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THE MAIN TEA ETA USA CEL20180190959A1 MAI TE RITA MARIA MATAT AN ( 19) United States ( 12) Patent Application Publication (10 ) Pub . No. : US 2018 /0190959 A1 ALKORDI et al. ( 43) Pub . Date : Jul. 5 , 2018 (54 ) NONOSTRUCTURED METAL ORGANIC Publication Classification MATERIAL ELECTRODE SEPARATORS AND (51 ) Int. CI. METHODS THEREFOR HOIM 2 / 16 (2006 .01 ) HOIM 4 /50 (2010 .01 ) (71 ) Applicant: KING ABDULLAH UNIVERSITY HOIM 2 / 14 (2006 .01 ) OF SCIENCE AND TECHNOLOGY, (52 ) U .S . CI. Thuwal (SA ) CPC ...... HOIM 2 / 1673 ( 2013 .01 ); HOTM 4 /50 ( 72 ) Inventors : Mohamed Helmi ALKORDI, Thuwal ( 2013 . 01 ) ; Y1OT 29/ 49115 ( 2015 .01 ) ; HOIM (SA ); Mohamed EDDAOUDI, Thuwal 2 / 145 ( 2013 .01 ) ; HOIM 2 / 1653 (2013 .01 ) (SA ) (21 ) Appl. No .: 15 /852 , 231 (57 ) ABSTRACT Provided herein are nano structured electrode separators (22 ) Filed : Dec. 22 , 2017 comprising metal organic materials capable of attaching to Related U .S . Application Data one or more electrodes and electrically insulating at least one electrode while allowing migration of ionic charge (62 ) Division of application No . 13 /861 , 775 , filed on Apr. carriers through the nanostructured electrode separator . 12, 2013 , now Pat. No . 9 , 853, 270 . Methods of using such electrode separators include posi (60 ) Provisional application No. 61 /625 ,973 , filed on Apr. tioning a nanostructured electrode separator between two 18 , 2012 electrodes of an electrochemical cell .

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NONOSTRUCTURED METAL ORGANIC [0013 ] Advantageously , the nanostructured separator can MATERIAL ELECTRODE SEPARATORS AND allow for unprecedented control over ion conductivity and METHODS THEREFOR related performance characteristics of batteries or electro chemical cells . CLAIM OF PRIORITY [0014 ] Other aspects , embodiments , and features will be apparent from the following description , the drawings , and [0001 ] This application is a divisional of U . S . application the claims. Ser. No . 13 / 861, 775 , filed on Apr. 12 , 2013 , which claims thebenefit of prior U . S . Provisional Application No. 61/ 625 , 973 , filed on Apr. 18 , 2012 , which is incorporated by DESCRIPTION OF DRAWINGS reference in its entirety . [0015 ] FIG . 1 is a diagram illustrating a portion of a battery or an electrochemical cell. TECHNICAL FIELD [ 0016 ] FIGS. 2A , 2B and 2C are diagrams illustrating a lattice structure that can be built to create a nanostructured [0002 ] This invention relates to an electrode separator for separator. use in a battery or an electrochemical cell . [0017 ] FIGS . 3A and 3B are photographs of electrode pellet and nanostructured separator coated electrode pellet . BACKGROUND [0018 ] FIGS . 4A and 4B are micrograph images of elec trode pellet and nanostructure separator coated electrode [0003 ] Batteries and electrochemical cells can be used as pellet. sources of energy. Generally , batteries and electrochemical [ 0019 ] FIGS. 5A and 5B are micrograph images of elec cells include a positive electrode , a negative electrode , a trode pellet and nanostructured separator coated electrode separator between the positive electrode and the negative pellet. electrode that prevents electrical contact between the two electrodes , and an electrolytic solution in contact with the [ 0020 ] FIG . 6 is a graph depicting the X - ray powder electrodes and separator that permits ion migration . Elec diffraction pattern of the nanostructured separator on the trons flow from electrode to electrode via a conductor. The electrode pellet . physical and chemical properties of the separator can affect [ 0021 ] FIG . 7 is a diagram depicting the X - ray crystal the performance properties of the battery or electrochemical structure of the nanostructured separator on the electrode pellet10 . cell. [0022 ] FIGS . 8A and 8B are photographs of electrode pellet and nanostructured separator coated electrode pellet . SUMMARY 10023 ) FIGS . 