US009853270B2 (12 ) United States Patent ( 10) Patent No. : US 9 ,853 , 270 B2 Alkordi et al. (45 ) Date of Patent: Dec. 26 , 2017

(54 ) NANOSTRUCTURED METAL ORGANIC HO1M 4 / 24 ; H01M 4 /64 ; HO1M 2/ 1673 ; MATERIAL ELECTRODE SEPARATORS AND HO1M 2 /1653 ; HO1M 2 /145 ; HOLM METHODS THEREFOR 10 /04 ; Y10T 29 / 49115 See application file for complete search history. @(71 ) Applicant: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY , (56 ) References Cited Thuwal (SA ) U .S . PATENT DOCUMENTS @( 72 ) Inventors : Mohamed Helmi Alkordi, Thuwal 5 , 378 ,571 A 1/ 1995 Macholdt ( SA ) ; Mohamed Eddaoudi, Thuwal 6 , 624, 318 B1 . 9 /2003 Mueller et al. (SA ) 6, 893 , 564 B2 * 5/ 2005 Mueller et al. 210 /502 . 1 6 , 929 , 679 B2 8 / 2005 Mueller et al. ( 73 ) Assignee : King Abdullah University of Science 6 , 930 , 193 B2 8 / 2005 Yaghi et al. and Technology , Thuwal (SA ) 7 , 196 , 210 B2 3 /2007 Yaghi et al . 7 ,279 , 517 B2 10 / 2007 Mueller et al . ( * ) Notice : Subject to any disclaimer, the term of this 7 , 880 , 026 B2 2 / 2011 Ni et al. patent is extended or adjusted under 35 7 , 981 , 818 B2 7 / 2011 Justice U .S .C . 154 (b ) by 507 days . (Continued ) (21 ) Appl. No. : 13/ 861 , 775 OTHER PUBLICATIONS (22 ) Filed : Apr. 12 , 2013 International Search Report and Written Opinion for PCT/ US2013 / 036329 dated Jul. 25 , 2013 . (65 65 ) Prior Publication Data (Continued ) US 2013 /0280611 A1 Oct . 24 , 2013 Primary Examiner — Raymond Alejandro Related U . S . Application Data (74 ) Attorney , Agent, or Firm — Billion & Armitage ; (60 ) Provisional application No . 61/ 625 , 973, filed on Apr. Benjamin Armitage 18 , 2012 . ( 57 ) ABSTRACT (51 ) Int. Ci. Provided herein are nanostructured electrode separators HOIM 4 /50 ( 2010 . 01 ) comprising metal organic materials capable of attaching to HOLM 2 / 16 ( 2006 .01 ) one or more electrodes and electrically insulating at least HOIM 2 / 14 ( 2006 .01 ) one electrode while allowing migration of ionic charge (52 ) U . S . CI. carriers through the nanostructured electrode separator. CPC ...... HOIM 2 / 1673 (2013 . 01 ) ; HOIM 2 / 1653 Methods of using such electrode separators include posi (2013 .01 ) ; HOTM 4 / 50 (2013 .01 ) ; HOIM 2 / 145 tioning a nanostructured electrode separator between two (2013 .01 ) ; Y1OT 29/ 49115 (2015 .01 ) ( 58 ) Field of Classification Search electrodes of an electrochemical cell . CPC ...... HO1M 4 /50 ; HOTM 4 / 13 ; HO1M 4 / 14 ; 17 Claims, 13 Drawing Sheets US 9, 853 ,270 B2 Page 2

(56 ) References Cited U . S . PATENT DOCUMENTS 8 , 034 , 952 B2 10 / 2011 Eddaoudi et al. 8 , 119 , 295 B2 2 / 2012 Drew et al. 8 , 123 , 834 B2 2 / 2012 Masel et al. 8 ,680 , 231 B2 3 / 2014 Po et al . 2003 /0222023 Al 12 / 2003 Mueller et al. 2009 /0148760 AL 6 / 2009 Justice 2009 /0305040 A1 * 12 / 2009 Schubert et al . 428 / 402 2010 /0132547 A1 6 / 2010 Masel et al. 2010 /0266897 A1 * 10 / 2010 Lee ...... B82Y 10 /00 429 /219 2011/ 0139331 A1 6 / 2011 Arora et al. 2011 /0143173 AL 6 / 2011 Drew et al. 2011/ 0287316 A1 * 11 /2011 Lu . . .. B82Y 30 / 00 429 /215 2011/ 0319573 Al 12 /2011 Po et al. 2012 / 0003475 A1 * 1 / 2012 Benin et al . 428/ 402 2012 /0028086 A12 / 2012 Shi et al . 2012 /0077092 A1 * 3 / 2012 Lee et al . 429 / 307 2012 /0082884 A1 4 / 2012 Orilall et al. 2013/ 0115453 A1 * 5 /2013 Fan ...... HO5K 1 /0213 428 /372 OTHER PUBLICATIONS International Preliminary Report on Patentability for PCT/ US2013 / 036329 dated Oct. 21, 2014 . Kundu , et al ., “ Alkali earth metal (Ca , Sr, Ba ) based thermostable metal- organic frameworks (MOFs ) for proton conduction ” , Chem . Commun . , 2012 , 48 , pp . 4998 - 5000 ., Mar. 27 , 2012 . * cited by examiner U . S . Patent Dec . 26 , 2017 Sheet 1 of 13 US 9 ,853 , 270 B2

