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US 20130280611A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2013/0280611 A1 ALKORDI et al. (43) Pub. Date: Oct. 24, 2013

(54) SEPARATOR Related US. Application Data (71) Applicant: King Abdullah University of Science (60) Provisional application No. 61/625,973, ?led on Apr. and Technology, (US) 18, 2012. Publication Classi?cation (72) Inventors: Mohamed Helmi ALKORDI, ThuWal (SA); Mohamed EDDAOUDI, ThuWal (51) Int. Cl. (SA) H01M 2/16 (2006.01) H01M 2/14 (2006.01) (73) Assignee: King Abdullah University of Science (52) US. Cl. and Technology, ThuWal (SA) CPC ...... H01M2/1673 (2013.01); H01M2/145 (2013.01) USPC ...... 429/224; 429/246; 29/623.5; 427/58 Appl. No.: 13/861,775 (21) (57) ABSTRACT A nanostructured separator for a battery or electrochemical (22) Filed: Apr. 12, 2013 cell can be a nanostructured separator.

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ELECTRODE SEPARATOR DESCRIPTION OF DRAWINGS [0015] FIG. 1 is a diagram illustrating a portion of a battery CLAIM OF PRIORITY or an . [0001] This application claims the bene?t of prior US. [0016] FIGS. 2A, 2B and 2C are diagrams illustrating a Provisional Application No. 61/625,973, ?led on Apr. 18, lattice structure that can be built to create a nanostructured 2012, which is incorporated by reference in its entirety. separator. [0017] FIGS. 3A and 3B are photographs of electrode pellet TECHNICAL FIELD and nanostructured separator coated electrode pellet. [0018] FIGS. 4A and 4B are micrograph images of elec [0002] This invention relates to an electrode separator for trode pellet and nanostructure separator coated electrode pel use in a battery or an electrochemical cell. let. [0019] FIGS. 5A and 5B are micrograph images of elec BACKGROUND trode pellet and nanostructured separator coated electrode [0003] Batteries and electrochemical cells can be used as pellet. sources of energy. Generally, batteries and electrochemical [0020] FIG. 6 is a graph depicting the X-ray powder dif cells include a positive electrode, a negative electrode, a sepa fraction pattern of the nanostructured separator on the elec rator between the positive electrode and the negative elec trode pellet. trode that prevents electrical contact between the two elec [0021] FIG. 7 is a diagram depicting the X-ray crystal struc trodes, and an electrolytic solution in contact with the ture of the nanostructured separator on the electrode pellet. and separator that permits migration. Electrons [0022] FIGS. 8A and 8B are photographs of electrode pellet ?ow from electrode to electrode via a conductor. The physical and nanostructured separator coated electrode pellet. and chemical properties of the separator can affect the per [0023] FIGS. 9A and 9B are micrograph images of elec formance properties of the battery or electrochemical cell. trode pellet and nanostructured separator coated electrode pellet. SUMMARY [0024] FIG. 10 is a graph depicting the X-ray powder dif fraction pattern of the nanostructured separator on the elec [0004] A separator for a battery or electrochemical cell can trode pellet. be a nanostructured separator. [0025] FIG. 11 is a diagram depicting the X-ray crystal [0005] In one aspect, an electrode material includes an elec structure of the nanostructured separator on the electrode trode substrate and a nanostructured separator on a surface of pellet. the electrode substrate. [0026] FIGS. 12A and 12B are micrograph images of the [0006] In another aspect, an electrochemical cell compris surface of an electrode pellet after pellet-press of a nanostruc ing an electrode substrate, a nanostructured separator on a tured separator. surface of the electrode substrate and a second electrode in [0027] FIG. 13 is a graph depicting the X-ray powder dif contact with the nanostructured separator. fraction pattern of the nanostructured separator on the elec [0007] In another aspect, a method of forming an electrode trode pellet. material includes forming the nanostructured separator on a surface of the electrode support. DETAILED DESCRIPTION [0008] In another aspect, a method of forming an electro chemical cell includes forming the nanostructured separator [0028] Referring to FIG. 1, a battery or electrochemical cell on a surface of the electrode support and contacting the nano can include a cathode, an anode and a separator between the structured separator with the second electrode. cathode and anode. The battery or electrochemical cell can be [0009] In certain embodiments, the nanostructured separa contained within a suitable housing (not shown). tor can include a metal-organic material. The metal-organic [0029] The battery and electrochemical cell include a pri material can be a metal-organic framework, a metal-organic mary cell or a non- or a secondary cell or polyhedron, or a coordination polymer. rechargeable battery. Examples of a includes an [0010] In other embodiments, the nanostructured separator , aluminum battery, chromic acid cell, Clark can be a covalent-organic framework. cell, , , Earth battery, , , , , lithium air