9A and 9B are micrograph images of elec [ 0004 ] A separator for a battery or electrochemical cell can trode pellet and nanostructured separator coated electrode be a nanostructured separator . pellet. [0005 ] In one aspect, an electrode material includes an [0024 ] FIG . 10 is a graph depicting the X -ray powder electrode substrate and a nanostructured separator on a diffraction pattern of the nanostructured separator on the electrode pellet . surface of the electrode substrate . [0025 ] FIG . 11 is a diagram depicting the X -ray crystal [0006 ] In another aspect , an electrochemical cell compris structure of the nanostructured separator on the electrode ing an electrode substrate , a nanostructured separator on a pellet. surface of the electrode substrate and a second electrode in [0026 ] FIGS. 12A and 12B are micrograph images of the contact with the nanostructured separator. surface of an electrode pellet after pellet -press of a nano [0007 ] In another aspect, a method of forming an electrode structured separator. material includes forming the nanostructured separator on a [ 0027 ] FIG . 13 is a graph depicting the X - ray powder surface of the electrode support. diffraction pattern of the nanostructured separator on the 10008 ] In another aspect, a method of forming an electro electrode pellet . chemical cell includes forming the nanostructured separator on a surface of the electrode support and contacting the DETAILED DESCRIPTION nanostructured separator with the second electrode . [0009 ] In certain embodiments , the nanostructured sepa [ 0028 ] Referring to FIG . 1 , a battery or electrochemical rator can include a metal- organic material. The metal cell can include a cathode , an anode and a separator between organic material can be a metal- organic framework , a metal the cathode and anode . The battery or electrochemical cell organic polyhedron , or a coordination polymer. can be contained within a suitable housing (not shown ). [0029 ] The battery and electrochemical cell include a [0010 ] In other embodiments , the nanostructured separa primary cell or a non - rechargeable battery or a secondary tor can be a covalent - organic framework . cell or rechargeable battery . Examples of a primary cell [0011 ] In certain embodiments , the nanostructured sepa includes an alkaline battery, aluminum battery , chromic acid rator can include a zinc or lead coordination compound , for cell , Clark cell, Daniell cell , dry cell, Earth battery , Galvanic example , a zinc terephthalate metal - organic framework or a cell , Grove cell , Leclanché cell , lithium battery , lithium air lead - ( 4 ,4 ' - sulfonyldibenzoate ) metal -organic framework . In battery , mercury battery , molten salt battery , nickel oxyhy other embodiments , the nanostructured separator can droxide battery, oxyride battery , organic radical battery , include a 2 ,5 - thiophenediboronicacid covalent- organic paper battery , Pulvermacher ' s chain reserve battery , silver framework . oxide battery , solid - state battery , voltaic pile , penny battery, [0012 ] In certain aspects , the electrode substrate can be a trough battery , water - activated battery, Weston cell , zinc - air manganese oxide . battery , zinc -carbon battery, or zinc chloride battery . US 2018 /0190959 A1 Jul. 5 , 2018

Examples of a secondary cell includes a flow battery , 0034 ] A nanostructured separator is a separator that has vanadium redox battery, zinc -bromine flow battery , fuel cell, nanometer or sub -nanometer sized features that provide the lead - acid battery, deep cycle battery , VRLA battery, AGM nanostructured separator with particular properties that can battery , gel battery , lithium air battery , lithium -ion battery , enhance the performance of a battery or electrochemical Beltway battery, lithium ion polymer battery , lithium iron cell . In general, the nanostructured separator can be built phosphate battery, lithium - sulfur battery, lithium -titanate from a framework ofmolecular structures depicted in FIGS . battery, molten salt battery , nickel -cadmium battery , nickel 2A , 2B and 2C , and combinations thereof . In these struc cadmium battery , vented cell type nickel hydrogen battery , tures , there is a polyvalent core , which can be a metal ion , nickel- iron battery , nickel metal hydride battery , low self atom , or other moiety capable of bonding with 2 , 3 , 4 , 5 , 7 , discharge NiMH battery, nickel - zinc battery , organic radical 8 , 9 , 10 , 11 or 12 bridging groups to form a scaffold . The battery, polymer- based battery , polysulfide bromide battery , bonds can be covalent bonds , ionic bonds or dative bonds , potassium - ion battery, rechargeable alkaline battery, silicon or combinations thereof. The scaffold or regions thereof can air battery, sodium - ion battery , sodium -sulfur battery, super be one - , two - or three - dimensional in structure and can iron battery, zinc -bromine flow battery, or zinc matrix bat consist of the various bonding motifs shown in FIGS . 2A , tery . 2B and 2C . [ 0030 ] The primary function of an electrode separator is to [0035 ] The polyvalent core can be carbon , silicon , a di- , sever as an electrical insulator between a positive electrode tri - , or quadravalent organic moiety ( for example , carbon and a negative electrode ( for example, a cathode and an atom , ethylene group , aryl group , and the like ), or a metal anode , respectively ) to prevent migration of electrons from ions of one or more main group element or transition metal electrode to electrode through the separator while allowing including ions of Li, Na, K , Cs, Mg, Ca, Sr, Ba , Sc , Y , Ti , for migration of ionic charge carriers through the separator. Zr , Hf, V , Nb , Ta , Cr, Mo, W , Mn, Re , Fe , Ru , Os , Co , Rh , The migration of ionic charge completes the electrical Jr, Ni, Pd , Pt, Cu , Ag , Au , Zn , Cd , Hg, Al, Ga, In , Ti , Si, Ge, circuit, permitting passage of current from positive electrode Sn , Pb , As, Sb , or Bi. to negative electrode in an electrochemical cell. [0036 ] The bridging group can be a polydentate group , for [0031 ] A nanostructured material, such as a metal- organic example , a C2 - 12 hydrocarbon chain optionally containing material (MOM ) , including a metal- organic framework at least one double bond, at least one triple bond , or at least (MOF ) , a metal- organic polyhedron (MOP ) , or a coordina one double bond and one triple bond and optionally inter tion polymer (CP ) , or a covalent- organic framework (COF ) rupted by at least one - o - , - N (Rc ) , or S , or C3 - 16 can serve as separator between electrodes in a battery or cyclic group , optionally aromatic and optionally heterocy electrochemical cell . clic , the briding group being optionally substituted with [0032 ] Metal- organic materials and coordination polymers alkyl, alkenyl, alkynyl, alkoxy, hydroxyl, hydroxylalkyl, refer to a large family of solids characterized by the nature halo , haloalkyl, amino , carboxyl, amido , C1- 4 alkyl, C2 -4 of coordination bonding between metal ions and organic alkenyl, C2 -4 alkynyl, C1 -4 alkoxy, nitro , cyano , C3 -5 linkers . The metal ions can include alkali metals , rare - earth cycloalkyl, 3 - 5 membered heterocycloalkyl, monocyclic metals , transition metals , lanthanides, or post - transition met aryl, 5 - 6 membered heteroaryl, C1 - 4 alkylcarbonyloxy, als . Organic linkers can include any organic molecule C1 - 4 alkyloxycarbonyl, C1- 4 alkylcarbonyl, or formyl capable of formation of coordination or ionic bond to metal group , which is capable of bonding to 2 , 3 , 4 , 5 , or 6 , or ions . Organic linkers generally possess functional groups more , of the polyvalent cores. Rc can be H or C1 - 4 alkyl. like carboxylic acids , amines , azoles , oxazoles , thiols , thi [0037 ] The nanostructured separator can have a permanent azoles and other heteroatom groups capable of bonding to a porosity , high surface area and appropriate chemical, ther metal ion . MOMs and CPs can exhibit various structures mal and physical