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VW comment mentionnel e tiserende diesentimes in del nostre te nen una entitate con la sensitie we ooreenkomsten . 5 10 15 20 25 30 35 40 45 29* Fig . 13 US 9 ,853 , 270 B2 NANOSTRUCTURED METAL ORGANIC Other aspects, embodiments , and features will be apparent MATERIAL ELECTRODE SEPARATORS AND from the following description , the drawings, and the METHODS THEREFOR claims. CLAIM OF PRIORITY DESCRIPTION OF DRAWINGS This application claims the benefit of prior U . S . Provi FIG . 1 is a diagram illustrating a portion of a battery or an sional Application No . 61 /625 ,973 , filed on Apr. 18 , 2012 , electrochemical cell. which is incorporated by reference in its entirety . FIGS. 2A , 2B and 2C are diagrams illustrating a lattice 10 structure that can be built to create a nanostructured sepa TECHNICAL FIELD rator. FIGS. 3A and 3B are photographs of electrode pellet and or use in nanostructured separator coated electrode pellet . This invention relates to an electrode separator for use in nanFIGS . 4A and 4B are micrograph images of electrode a battery or an electrochemical cell. 15 pellet and nanostructure separator coated electrode pellet. FIGS . 5A and 5B are micrograph images of electrode BACKGROUND pellet and nanostructured separator coated electrode pellet. FIG . 6 is a graph depicting the X -ray powder diffraction Batteries and electrochemical cells can be used as sources pattern of the nanostructured separator on the electrode of energy . Generally, batteries and electrochemical cells 20 pellet . include a positive electrode , a negative electrode , a separator FIG . 7 is a diagram depicting the X -ray crystal structure between the positive electrode and the negative electrode of the nanostructured separator on the electrode pellet . that prevents electrical contact between the two electrodes , FIGS . 8A and 8B are photographs of electrode pellet and and an electrolytic solution in contact with the electrodes nanostructured separator coated electrode pellet . and separator that permits ion migration . Electrons flow 25 FIGS . 9A and 9B are micrograph images of electrode from electrode to electrode via a conductor. The physical pellet and nanostructured separator coated electrode pellet. and chemical properties of the separator can affect the FIG . 10 is a graph depicting the X -ray powder diffraction performance properties of the battery or electrochemical pattern of the nanostructured separator on the electrode cell . pellet. 30 FIG . 11 is a diagram depicting the X - ray crystal structure SUMMARY of the nanostructured separator on the electrode pellet. FIGS . 12A and 12B are micrograph images of the surface A separator for a battery or electrochemical cell can be a of an electrode pellet after pellet -press of a nanostructured nanostructured separator. separator. In one aspect, an electrode material includes an electrode 35 FIG . 13 is a graph depicting the X - ray powder diffraction substrate and a nanostructured separator on a surface of the pattern of the nanostructured separator on the electrode electrode substrate . pellet. In another aspect , an electrochemical cell comprising an DETAILED DESCRIPTION electrode substrate , a nanostructured separator on a surface 40 of the electrode substrate and a second electrode in contact Referring to FIG . 1 , a battery or electrochemical cell can with the nanostructured separator. include a cathode , an anode and a separator between the In another aspect, a method of forming an electrode cathode and anode . The battery or electrochemical cell can material includes forming the nanostructured separator on a be contained within a suitable housing (not shown ). surface of the electrode support . 45 The battery and electrochemical cell include a primary In another aspect, a method of forming an electrochemical cell or a non - rechargeable battery or a secondary cell or cell includes forming the nanostructured separator on a rechargeable battery . Examples of a primary cell includes an surface of the electrode support and contacting the nano alkaline battery , aluminum battery , chromic acid cell , Clark structured separator with the second electrode . cell , Daniell cell, dry cell, Earth battery , Galvanic cell , In certain embodiments , the nanostructured separator can 50 Grove cell , Leclanché cell , lithium battery, lithium air bat include a metal - organic material. The metal - organic material tery ,mercury battery , molten salt battery , nickel oxyhydrox can be a metal -organic framework, a metal- organic polyhe - ide battery , oxyride battery, organic radical battery , paper dron , or a coordination polymer . battery , Pulvermacher ' s chain reserve battery, silver -oxide In other embodiments , the nanostructured separator can battery , solid - state battery , voltaic pile , penny battery , trough be a covalent - organic framework . 