Displayed in FIG . 26B is the relationship between coin cells AL + PVDF + G Al mesh 35 65 0 : with different polymer coated slurry and Q1 , which is defined as the double - layer capacitance . Finally, displayed in [ 0214 ] The coating weights per area of these separators are FIG . 26C is the relationship between coin cells with different displayed in FIG . 21. PVDF slurry coated on Al substrates polymer coated electrolyte and R2 , which is defined as the gave higher coating weights on average , with the formula polarization resistance . tion of PVDF with Graphite giving the highest coating [ 0222 ] In general, relationship between R1 , R2 and Q1 are loading within the group of tests . Weights are in g / cm² . inversely proportional. The increase in R1 or R2 indicates [ 0215 ] Microscope images of substrates coated with internal resistance increases inside of the cell . In this case all PVDF base slurries : FIG . 22A : Kapton coated with PVDF the coin cells were attempted to be made the same way , with and LTO slurry. FIG . 22B : Kapton coated with PVDF , LTO , the only component that was changed was the different and CF slurry. FIG . 22C : Kapton coated with PVDF, and polymer electrolytes coated on different substrates in theory. graphite slurry . FIG . 22D : Al mesh coated with PVDF and Therefore, the internal resistance differences can be attrib LTO slurry. FIG . 22E : Al mesh coated with PVDF , LTO and uted to the different polymer electrolytes substrates used . It CF slurry . FIG . 22F : Al mesh coated with PVDF, and is difficult to conclude from this initial data which polymer graphite slurry. electrolyte coated separator is the best performing. As can be [ 0216 ] The microscope images of these Kapton and Al seen in overlaid Nyquist plot in FIG . 27 the data was very mesh coated PVDF based slurry in FIGS . 22A - 22F show inconsistent. These inconsistent results could have been a that on both substrates the slurry coated with PVDF and result of two different electrolyte lots that were needed to graphite formulation covers the surfaces more smoothly and complete the series of experiments. Ideally no other changes uniformly in comparison to coatings with PVDF and LTO would have been made during the assembly of these cells . slurry . Rough surfaces can result in micro shorts during the However, the coin cell spacers and the springs were changed coin cell assembly. FIGS . 22A - 22F also shows that with through the series of builds and so drawing a firm conclusion manipulation of the slurry viscosity it is possible to fill in the from one cell to the next is not reliable . To get a reliable data all the pores of the substrate . Further experiments can be it is important to the experiments consistent with only one conducted . The PVDF polymer can fill in the holes com variable changed at a time . It is recommended that these pletely at the current dimensions as can be seen in FIG . 23D results obtained are repeated . In the legend for FIG . 27 , the and SEM image of FIG . 23 showing Al mesh coated with identifier Al -PVdf - 1_02_GBS_C01.mpr has been abbrevi PVDF . ated as Al- PVdf ; the identifier K -PVDF -LTO - 3_03_GBS_ [ 0217 ] FIGS . 24A and 24B show SEM images of Al ( FIG . C01.mpr has been abbreviated as K - PVDF -LTO ; the iden 24A ) mesh and Kapton ( FIG . 24B ) coated with PVDF and tifier ctl -2_02_GBS_C01.mpr has been abbreviated as ctl - 2 ; graphite slurry . the identifier K - PVDF - G - 2_03_GBS_C01.mpr has been [ 0218 ] Displayed in FIGS . 24A and 24B are Kapton and abbreviated as K - PVDF - G ; the identifier Al- PVDF -LTO - 3_ Al mesh coated with PVDF and graphite slurry with an edge 03_GBS_C01.mpr has been abbreviated as Al -PVDF - LTO ; on view . It is difficult to distinguish the difference between the identifier K - PVdf -LTO -CF - 2_02_GBS_C01.mpr has substrate and the polymer electrolyte layers for precise been abbreviated as K -PVdf -LTO_CF ; the identifier US 2020/0365862 A1 Nov. 19 , 2020 16
Al -PVDF -LTO - CF -2_03_GBS_C01.mpr has been abbrevi or any combination of items in a list separated by “ and / or ” ated as Al -PVDF - LTO - CF ; the identifier K - PVdf - 1_02_ are included in the list ; for example “ 1 , 2 and / or 3 ” is GBS_C01.mpr has been abbreviated as K - PVdf; and the equivalent to “ l’or “ 2 ' or “ 3 ' or ‘ 1 and 2 or ‘ 1 and 3 ' or 62 identifier Al- PVDF - G -3_03_GBS_C01.mpr has been abbre and 3 ' or ' 1 , 2 and 3 ” ” . viated as Al - PVDF - G . [ 0229 ] Every formulation or combination of components [ 0223 ] Due to the number of Arbin channels available , described or exemplified can be used to practice the inven only the PVDF and graphite slurry coated Kapton and Al tion , unless otherwise stated . Specific names of materials are mesh cell were selected to be cycled . The electrochemical intended to be exemplary, as it is known that one of ordinary data displayed in FIG . 28 is of those cells , where the 1st cycle skill in the art can name the same material differently. One is shown . FIG . 