stability suitable of use in a battery or ranging from discrete supermolecules (known also as metal electrochemical cell . In other embodiments , enclathrated or organic polyhedra , MOPs ) to chains to layers and sheets to encapsulated guest molecules or ions can undergo guest 3D structures . MOMs and CPs can exhibit permanent poros exchange with other molecular or ionic species in the ity as indicated by reversible gas sorption isotherms and /or nanostructured separator to alter properties of the separator. reversible guest exchange behavior. The surface area may be determined by using the BET [0033 ] Covalent- organic frameworks refer to a large fam method (“ BET surface area ” ) . This refers to the Brunauer , ily of solids characterized by the nature of covalent bonding Emmett and Teller (BET ) method for surface area determi between organic monomers. The organic monomers can nation , which utilizes the isothermal adsorption of nitrogen contain metal ions include alkali metals , rare - earth metals , to measure total surface area of a material. Another method transition metals , lanthanides , or post - transition metals . uses the Langmuir model. Thermal stability can be deter Organic monomers include any organic molecule capable of mined using differential scanning calorimetry (DSC ) , dif formation of covalent bonds to the same molecule to form ferential thermal analysis (DTA ) , or thermogravimetric homo- polymer or other type of molecules to form hetero analysis ( TGA ). Porosity can be determined by porosimitry polymer. Organic monomers generally possess functional measurements. groups like carboxylic acids , amines , azoles , oxazoles , [0038 ]. The nanostructured separator can include design thiols , thiazoles, terminal alkynes, halogenated aromatics able and tunable pore sizes , pore distribution and pore shape . like iodo / bromo benzenes , boronic acids , aldehydes , amides , In another embodiment, the nanostructured separator can acyl halides or other functional groups . COFs can exhibit include designable and tunable pore functionality . For various structures ranging from discrete supermolecules to example , accessible voids inside the porous material can chains to layers and sheets to 3D structures . COFs can incorporate a variety of guest molecules , ions or gases of exhibit permanent porosity as indicated by reversible gas desirable functionality for the nanostructured separator. In sorption isotherms and /or reversible guest exchange behav another embodiment, the nanostructured separator can ior . include a designable and tunable composition of the organic ! US 2018 /0190959 A1 Jul. 5 , 2018 inorganic parts of the separator , which can provide control Kundu , et al. , ChemComm 2012 , DOI: 10 . 1039/ c2cc31135f, and enhancement in the design and selection of suitable which is incorporated by reference in its entirety . material specific electrochemical systems. In another [0043 ] The MOFs described in U . S . Pat. No .: 8, 123 ,834 embodiment, the nanostructured separator can have a neutral include Zn -MOF1 , Zn -MOF2 , Zn -MOF3 , Zn -MOF4 , or charged backbone (cationic or anionic ) where in charged ZnMOFS , Cu -MOF1 , Cu -MOF2 , Tb -MOF1 , Tb -MOF2 , backbone the presence of encapsulated / enclathrated coun Cd -MOF1 , Cd -MOF2 , CdMOF3 , Co -MOF1 , CO -MOF2 , terions can provide control and enhancement in the design Zn -MOF6 , MOF - 5, Cu( 4 ,4 '- bpy ) , - NO3 (H2O ) 1. 253 and selection of suitable material specific electrochemical IRMOF2, [ Cuz ( TMA ) 2 ] n , [Cu (OH ) – (C3H _ NCO2) , MOF systems. The high crystallinity of the nanostructured sepa 38 , Ag( 4 , 4 '- bpy )NO3 , IRMO3 and IRMOF7, among others . rator enables accurate structural characterization and control [0044 ] The MOFs described in U .S . Pat. No .: 8 ,034 ,952 of desirable properties including ion conductivity , ion include supramolecular assemblies comprising a 1 : 8 ratio of exchange, or void dimensions. a supermolecular polyhedral building block and a triangular [0039 ] For example , the nanostructured separator can have molecular building block , which form a ( 3 ,24 ) - connected rht channels /cages / windows within a relatively wide range in net , among others . The supermolecular polyhedral building diameter (0 . 