55 battery , water- activated battery, Weston cell, zinc - air battery , In certain embodiments , the nanostructured separator can zinc - carbon battery , or zinc chloride battery . Examples of a include a zinc or lead coordination compound , for example , secondary cell includes a flow battery, vanadium redox a zinc terephthalate metal- organic framework or a lead - (4 , battery , zinc -bromine flow battery , fuel cell , lead -acid bat 4 '- sulfonyldibenzoate ) metal- organic framework . In other tery, deep cycle battery , VRLA battery, AGM battery, gel embodiments , the nanostructured separator can include a 60 battery , lithium air battery , lithium - ion battery , Beltway 2 , 5 - thiophenediboronicacid covalent- organic framework . battery , lithium ion polymer battery , lithium iron phosphate In certain aspects , the electrode substrate can be a man - battery , lithium - sulfur battery, lithium - titanate battery , mol ganese oxide. ten salt battery, nickel- cadmium battery , nickel- cadmium Advantageously , the nanostructured separator can allow battery , vented cell type nickel hydrogen battery , nickel- iron for unprecedented control over ion conductivity and related 65 battery, nickel metal hydride battery , low self -discharge performance characteristics of batteries or electrochemical NiMH battery , nickel - zinc battery , organic radical battery , cells . polymer - based battery , polysulfide bromide battery, potas US 9 ,853 , 270 B2 sium - ion battery , rechargeable alkaline battery , silicon air be one - , two - or three - dimensional in structure and can battery , sodium - ion battery , sodium - sulfur battery , super consist of the various bonding motifs shown in FIGS. 2A , iron battery, zinc -bromine flow battery, or zinc matrix bat- 2B and 2C . tery . The polyvalent core can be carbon , silicon , a di- , tri -, or The primary function of an electrode separator is to sever 5 quadravalent organic moiety ( for example , carbon atom , as an electrical insulator between a positive electrode and a ethylene group , aryl group , and the like) , or a metal ions of negative electrode ( for example , a cathode and an anode , one or more main group element or transition metal includ respectively ) to prevent migration of electrons from elec ing ions of Li, Na, K , Cs, Mg, Ca, Sr, Ba , Sc, Y , Ti, Zr, Hf, V , Nb , Ta , Cr, Mo , W , Mn , Re, Fe , Ru, Os, Co , Rh , Ir , Ni, trode to electrode through the separator while allowing for 10 Pd , Pt, Cu , Ag , Au , Zn , Cd , Hg, Al, Ga, In , Ti, Si, Ge, Sn , migration of ionic charge carriers through the separator. The Pb , As , Sb , or Bi. migration of ionic charge completes the electrical circuit, The bridging group can be a polydentate group , for permitting passage of current from positive electrode to example , a C2 - 12 hydrocarbon chain optionally containing negative electrode in an electrochemical cell . at least one double bond, at least one triple bond, or at least A nanostructured material, such as a metaltal -organic mate - 15 one double bond and one triple bond and optionally inter al (MOM ), including a metal- organic framework (MOF ), a rupted by at least one 0 - , - N (Rc )- , or S , or C3 - 16 metal - organic polyhedron (MOP ) , or a coordination poly cyclic group, optionally aromatic and optionally heterocy mer ( CP ) , or a covalent- organic framework (COF ) can serve clic , the briding group being optionally substituted with as separator between electrodes in a battery or electrochemi- alkyl, alkenyl , alkynyl, alkoxy, hydroxyl, hydroxylalkyl , cal cell. 20 halo , haloalkyl , amino , carboxyl, amido , C1- 4 alkyl, C2 - 4 Metal -organic materials and coordination polymers refer a lkenyl, C2 -4 alkynyl , C1- 4 alkoxy, nitro , cyano , C3 -5 to a large family of solids characterized by the nature of cycloalkyl, 3 - 5 membered heterocycloalkyl, monocyclic coordination bonding between metal ions and organic link - aryl, 5 - 6 membered heteroaryl, C1 - 4 alkylcarbonyloxy , ers . The metal ions can include alkali metals , rare - earth C1 - 4 alkyloxycarbonyl, C1- 4 alkylcarbonyl, or formyl metals , transition metals , lanthanides, or post - transition met - 25 group , which is capable of bonding to 2 , 3 , 4 , 5 , or 6 , or als . Organic linkers can