28 : First cycle charge capacity , discharge of ordinary skill in the art will appreciate that methods, capacity, and percent retention of the coin cells with Kapton device elements, starting materials, and synthetic methods and Al mesh coated with PVDF and graphite slurry . The other than those specifically exemplified can be employed in charge capacity indicated by the left column and the dis the practice of the invention without resort to undue experi charge capacity indicated by the right column are plotted on mentation . All art - known functional equivalents, of any such the Y1 axis ( left side ) and the percent retention of the charge methods, device elements, starting materials, and synthetic capacity indicated with by the curve is plotted on Y2 axis methods are intended to be included in this invention . ( right side ). Whenever a range is given in the specification , for example, [ 0224 ] The cells were charged at C / 10 to 4.2V and dis a temperature range , a time range, or a composition range, charged at rate of C / 10 to 2.5 V. The designed capacity for all intermediate ranges and subranges, as well as all indi the cells was calculated to be 6 mAh and on an average 5 vidual values included in the ranges given are intended to be mAh was extracted from these cells . The early results show included in the disclosure . that cells with Al substrate displayed the lowest percent "[ 0230including ] As , " used" containing herein , , “" comprising or " characterized” is synonymous by , " and with is retention at 66 % , in comparison to cells with the Kapton inclusive or open - ended and does not exclude additional, substrate at 97 % . unrecited elements or method steps. As used herein , " con [ 0225 ) Shown in FIG . 29A is the charge capacity cycle life sisting of ” excludes any element, step , or ingredient not comparison of cells with K + PVDG + G , Al + PVDF + G , and specified in the claim element. As used herein , “ consisting the control separator. Other than the initial drop in charge essentially of” does not exclude materials or steps that do not capacity there is no difference that can yet be observed materially affect the basic and novel characteristics of the between polymer electrolytes coated on Kapton or Al mesh claim . Any recitation herein of the term “ comprising ” , in the cycle history. This will continue to be monitored over particularly in a description of components of a composition time for variations . Shown in FIG . 29B is the discharge or in a description of elements of a device , is understood to capacity cycle life comparison of cell with K + PVDG + G , encompass those compositions and methods consisting Al+ PVDF + G and the control separator. At this time , more essentially of and consisting of the recited components or cycles are still needed for any conclusions to be drawn and elements . The invention illustratively described herein suit the cycling will continue. ably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically STATEMENTS REGARDING INCORPORATION disclosed herein . BY REFERENCE AND VARIATIONS [ 0231 ] The terms and expressions which have been [ 0226 ] All references throughout this application, for employed are used as terms of description and not of example patent documents including issued or granted pat limitation , and there is no intention in the use of such terms ents or equivalents; patent application publications; and and expressions of excluding any equivalents of the features non - patent literature documents or other source material; are shown and described or portions thereof, but it is recognized hereby incorporated by reference herein in their entireties, as that various modifications are possible within the scope of though individually incorporated by reference, to the extent the invention claimed . Thus, it should be understood that each reference is at least partially not inconsistent with the although the present invention has been specifically dis disclosure in this application ( for example, a reference that closed by preferred embodiments and optional features, is partially inconsistent is incorporated by reference except modification and variation of the concepts herein disclosed for the partially inconsistent portion of the reference ). may be resorted to by those skilled in the art, and that such [ 0227] All patents and publications mentioned in the modifications and variations are considered to be within the specification are indicative of the levels of skill of those scope of this invention as defined by the appended claims . skilled in the art to which the invention pertains. References 1-36 . ( canceled ) cited herein are incorporated by reference herein in their 37. An electrochemical cell comprising: entirety to indicate the state of the art, in some cases as of their filing date , and it is intended that this information can a positive electrode ; be employed herein , if needed , to exclude ( for example , to a negative electrode ; disclaim ) specific embodiments that are in the prior art. For a composite membrane layer positioned between the said example , when a compound is claimed , it should be under electrodes comprising stood that compounds known in the prior art, including at least one porous separator layer ; and certain compounds disclosed in the references disclosed at least one ionically conductive and electrochemically herein ( particularly in referenced patent documents ), are not active solid - state material; and intended to be included in the claim . [ 0228 ] When a group of substituents is disclosed herein , it one or more electrolytes positioned between said positive is understood that all individual members of those groups electrode and said negative electrode; said one or more and all subgroups and classes that can be formed using the electrolytes capable of conducting ionic charge carri substituents are disclosed separately. When a Markush group ers ; or other grouping is used herein , all individual members of wherein the said ionically conductive and electrochemi the group and all combinations and subcombinations pos cally active material is in the form of a coating on at sible ofthe group are intended to be individually included in least one side of the separator layer or a coating on any the disclosure . As used herein , “ and / or ” means that one , all , of the electrodes; and US 2020/0365862 A1 Nov. 19 , 2020 17