5 ~ 5 nm ) , or with a wide range of surface area block has points of extension corresponding to the vertices ( few m - / g to several hundred mº/ g . The nanostructured of a rhombicuboctahedron ( and other regular polyhedra that separator can demonstrate good thermal stability (usually have 24 vertices and the edge skeleton shared by small rhombihexahedron , small cubicuboctahedron , and rhombi stable to 200° C . - 300° C .) and chemical stability ( stable cuboctahedron ) for linking the supermolecular polyhedral against structural disintegration in neutral, acidic ,or basic building block to the triangular building blocks . In the solutions. assembly, an individual supermolecular polyhedral building [0040 ] The nanostructured separator should be thick block is linked to twenty - four different triangular building enough to reduce or eliminate shorting between the positive blocks and an individual triangular building block is linked electrode and the negative electrode by impedance or by to three different supermolecular polyhedral building blocks preventing electrode dendrite formation . It is important that with the linkages comprising covalent bonds , coordinate the nanostructured separator also allow for facile ion migra tion between the positive electrode and the negative elec covalent bonds, noncovalent bonds , or a combination trode. For example , the pore size in the nanostructured thereof. separator must be small enough to avoid formation of [0045 ] The MOFs described in U . S . Pat . No .: 7 , 880 ,026 dendrites through the membrane, but large enough to permit include IRMOF - 1 , IRMOF - 2 , IRMOF - 3 , Zn -MOF - 1 , Zn ion migration . The impedance of the nanostructured sepa MOF - 2 , Zn -MOF - 3 , Zn -MOF - 4 , Zn -MOF - 5 , Cu -MOF - 1 , rator should be high enough to prevent electrical shorting Cu -MOF - 2 , Tb -MOF - 1 , Tb -MOF - 2 , Cd -MOF - 1 , Cd- MOF between the positive electrode and the negative electrode 2 , Cd -MOF - 3 , CO -MOF - 1 , CO -MOF - 2 , Zn -MOF - 6 , MOF - 5 , while optimizing the efficiency of the battery or electro Cu ( 4 , 4 ' -bpy ) . 5NO3( H2O ) 1. 25, [ Cuz ( TMA ) 2 ]n , [Cu ( OH ) chemical cell. For example , the average pore diameter of the (C3H _ NCO2] n , MOF - 38 , Ag ( 4 , 4 '- bpy )NO3 , and IRMOF - 7 , nanostructured separator can be less than 20 nm , less than 10 among others . nm , less than 5 nm , less than 1 nm , or greater than 0 . 5 nm . 0046 ] Referring again to FIG . 2 , the battery or electro The average thickness of the nanostructured separator can be chemical cell can include three layers. The first layer can be less than 100 microns, less than 50 microns , less than 10 a substrate , and can be one electrode of the battery or the microns, less than 1 micron , less than 500 nm , less than 200 electrochemical cell. The nanostructured separator can be nm , less than 100 nm , less than 50 nm , less than 40 nm , less grown on a substrate , such as a first electrode of a battery or than 30 nm , less than 20 nm , less than 10 nm , less than 5 nm , electrochemical cell. For example , the nanostructured sepa rator can be grown on an anode material. The substrate can less than 1 nm , or greater than 0 .5 nm . be any solid support, for example , a porous , conductor, 0041 ] Materials appropriate for use for the nanostruc semi- conductor, magnetic , metallic , non -metallic , photoac tured separator can include a metal- organic material tive , polymer , or heat responsive material. The substrate can (MOM ) , including a metal -organic framework (MOF ) , a be conducting , semiconducting or insulating . The substrate metal- organic polyhedron (MOP ) , or a coordination poly can be quartz , diamond , silica , alumina , a metal oxide , a mer ( CP ) , or a covalent- organic