include any organic molecule more , of the polyvalent cores . Rc can be H or C1- 4 alkyl. capable of formation of coordination or ionic bond to metal The nanostructured separator can have a permanent ions. Organic linkers generally possess functional groups porosity, high surface area and appropriate chemical, ther mal and physical stability suitable of use in a battery or like carboxylic acids, amines, azoles, oxazoles, thiols , thi 30 electrochemical cell. In other embodiments , enclathrated or azoles and other heteroatom groups capable of bonding to a encapsulated guest molecules or ions can undergo guest metal ion . MOMs and CPs can exhibit various structures exchange with other molecular or ionic species in the ranging from discrete supermolecules (known also asmetal nanostructured separator to alter properties of the separator. organic polyhedra , MOPs ) to chains to layers and sheets to The surface area may be determined by using the BET 3D structures . MOMs and CPs can exhibit permanent poros - 35 method ( “ BET surface area ” ) . This refers to the Brunauer . ity as indicated by reversible gas sorption isotherms and /or Emmett and Teller (BET ) method for surface area determi reversible guest exchange behavior . nation , which utilizes the isothermal adsorption of nitrogen Covalent- organic frameworks refer to a large family of to measure total surface area of a material. Another method solids characterized by the nature of covalent bonding uses the Langmuir model. Thermal stability can be deter between organic monomers. The organic monomers can 40 mined using differential scanning calorimetry (DSC ) , dif contain metal ions include alkali metals , rare - earth metals , ferential thermal analysis (DTA ) , or thermogravimetric transition metals , lanthanides , or post -transition metals . analysis ( TGA ) . Porosity can be determined by porosimetry Organic monomers include any organic molecule capable of measurements . formation of covalent bonds to the same molecule to form The nanostructured separator can include designable and homo- polymer or other type of molecules to form hetero - 45 tunable pore sizes , pore distribution and pore shape . In polymer . Organic monomers generally possess functional another embodiment, the nanostructured separator can groups like carboxylic acids , amines, azoles , oxazoles , include designable and tunable pore functionality . For thiols , thiazoles, terminal alkynes , halogenated aromatics example , accessible voids inside the porous material can like iodo / bromo benzenes , boronic acids , aldehydes , amides , incorporate a variety of guest molecules , ions or gases of acyl halides or other functional groups . COFs can exhibit 50 desirable functionality for the nanostructured separator. In various structures ranging from discrete supermolecules to another embodiment, the nanostructured separator can chains to layers and sheets to 3D structures . COFs can include a designable and tunable composition of the organic ! exhibit permanent porosity as indicated by reversible gas inorganic parts of the separator, which can provide control sorption isotherms and / or reversible guest exchange behav - and enhancement in the design and selection of suitable ior. 55 material specific electrochemical systems. In another A nanostructured separator is a separator that has nano - embodiment, the nanostructured separator can have a neutral meter or sub - nanometer sized features that provide the or charged backbone ( cationic or anionic ) where in charged nanostructured separator with particular properties that can backbone the presence of encapsulated / enclathrated coun enhance the performance of a battery or electrochemical terions can provide control and enhancement in the design cell. In general , the nanostructured separator can be built 60 and selection of suitable material specific electrochemical from a framework ofmolecular structures depicted in FIGS. systems. The high crystallinity of the nanostructured sepa 2A , 2B and 2C , and combinations thereof . In these struc - rator enables accurate structural characterization and control tures , there is a polyvalent core , which can be a metal ion , of desirable properties including ion conductivity , ion atom , or other moiety capable of bonding with 2 , 3 , 4 , 5 , 7 , exchange , or void dimensions . 