wherein the ionically and electronically active material 50. The electrochemical cell of claim 44 , wherein the comprises a material selected from the group consisting ionically conductive and electrochemically active material of carbon , lithium titanate, Li202 , Li20 , titanium dis comprises a material selected from the group consisting of ulfide, iron phosphate , SiO2 , V205 , lithium iron phos carbon , lithium titanate , Li2O2 , Li20 , titanium disulfide , phate , MnO , A1,03, TiO , LIPF . , Li P , LizN , LINO3, iron phosphate , SiO2 , V205 , lithium iron phosphate , MnO2, A1203 , TiO2 , LiPF6 , Li3P , Li3N , LINO3 , LiC104 , LiOH , LiC104 , LiOH , PEO , P2O5 , LIPON , LISICON , Thio PEO , P205 , LIPON , LISICON , ThioLISICO , Ionic Liquids, LISICO , Ionic Liquids, A1 , Cu , Ti , Stainless Steel , Iron , Al , Cu , Ti , Stainless Steel , Iron , Ni , graphene oxide , Ni , graphene oxide , PEDOT- PSS , and combinations PEDOT- PSS , and combinations thereof. thereof. 51. The electrochemical cell of claim 37 , wherein the cell 38. (canceled ) is a Li - ion or Na - ion cell . 39. The electrochemical cell of claim 37 , wherein the 52. The electrochemical cell of claim 44 , wherein the cell composite membrane layer is from to 10 nm to 50 um in is a Li - ion or Na - ion cell . thickness. 53. The electrochemical cell of claim 37 , wherein the 40. The electrochemical cell of claim 37 , wherein the ionically and electronically active material comprises a ionically and electrochemically active material comprises at material selected from the group consisting of lithium titan least an electrochemically active material, with arbitrary ate , titanium disulfide, V205 , lithium iron phosphate , MnO2, voltage ranges of reduction and oxidation, with values TiO2 , LiC104 , and combinations thereof. between the charge - discharge voltage limits of the said 54. The electrochemical cell of claim 44 , wherein the electrochemical cell . ionically and electronically active material comprises a 41. ( canceled ) material selected from the group consisting of lithium titan 42. ( canceled ) ate , titanium disulfide, V205 , lithium iron phosphate, MnO2, 43. ( canceled ) TiO2 , LiC104 , and combinations thereof . 44. An electrochemical cell comprising: 55. The electrochemical cell of claim 37 , wherein the a positive electrode; ionically and electronically active material comprises a a negative electrode ; material selected from the group consisting of Li2O2 , Li20 , a composite porous separator layer positioned between iron phosphate , SiO2 , Al2O3 , TiO2 , LIPF . LizP, LizN , the said electrodes comprising LiNO3 , LiOH , PEO , P2O5 , LIPON , LISICON , ThioLISICO , at least one ionically conductive and electrochemically Ionic Liquids, Al , Cu , Ti , Stainless Steel , Iron, Ni , graphene active solid - state material, and oxide, PEDOT- PSS , and combinations thereof. at least one solid - state binder material; and 56. The electrochemical cell of claim 44 , wherein the one or more electrolytes positioned between said positive ionically conductive and electrochemically active solid - state electrode and said negative electrode ; said one or more material is supported by an electronically conducting porous electrolytes capable of conducting ionic charge carri support or frame. ers . 57. The electrochemical cell of claim 44 , wherein the 45. The electrochemical cell of claim 44 , wherein the said electronically conducting porous support or frame is a ionically conductive and electrochemically active material is metallic frame. in the form of a coating on at least one side of one of the 58. The electrochemical cell of claim 44 , wherein the electrodes . metallic frame is coated with an electronically insulating 46. The electrochemical cell of claim 44 , wherein the material . separator layer is from to 10 nm to 50 um in thi ness . 59. The electrochemical cell of claim 44 , wherein the 47. The electrochemical cell of claim 44 , wherein the ionically conductive and electrochemically active solid - state separator layer has at least 30 % porosity . material is provided in the form of bulk pieces , particles or 48. The electrochemical cell of claim 44 , wherein the fibers . separator layer has less than 5 % conductive carbon . 60. The electrochemical cell of claim 44 , wherein the 49. The electrochemical cell of claim 44 , wherein the ionically conductive and electrochemically active solid - state separator layer comprises an electrochemically active mate material is bonded to the electronically conducting porous rial , with arbitrary voltage ranges of reduction and oxida support or frame using the at least one solid - state binder tion , with values between the charge -discharge voltage material. limits of the said electrochemical cell .