framework (COF ) that is metal hydroxide, a metal in elemental state or other suitable substantially inert to the electrolytic solution and capable of material. The substrate can be amorphous , polycrystalline , reducing or eliminating electron transfer between electrodes . or a single crystal. The substrate surface in contact with the The nanostructured separator can include wettable material nanostructured separator can have a polished , rough , pat coatings , polymers , gels , or fillers such as , for example , terned , or functionalized surface , for example , with surface inorganic particles, biopolymers , polysaccharides, cellulose , active molecules (SAMs ) . Each electrode , independently , dixtrans, cyclodextrins, silicates, or nanoparticles . can include a metal, metal oxide, metal salt, metal complex , [ 0042 ] Examples of possibly suitable nanostructured metal nanoparticle , molten salt or gas. materials include the metal- organic framework materials 10047 ] The second layer can be a nanostructured separator. described , for example, in U . S . Pat . Nos . 8 , 123 ,834 , 8 , 034 , The nanostructured separator can be any MOF , MOP , CP, or 952, 7 ,880 ,026 , 7 ,279 ,517 , 6 ,929 ,679 , 6 ,893 , 564 , and 6 ,624 , COF of desirable structure or functionality . For example , the 318 , each of which is incorporated by reference in its nanostructured separator can be non - porous , microporous , entirety . The design of pores in metal organic framework or mesoporous . The nanostructured separator can form materials is described , for example , in U . S . Pat. Nos . 7 , 196 , chains , sheets , or a 3D polymer or crystalline network . In 210 , and 6 ,930 , 193 , each of which is incorporated by addition , the nanostructured separator can be neutral, reference in its entirety . Other examples of possibly suitable anionic , or cationic and can include different counterions, nanostructured materials are described , for example , in T. combining any one or more metal, transition metal, lan US 2018 /0190959 A1 Jul. 5 , 2018

thanides , alkaloids, rare - earth metals , chalcogenides, and 4B ) . FIGS . 5A and 5B represent SEM images showing the one or more organic molecule as linker . In certain embodi cross section of the MOF thin film on top of the MnO , ments , the nanostructured separators can include accessible substrate at two different magnifications. The average cross voids inside the structure , which can be empty or occupied section of the MOF thin film was 60 microns. by guest molecules that can be solvent, organic substance , 10053 ] Referring to FIG . 6 , the X - ray powder diffraction counterions, ionic species , gases, or other species. The pattern of the Zn - terephthalate MOF film grown on the dimension and chemical composition of the nanostructured Mno , substrate . FIG . 7 represents the X - ray single crystal separator along with the nature of optional enclosed guest structure of the Zn - terephthalate MOF film grown on the molecules orions can provide control over ion migration MnO , substrate . The disordered parts of the framework , characteristics through the separator , thus enabling enhance hydrogen atoms and disordered guest solventmolecules are ment and / or control of the battery orelectrochemical cell omitted for clarity . performance . [0048 ] The third layer can be the second electrode , or Example 2 cathode , of the battery or electrochemical cell . The second electrode can be any solid support, for example , a porous , [0054 ] 180 mg of finely grinded MnO2 was pressed at conductor, semi- conductor, magnetic , metallic , non -metal 15, 000 lb /inch ? to prepare the solid support. A mixture of lic , photoactive , polymer , or heat responsive material. The 4 ,4 '- sulfonyldibenzoic acid (0 . 1 mmol, 30 mg) and second electrode can be conducting , semiconducting or Pb ( NO3) 2 (0 . 