battery, mer [0011] In certain embodiments, the nanostructured separa cury battery, molten salt battery, nickel oxyhydroxide battery, tor can include a Zinc or lead coordination compound, for oxyride battery, organic radical battery, paper battery, Pulver example, a Zinc terephthalate metal-organic framework or a macher’s chain reserve battery, silver-oxide battery, solid lead-(4,4'-sulfonyldibenZoate) metal-organic framework. In state battery, , penny battery, trough battery, water other embodiments, the nanostructured separator can include activated battery, Weston cell, Zinc-air battery, Zinc-carbon a 2,5-thiophenediboronicacid covalent-organic framework. battery, or Zinc chloride battery. Examples of a secondary cell [0012] In certain aspects, the electrode substrate can be a includes a ?ow battery, , Zinc-bro manganese oxide. mine ?ow battery, , lead-acid battery, deep cycle [0013] Advantageously, the nanostructured separator can battery, VRLA battery, AGM battery, gel battery, lithium air allow for unprecedented control over ion conductivity and battery, lithium-ion battery, Beltway battery, lithium ion related performance characteristics of batteries or electro polymer battery, lithium iron phosphate battery, lithium-sul chemical cells. fur battery, lithium-titanate battery, molten salt battery, [0014] Other aspects, embodiments, and features will be nickel- battery, nickel-cadmium battery, vented cell apparent from the following description, the drawings, and type nickel hydrogen battery, nickel-iron battery, nickel metal the claims. hydride battery, low self-discharge NiMH battery, nickel-Zinc US 2013/0280611A1 Oct. 24, 2013

battery, organic radical battery, polymer-based battery, The scaffold or regions thereof can be one-, tWo- or three polysul?de bromide battery, potas sium-ion battery, recharge dimensional in structure and can consist of the various bond able alkaline battery, silicon air battery, sodium-ion battery, ing motifs shoWn in FIGS. 2A, 2B and 2C. sodium-sulfur battery, super iron battery, zinc-bromine ?oW [0035] The polyvalent core canbe carbon, silicon, a di-, tri-, battery, or zinc matrix battery. or quadravalent organic moiety (for example, carbon atom, [0030] The primary function of an electrode separator is to ethylene group, aryl group, and the like), or a metal of sever as an electrical insulator betWeen a positive electrode one or more main group element or transition metal including and a negative electrode (for example, a cathode and an ions ofLi, Na, K, Cs, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, anode, respectively) to prevent migration of electrons from Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, electrode to electrode through the separator While alloWing Ag, Au, Zn, Cd, Hg, Al, Ga, In, Ti, Si, Ge, Sn, Pb, As, Sb, or for migration of ionic charge carriers through the separator. Bi. The migration of ionic charge completes the electrical circuit, permitting passage of current from positive electrode to nega [0036] The bridging group can be a polydentate group, for tive electrode in an electrochemical cell. example, a C2-l2 hydrocarbon chain optionally containing at [0031] A nanostructured material, such as a metal-organic least one double bond, at least one triple bond, or at least one material (MOM), including a metal-organic framework double bond and one triple bond and optionally interrupted by (MOF), a metal-organic polyhedron (MOP), or a coordina at least one ‘Of, iN(Rc)-, or S, or C3-l6 cyclic group, tion polymer (CP), or a covalent-organic framework (COF) optionally aromatic and optionally heterocyclic, the briding can serve as separator betWeen electrodes in a battery or group being optionally substituted With alkyl, alkenyl, alky electrochemical cell. nyl, alkoxy, hydroxyl, hydroxylalkyl, halo, haloalkyl, amino, carboxyl, amido, Cl -4 alkyl, C2-4 alkenyl, C2-4 alkynyl, [0032] Metal-organic materials and coordination polymers Cl -4 alkoxy, nitro, cyano, C3-5 cycloalkyl, 3-5 membered refer to a large family of solids characterized by the nature of heterocycloalkyl, monocyclic aryl, 5-6 membered heteroaryl, coordination bonding betWeen metal ions and organic linkers. Cl-4 alkylcarbonyloxy, Cl-4 alkyloxycarbonyl, Cl-4 alkyl The metal ions can include alkali metals, rare-earth metals, carbonyl, or formyl group, Which is capable of bonding to 2, transition metals, lanthanides, or post-transition metals. 