8 , 9 , 10 , 11 or 12 bridging groups to form a scaffold . The 65 For example , the nanostructured separator can have chan bonds can be covalent bonds , ionic bonds or dative bonds , nels / cages /windows within a relatively wide range in diam or combinations thereof. The scaffold or regions thereof can eter ( 0 . 5 - 5 nm ), or with a wide range of surface area ( few US 9 ,853 , 270 B2 m²/ g to several hundred m / g . The nanostructured separator assembly , an individual supermolecular polyhedral building can demonstrate good thermal stability (usually stable to block is linked to twenty - four different triangular building 200° C . ~ 300° C .) and chemical stability ( stable against blocks and an individual triangular building block is linked structural disintegration in neutral, acidic , or basic solutions. to three different supermolecular polyhedral building blocks The nanostructured separator should be thick enough to 5 with the linkages comprising covalent bonds , coordinate reduce or eliminate shorting between the positive electrode covalent bonds, noncovalent bonds , or a combination and the negative electrode by impedance or by preventing thereof. electrode dendrite formation . It is important that the nano - The MOFs described in U .S . Pat. No . 7 ,880 ,026 include structured separator also allow for facile ion migration IRMOF - 1 , IRMOF - 2 , IRMOF - 3 , Zn -MOF - 1 , Zn -MOF - 2 , between the positive electrode and the negative electrode . 10 Zn -MOF - 3 , Zn -MOF - 4 , Zn -MOF - 5 , Cu -MOF - 1 , Cu -MOF For example , the pore size in the nanostructured separator 2 , Tb -MOF - 1, Tb -MOF -2 , Cd -MOF - 1 , Cd -MOF -2 , Cd must be small enough to avoid formation of dendrites MOF - 3 , Co -MOF - 1 , Co -MOF - 2 , Zn -MOF -6 ,MOF - 5 , Cu ( 4 , through the membrane, but large enough to permit ion 4 '- bpy ) , 5NO3 (H2O ) 1. 25 , [Cuz ( TMA )2 ]n [Cu (OH ) — migration . The impedance of the nanostructured separator ( C HANCO2] n , MOF- 38 , Ag ( 4 , 4 ' -bpy )NO3 , and IRMOF - 7 , should be high enough to prevent electrical shorting between 15 among others . the positive electrode and the negative electrode while Referring again to FIG . 2 , the battery or electrochemical optimizing the efficiency of the battery or electrochemical cell can include three layers. The first layer can be a cell. For example , the average pore diameter of the nano substrate , and can be one electrode of the battery or the structured separator can be less than 20 nm , less than 10 nm , electrochemical cell . The nanostructured separator can be less than 5 nm , less than 1 nm , or greater than 0 . 5 nm . The 20 grown on a substrate , such as a first electrode of a battery or average thickness of the nanostructured separator can be less electrochemical cell . For example , the nanostructured sepa than 100 microns , less than 50 microns , less than 10 rator can be grown on an anode material. The substrate can microns , less than 1 micron , less than 500 nm , less than 200 be any solid support, for example , a porous , conductor, nm , less than 100 nm , less than 50 nm , less than 40 nm , less semi- conductor, magnetic , metallic , non -metallic , photoac than 30 nm , less than 20 nm , less than 10 nm , less than 5 nm , 25 tive , polymer, or heat responsive material. The substrate can less than 1 nm , or greater than 0 .5 nm . be conducting , semiconducting or insulating. The substrate Materials appropriate for use for the nanostructured sepa can be quartz , diamond , silica , alumina , a metal oxide , a rator can include a metal- organic material (MOM ) , includ - metal hydroxide , a metal in elemental state or other suitable ing a metal - organic framework (MOF ) , a metal- organic material. The substrate can be amorphous , polycrystalline , polyhedron MOP( ) , or a coordination polymer (CP ) , or a 30 or a single crystal. The substrate surface in contact with the covalent- organic framework (COF ) that is substantially inert n anostructured separator can have a polished , rough , pat to the electrolytic solution and capable of reducing or terned , or functionalized surface , for example , with surface eliminating electron transfer between electrodes . The nano - active molecules (SAMs ) . Each electrode , independently , structured separator can include wettable material coatings , can include a metal, metal oxide, metal salt, metal complex , polymers , gels, or fillers such as , for example , inorganic 35 metal nanoparticle , molten salt or gas . particles , biopolymers , polysaccharides , cellulose , dixtrans, The second layer can be a nanostructured separator. The cyclodextrins, silicates , or nanoparticles . nanostructured separator can be any MOF, MOP , CP , or COF Examples of possibly suitable nanostructured materials of desirable structure or functionality. For example, the include the metal- organic framework materials described , nanostructured separator can be non - porous, microporous, for example , in U . S . Pat. Nos . 8 , 123 , 834 , 8 ,034 , 952 , 7 , 880 , 40 or mesoporous . The nanostructured separator can form 026 , 7 ,279 ,517 , 6 , 929 ,679 , 6 ,893 ,564 , and 6 ,624 ,318 , each chains, sheets , or a 3D polymer or crystalline network . In of which is incorporated by reference in its entirety . The addition , the nanostructured separator can be neutral , design of pores in metal organic framework materials is anionic , or cationic and can include different counterions, described , for example , in U . S . Pat. Nos. 7 , 196 ,210 , and combining any one or more metal, transition metal, lan 6 , 930 , 193 , each of which is incorporated by reference in its 45 thanides , alkaloids , rare - earth metals , chalcogenides , and entirety . Other examples of possibly suitable nanostructured one or more organic molecule as linker. In certain embodi materials are described , for example, in T . Kundu , et al ., ments , the nanostructured separators can include accessible ChemComm 2012 , DOI: 10 . 1039 /c2cc31135f , which is voids inside the structure, which can be empty or occupied incorporated by reference in its entirety . by guest molecules that can be solvent, organic substance , The MOFs described in U . S . Pat . No. 8 , 123 ,834 include 50 counterions, ionic species, gases , or other species . The Zn -MOF1 , Zn -MOF2 , Zn -MOF3 , Zn -MOF4 , ZnMOF5 , Cu dimension and chemical composition of the nanostructured MOF1 , Cu -MOF2 , Tb -MOF1 , Tb -MOF2 , Cd -MOF1 , Cd separator along with the nature of optional enclosed guest MOF2 , CdMOF3 , Co -MOF1 , Co -MOF2 , Zn- MOF6 , MOF molecules or ions can provide control over ion migration 5 , Cu (4 , 4' - bpy ) 1 5NO3( H2O )1 . 25 , IRMOF2, [Cuz ( TMA )2 ]n characteristics through the separator, thus enabling enhance [Cu (OH ) (C3H _NCO2 ) , MOF - 38 , Ag (4 , 4' - bpy )NO3 , 55 ment and /or control of the battery or electrochemical cell IRMOF3 and IRMOF7, among others . performance . The MOFs described in U .S . Pat. No . 8 , 034 ,952 include The third layer can be the second electrode, or cathode , of supramolecular assemblies comprising a 1 : 8 ratio of a the battery or electrochemical cell. The second electrode can supermolecular polyhedral building block and a triangular be any solid support , for example , a porous , conductor, molecular building block , which form a (3 ,24 ) -connected rht 60 semi- conductor , magnetic , metallic , non -metallic , photoac net , among others . The supermolecular polyhedral building tive , polymer, or heat responsive material. The second block has points of extension corresponding to the vertices electrode can be conducting , semiconducting or insulating. of a rhombicuboctahedron ( and other regular polyhedra that The second electrode can be quartz , diamond , silica , alu have 24 vertices and the edge skeleton shared by small mina , a metal oxide , a metal hydroxide , a metal salt, a metal rhombihexahedron , small cubicuboctahedron , and rhombi - 65 in elemental state , metalloid , or other suitable material . The cuboctahedron ) for linking the supermolecular polyhedral second electrode can be amorphous, polycrystalline, or a building block to the triangular building blocks . In the single crystal. The second electrode surface in contact with US 9 ,853 , 270 B2 the nanostructured separator can have a polished , rough , represent SEM images of the surface of the MnO2 support patterned , or functionalized surface , for example , with sur (FIG . 9A ) and after growth of the Pb - ( 4 , 4 '- sulfonyldiben face - active molecules (SAMs ) . The second electrode can be zoate ) MOF film on the support (FIG . 