1 mmol, 33 mg) was prepared and dissolved in insulating . The second electrode can be quartz , diamond , N ,N - dimethylformamide (2 mL ) and this mixture added to silica , alumina, a metal oxide , a metal hydroxide , a metal the support in a closed vial, heated at 115º C . for 12 h to salt , a metal in elemental state , metalloid , or other suitable result in a homogenous coverage of the substrate by the material. The second electrode can be amorphous, polycrys Pb - ( 4 , 4 '- sulfonyldibenzoate ) MOF. talline, or a single crystal. The second electrode surface in [0055 ] FIGS . 8A and 8B represent photographs of MnO2 contact with the nanostructured separator can have a pol press -pellet as substrate (FIG . 8A ) and after coating by ished , rough , patterned , or functionalized surface, for Pb - ( 4 , 4 ' - sulfonyldibenzoate ) MOF ( FIG . 8B ) . FIGS . 9A and example , with surface - active molecules (SAMs ). The sec 9B represent SEM images of the surface of the MnO2 ond electrode can be metals , metal oxides, metal salts , metal support ( FIG . 9A ) and after growth of the Pb - ( 4 , 4 '- sulfo complexes , metalloid , metal or metalloid nanoparticles , nyldibenzoate ) MOF film on the support (FIG . 9B ). molten salts or gases . The second electrode can be electro [0056 ] Referring to FIG . 10 , the X - ray powder diffraction chemically complementary to the first electrode. For pattern of the Pb - ( 4 , 4 - sulfonyldibenzoate ) MOF film grown example , the first electrode can be a manganese oxide and on the MnO , substrate . FIG . 11 represents the X -ray single the second electrode can be lithium . crystal structure of the Pb - ( 4 , 4 ' - sulfonyldibenzoate ) MOF [0049 ] Each of the anode or cathode can be fabricated film grown on the MnO , substrate . The disordered parts of through a variety of techniques such as pressing from the framework , hydrogen atoms and disordered guest sol powder, chemical or electrical plating or deposition , spray vent molecules are omitted for clarity deposition , monolith , sputtering , or casting . The nanostruc tured separator, such as MOM , CP, or COF can be deposited Example 3 on one or more of the anode or cathode through solvother [0057 ] A solution of 2 , 5 - thiophenediboronicacid (70 mg) mal syntheses , spraying , dry grinding, vapor deposition , in tetrahydrofuran ( 2 mL ) and toluene ( 2 mL ) was prepared pellets pressing, or printing. The nanostructured separator and heated in closed vial at 105° C . for 24 h . The resulting can be deposited as phase pure material or as a mixture with finely crystalline solid was air dried and spread on the other ingredients in the form of composite material. Alter surface of gently pressed Mno , powder ( 180 mg) inside the natively , the nanostructured separator can include a MOM , pellet- press . The solids were pressed together at 15 ,000 lb CP or COF supported inside cavities or channels of a gel, a for 5 minutes to result in uniformly covered surface by the sol -gel , a porous inorganic support , or an organic polymer . COF . FIGS . 12A and 12B represent SEM images of the [ 00501 Examples of fabricating a nanostructured separator surface of the MnO , support after pellet - press of microc follow . In one example , a thin film of the nanostructured rystalline COF into a thin film (FIG . 12A ), and side view separator can be formed on a pressed pellet of manganese indicating average cross section of 80 microns ( FIG . 12B ) . oxide , which can be used as an electrode in battery or Referring to FIG . 13 , the X - ray powder diffraction pattern of electrochemical cell. the 2 , 5 - thiophenediboronicacid COF film grown on the Mno , substrate . Example 1 10058 ) A number of embodiments of the invention have [ 0051] 180 mg of finely grinded MnO , was pressed at been described . Nevertheless , it will be understood that 15 ,000 lb / inch to prepare the solid support . A mixture of various modifications may be made without departing from terephthalic acid ( 0 . 