3, 4, 5, or 6, or more, ofthe polyvalent cores. Rc can be H or Organic linkers can include any organic molecule capable of C1-4 alkyl. formation of coordination or ionic bond to metal ions. Organic linkers generally possess functional groups like car [0037] The nano structured separator can have a permanent boxylic acids, amines, azoles, oxazoles, thiols, thiazoles and porosity, high surface area and appropriate chemical, thermal other heteroatom groups capable of bonding to a metal ion. and physical stability suitable of use in a battery or electro MOMs and CPs can exhibit various structures ranging from chemical cell. In other embodiments, enclathrated or encap discrete supermolecules (knoWn also as metal-organic poly sulated guest molecules or ions can undergo guest exchange hedra, MOPs) to chains to layers and sheets to 3D structures. With other molecular or ionic species in the nanostructured MOMs and CPs can exhibit permanent porosity as indicated separator to alter properties of the separator. The surface area by reversible gas sorption isotherms and/or reversible guest may be determined by using the BET method (“BET surface exchange behavior. area”). This refers to the Brunauer, Emmett and Teller (BET) [0033] Covalent-organic frameWorks refer to a large family method for surface area determination, Which utilizes the of solids characterized by the nature of covalent bonding isothermal adsorption of nitrogen to measure total surface betWeen organic monomers. The organic monomers can con area of a material. Another method uses the Langmuir model. tain metal ions include alkali metals, rare-earth metals, tran Thermal stability can be determined using differential scan sition metals, lanthanides, or post-transition metals. Organic ning calorimetry (DSC), differential thermal analysis (DTA), monomers include any organic molecule capable of forma or thermogravimetric analysis (TGA). Porosity can be deter tion of covalent bonds to the same molecule to form homo mined by porosimitry measurements. polymer or other type of molecules to form hetero-polymer. [0038] The nanostructured separator can include design Organic monomers generally possess functional groups like able and tunable pore sizes, pore distribution and pore shape. carboxylic acids, amines, azoles, oxazoles, thiols, thiazoles, In another embodiment, the nanostructured separator can terminal alkynes, halogenated aromatics like iodo/bromo include designable and tunable pore functionality. For benzenes, boronic acids, aldehydes, amides, acyl halides or example, accessible voids inside the porous material can other functional groups. COFs can exhibit various structures incorporate a variety of guest molecules, ions or gases of ranging from discrete supermolecules to chains to layers and desirable functionality for the nanostructured separator. In sheets to 3D structures. COFs can exhibit permanent porosity another embodiment, the nanostructured separator can as indicated by reversible gas sorption isotherms and/or include a designable and tunable composition of the organic/ reversible guest exchange behavior. inorganic parts of the separator, Which can provide control [0034] A nanostructured separator is a separator that has and enhancement in the design and selection of suitable mate nanometer or sub-nanometer sized features that provide the rial speci?c electrochemical systems. In another embodi nanostructured separator With particular properties that can ment, the nanostructured separator can have a neutral or enhance the performance of a battery or electrochemical cell. charged backbone (cationic or anionic) Where in charged In general, the nanostructured separator can be built from a backbone the presence of encapsulated/enclathrated counte frameWork of molecular structures depicted in FIGS. 2A, 2B rions can provide control and enhancement in the design and and 2C, and combinations thereof. In these structures, there is selection of suitable material speci?c electrochemical sys a polyvalent core, Which can be a metal ion, atom, or other tems. The high crystallinity of the nanostructured separator moiety capable ofbonding With 2,3,4, 5,7,8, 9, 10, 11 or 12 enables accurate structural characterization and control of bridging groups to form a scaffold. The bonds can be covalent desirable properties including ion conductivity, ion bonds, ionic bonds or dative bonds, or combinations thereof. exchange, or void dimensions. US 2013/02806111411 Oct. 24, 2013

[0039] For example, the nanostructured separator can have hydroxide, a metal in elemental state or other suitable mate channels/cages/WindoWs Within a relatively Wide range in rial. The substrate can be amorphous, polycrystalline, or a diameter (0.5~5 nm), or With a Wide range of surface area single crystal. The substrate surface in contact With the nano (feW m2/ g to several hundred m2/ g. The nano structured sepa structured separator can have a polished, rough, patterned, or rator can demonstrate goodthermal stability (usually stable to functionaliZed surface, for example, With surface-active mol 2000 C.