9B ) . metals , metal oxides , metal salts , metal complexes , metal Referring to FIG . 10 , the X -ray powder diffraction pattern loid , metal or metalloid nanoparticles , molten salts or gases . 5 of the Pb -( 4 ,4 ' - sulfonyldibenzoate ) MOF film grown on the The second electrode can be electrochemically complemen - MnO2 substrate . FIG . 11 represents the X -ray single crystal tary to the first electrode . For example , the first electrode can structure of the Pb - ( 4 , 4 ' - sulfonyldibenzoate ) MOF film be a manganese oxide and the second electrode can be grown on the MnO , substrate . The disordered parts of the lithium . framework , hydrogen atoms and disordered guest solvent Each of the anode or cathode can be fabricated through a 10 molecules are omitted for clarity variety of techniques such as pressing from powder, chemi cal or electrical plating or deposition , spray deposition , Example 3 monolith , sputtering, or casting . The nanostructured sepa rator, such as MOM , CP, or COF can be deposited on one or A solution of 2 , 5 -thiophenediboronicacid ( 70 mg) in more of the anode or cathode through solvothermal synthe - 15 tetrahydrofuran ( 2 mL ) and toluene ( 2 mL) was prepared ses, spraying , dry grinding , vapor deposition , pellets press and heated in closed vial at 105° C . for 24 h . The resulting ing, or printing . The nanostructured separator can be depos finely crystalline solid was air dried and spread on the ited as phase pure material or as a mixture with other surface of gently pressed MnO2 powder ( 180 mg) inside the ingredients in the form of composite material. Alternatively, pellet- press . The solids were pressed together at 15, 000 lb the nanostructured separator can include a MOM , CP or 20 for 5 minutes to result in uniformly covered surface by the COF supported inside cavities or channels of a gel , a sol - gel, COF. FIGS . 12A and 12B represent SEM images of the a porous inorganic support , or an organic polymer . surface of the MnO2 support after pellet- press of microc Examples of fabricating a nanostructured separator fol rystalline COF into a thin film ( FIG . 12A ) , and side view low . In one example , a thin film of the nanostructured indicating average cross section of 80 microns ( FIG . 12B ) . separator can be formed on a pressed pellet of manganese 25 Referring to FIG . 13 , the X - ray powder diffraction pattern of oxide, which can be used as an electrode in battery or the 2 , 5 - thiophenediboronicacid COF film grown on the electrochemical cell. MnO2 substrate . A number of embodiments of the invention have been Example 1 described . Nevertheless , it will be understood that various 30 modifications may be made without departing from the spirit 180 mg of finely grinded MnO , was pressed at 15 . 000 and scope of the invention . Other embodiments are within lb / inch to prepare the solid support . A mixture of the scope of the following claims. terephthalic acid ( 0 . 5 mmol, 83 mg ) and Zn (NO3 ) 2 .6H20 ( 1 mmol, 297 mg ) was prepared and dissolved in N , N - dieth - What is claimed is : ylformamide ( 5 mL ) and 1 mL of this mixture added to the 35 1 . A nanostructured electrode separator, consisting essen support in a closed vial, heated at 105° C . for 12 h to result t ially of: in a homogenous coverage of the substrate by the MOF . a metal organic material, FIGS. 3A and 3B represent photographs of MnO2 press wherein the nanostructured electrode separator is attached pellet as substrate (FIG . 3A ) and after coating by Zn to a surface of a manganese oxide electrode, is a terephthalate MOF ( FIG . 3B ) . FIGS . 4A and 4B represent 40 phase -pure material, and serves as an electrical insula SEM images of the surface of the MnO support (FIG . 4A ) tor between the manganese oxide electrode and a and after growth of the MOF film on the support (FIG . 4B ) . second electrode and has an average pore diameter less FIGS . 5A and 5B represent SEM images showing the cross than 20 nm and greater than 10 nm . section of the MOF thin film on top of the MnO , substrate 2 . The electrode material of claim 1 , wherein the metal at two differentmagnifications . The average cross section of 45 organic material is a metal -organic framework . the MOF thin film was 60 microns . 