5 mmol, 83 mg) and Zn (NO3 ) 2 .6H20 ( 1 the spirit and scope of the invention . Other embodiments are mmol, 297 mg ) was prepared and dissolved in N , N - dieth within the scope of the following claims. ylformamide ( 5 mL ) and 1 mL of this mixture added to the 1 -24 . (canceled ) support in a closed vial, heated at 105° C . for 12 h to result 25 . A nanostructured electrode separator, consisting in a homogenous coverage of the substrate by the MOF . essentially of: [ 0052 ] FIGS . 3A and 3B represent photographs of MnO2 a covalent organic framework , wherein the nanostruc press -pellet as substrate ( FIG . 3A ) and after coating by tured electrode separator is a phase - pure material. Zn - terephthalate MOF (FIG . 3B ) . FIGS. 4A and 4B repre 26 . The separator of claim 25 , wherein the nanostructured sent SEM images of the surface of the MnO , support ( FIG . electrode separator serves as an electrical insulator between 4A ) and after growth of the MOF film on the support ( FIG . a first electrode and a second electrode . US 2018 /0190959 A1 Jul. 5 , 2018

27 . The separator of claim 25 , wherein the nanostructured rator consists essentially of a metal organic material or electrode separator is attached to a surface of a first electrode covalent organic framework ; and or a second electrode . contacting the nanostructured electrode separator with a 28 . The separator of claim 27 , wherein the first electrode second electrode . or second electrode is a manganese oxide electrode . 37 . The method of claim 36 , wherein the metal organic material is a metal -organic framework . 29 . The separator or claim 25 , wherein the nanostructured 38 . The method of claim 36 , wherein the metal organic electrode separator includes a 2, 5 -thiophenediboronic acid material is a metal -organic polyhedron . covalent organic framework . 39 . The method of claim 36 , wherein the metal organic 30 . The separator of claim 25 , wherein the nanostructured material is a coordination polymer. electrode separator has an average pore diameter of less than 40 . The method of claim 36 , wherein the nanostructured about 20 nm and greater than about 10 nm . separator includes a zinc or lead coordination compound. 31 . An electrochemical cell, comprising: 41. The method of claim 36 , wherein the nanostructured a first electrode; separator includes a zinc terephthalate metal- organic frame a nanostructured electrode separator attached to a surface work . of the first electrode and consisting essentially of a 42 . The method of claim 36 , wherein the nanostructured covalent organic framework ; and separator includes a lead - ( 4 , 4 ' - sulfonyldibenzoate ) metal a second electrode electrically insulated from the first organic framework . electrode . 43. The method of claim 36 , where in the nanostructured 32 . The cell of claim 31 , wherein the nanostructured separator includes a 2 , 5 - thiophenediboronic acid covalent electrode separator is a phase - pure material. organic framework . 33 . The cell of claim 31 , wherein the nanostructured 44 . The method of claim 36 , wherein the metal organic electrode separator includes a 2, 5 - thiophenediboronic acid material comprises Zn -MOF1 , Zn -MOF2 , Zn -MOF3 , Zn covalent organic framework . MOF4 , ZnMOF5 , Cu -MOF1 , Cu -MOF2 , Tb -MOF1 , Tb 34 . The cell of claim 31 , wherein one of the first electrode MOF2 , Cd -MOF1 , Cd -MOF2 , CdMOF3 , Co -MOF1 , Co and second electrode is a manganese oxide electrode . MOF2 , Zn -MOF6 , MOF -5 , Cu (4 , 4 '- bpy ) 1 .5NO3 ( H20 ) 1. 35 . The cell of claim 31, wherein the nanostructured 25 , [ Cu3 ( TMA ) 2 ] n , [Cu ( OH ) – ( C5H4NC2) , MOF - 38 , electrode separator has an average pore diameter less than Ag ( 4 , 4 '- bpy )NO3 , IRMOF - 1 , IRMOF - 2 and IRMOF - 3 , about 20 nm and greater than about 10 nm . IRMOF3 , IRMOF7 , or a supramolecular assembly compris 36 . A method of forming an electrochemical cell , com ing a 1 : 8 ratio of a supermolecular polyhedral building prising : blocks and a triangular molecular building blocks which depositing a nanostructured electrode separator on a first form a ( 3 ,24 )- connected rht net . electrode, wherein the nanostructured electrode sepa * * * * *