3 . The electrode material of claim 1 , wherein the metal Referring to FIG . 6 , the X -ray powder diffraction pattern organic material is a metal- organic polyhedron . of the Zn - terephthalate MOF film grown on the MnO2 4 . The electrode material of claim 1 , wherein the metal substrate . FIG . 7 represents the X - ray single crystal structure organic material is a coordination polymer. of the Zn -terephthalate MOF film grown on the MnO , 50 5 . The electrode material of claim 1 , wherein the nano substrate . The disordered parts of the framework , hydrogen structured separator includes a zinc or lead coordination atoms and disordered guest solvent molecules are omitted compound . for clarity . 6 . The electrode material of claim 5 , wherein the nano structured separator includes a zinc terephthalate metal Example 2 55 organic framework . 7 . The electrode material of claim 5 , wherein the nano 180 mg of finely grinded MnO , was pressed at 15, 000 structured separator includes a lead -( 4 ,4 '- sulfonyldibenzo 1b / inch ? to prepare the solid support . A mixture of 4 ,4 ! ate ) metal- organic framework . sulfonyldibenzoic acid ( 0 . 1 mmol, 30 mg) and Pb ( NO3) 2 8 . The nanostructured electrode separator of claim 1 , ( 0 . 1 mmol, 33 mg) was prepared and dissolved in N , N - 60 wherein the metal organic material comprises Zn -MOF1 , dimethylformamide ( 2 mL ) and this mixture added to the Zn -MOF2 , Zn -MOF3 , Zn -MOF4 , ZnMOF5 , Cu -MOF1 , support in a closed vial , heated at 115º C . for 12 h to result Cu -MOF2 , Tb -MOF1 , Tb -MOF2 , Cd -MOF1 , Cd -MOF2 , in a homogenous coverage of the substrate by the Pb - ( 4 , 4 ' - CdMOF3 , Co -MOF1 , Co -MOF2 , Zn -MOF6 , MOF - 5 , Cu ( 4 , sulfonyldibenzoate ) MOF . 4 '- bpy ). 5N03 (H2O ) 1. 25 , [Cuz ( TMA )2 ]n [Cu (OH ) — FIGS. 8A and 8B represent photographs of MnO2 press - 65 (C3H _NCO2 ) , MOF - 38 , Ag (4 ,4 ' -bpy )NO3 , IRMOF - 1, pellet as substrate ( FIG . 8A ) and after coating by Pb -( 4 , 4 ' IRMOF- 2 and IRMOF- 3 , IRMOF3, IRMOF7 , or a supra sulfonyldibenzoate ) MOF (FIG . 8B ). FIGS. 9A and 9B molecular assembly comprising a 1 :8 ratio of a supermo US 9 ,853 , 270 B2 10 lecular polyhedral building blocks and a triangular molecu 14 . The electrochemical cell of claim 13, wherein the lar building blocks which form a ( 3 ,24 ) -connected rht net. nanostructured separator includes a zinc terephthalate metal 9 . An electrochemical cell comprising: organic framework . a first electrode ; 15 . The electrochemical cell of claim 13 , wherein the a nanostructured electrode separator consisting essentially 5 nanostructured separator includes a lead - ( 4 , 4 ' -sulfo of a metal organic material, wherein the nanostructured nyldibenzoate ) metal- organic framework . electrode separator is phase -pure and attached to a surface of the first electrode and has an average pore 16 . The electrochemical cell of claim 9 , wherein the metal diameter less than 20 nm and greater than 10 nm ; and organic material nanostructured separator comprises Zn a second electrode electrically insulated from the first 10 MOF1, Zn -MOF2 , Zn -MOF3 , Zn -MOF4 , ZnMOF5 , Cu electrode by the nanostructured electrode separator , MOF1, Cu- MOF2 , Tb -MOF1 , Tb -MOF2 , Cd -MOF1 , Cd wherein one of the first electrode and second electrode MOF2 , CdMOF3 , Co -MOF1 , Co -MOF2 , Zn -MOF6 , MOF is a manganese oxide electrode. 5 , Cu ( 4 ,4 '- bpy ) . 5NO2 (H2O ) 1 .25 , [Cuz ( TMA )2 ]n , [Cu 10 . The electrochemical cell of claim 9 , wherein the (OH ) – ( C2H4NCO2 ], MOF - 38 , Ag( 4 , 4 '- bpy )NO3 , IRMOF metal- organic material is a metal - organic framework . 15 1 , IRMOF- 2 and IRMOF - 3 , IRMOF3 , IRMOF7 , or a 11 . The electrochemical cell of claim 9 , wherein the supramolecular assembly comprising a 1 : 8 ratio of a super metal- organic material is a metal - organic polyhedron . molecular polyhedral building blocks and a triangular 12 . The electrochemical cell of claim 9, wherein the molecular building blocks which form a ( 3 ,24 ) -connected metal- organic material is a coordination polymer. rht net . 13. The electrochemical cell of claim 9, wherein the 20 17 . The electrochemical cell of claim 9 , wherein the nanostructured separator includes a zinc or lead coordination cu second electrode comprises lithium . compound . * * * * *