~300o C.) and chemical stability (stable against struc ecules (SAMs). Each electrode, independently, can include a tural disintegration in neutral, acidic,or basic solutions. metal, metal oxide, metal salt, metal complex, metal nano [0040] The nanostructured separator should be thick particle, molten salt or gas. enough to reduce or eliminate shorting betWeen the positive electrode and the negative electrode by impedance or by [0044] The second layer can be a nanostructured separator. preventing electrode dendrite formation. It is important that The nanostructured separator can be any MOF, MOP, CP, or the nanostructured separator also alloW for facile ion migra COF of desirable structure or functionality. For example, the tion betWeen the positive electrode and the negative elec nanostructured separator can be non-porous, microporous, or trode. For example, the pore siZe in the nanostructured sepa mesoporous. The nanostructured separator can form chains, rator must be small enough to avoid formation of dendrites sheets, or a 3D polymer or crystalline netWork. In addition, through the membrane, but large enough to permit ion migra the nanostructured separator can be neutral, anionic, or cat tion. The impedance of the nanostructured separator should ionic and can include different counterions, combining any be high enough to prevent electrical shorting betWeen the one or more metal, transition metal, lanthanides, alkaloids, positive electrode and the negative electrode While optimiZ rare-earth metals, chalcogenides, and one or more organic ing the ef?ciency of the battery or electrochemical cell. For molecule as linker. In certain embodiments, the nanostruc example, the average pore diameter of the nanostructured tured separators can include accessible voids inside the struc separator can be less than 20 nm, less than 10 nm, less than 5 ture, Which can be empty or occupied by guest molecules that nm, less than 1 nm, or greater than 0.5 nm. The average can be solvent, organic substance, counterions, ionic species, thickness of the nanostructured separator can be less than 100 gases, or other species. The dimension and chemical compo microns, less than 50 microns, less than 10 microns, less than sition of the nanostructured separator along With the nature of 1 micron, less than 500 nm, less than 200 nm, less than 100 optional enclosed guest molecules orions can provide control nm, less than 50 nm, less than 40 nm, less than 30 nm, less over ion migration characteristics through the separator, thus than 20 nm, less than 10 nm, less than 5 nm, less than 1 nm, or enabling enhancement and/or control of the battery orelec greater than 0.5 nm. trochemical cell performance. [0041] Materials appropriate for use for the nanostructured [0045] The third layer can be the second electrode, or cath separator can include a metal-organic material (MOM), ode, of the battery or electrochemical cell. The second elec including a metal-organic framework (MOF), a metal-or trode can be any solid support, for example, a porous, con ganic polyhedron (MOP), or a coordination polymer (CP), or ductor, semi-conductor, magnetic, metallic, non-metallic, a covalent-organic frameWork (COF) that is substantially photoactive, polymer, or heat responsive material. The sec inert to the electrolytic solution and capable of reducing or ond electrode can be conducting, semiconducting or insulat eliminating electron transfer betWeen electrodes. The nano ing. The second electrode can be quartz, diamond, silica, structured separator can include Wettable material coatings, alumina, a metal oxide, a metal hydroxide, a metal salt, a polymers, gels, or ?llers such as, for example, inorganic par metal in elemental state, metalloid, or other suitable material. ticles, biopolymers, polysaccharides, cellulose, dixtrans, The second electrode can be amorphous, polycrystalline, or a cyclodextrins, silicates, or nanoparticles. single crystal. The second electrode surface in contact With [0042] Examples of possibly suitable nanostructured mate the nanostructured separator can have a polished, rough, pat rials include the metal-organic frameWork materials terned, or functionaliZed surface, for example, With surface described, for example, in Us. Pat. Nos. 8,123,834, 8,034, active molecules (SAMs). The second electrode can be met 952, 7,880,026, 7,279,517, 6,929,679, 6,893,564, and 6,624, als, metal oxides, metal salts, metal complexes, metalloid, 318, each of Which is incorporated by reference in its entirety. metal or metalloid nanoparticles, molten salts or gases. The The design of pores in metal organic frameWork materials is second electrode can be electrochemically complementary to described, for example, in Us. Pat. Nos. 7,196,210, and the ?rst electrode. For example, the ?rst electrode can be a 6,930,193, each of Which is incorporated by reference in its manganese oxide and the second electrode can be lithium. entirety. Other examples of possibly suitable nanostructured materials are described, for example, in T. Kundu, et al., [0046] Each of the anode or cathode can be fabricated ChemComm 2012, DOI: 10.1039/c2cc31135f, Which is through a variety of techniques such as pressing from poWder, incorporated by reference in its entirety. chemical or electrical plating or deposition, spray deposition, [0043] Referring again to FIG. 2, the battery or electro monolith, sputtering, or casting. The nanostructured separa tor, such as MOM, CP, or COF can be deposited on one or chemical cell can include three layers. The ?rst layer can be a more of the anode or cathode through solvothermal synthe substrate, and can be one electrode of the battery or the ses, spraying, dry grinding, vapor deposition, pellets press electrochemical cell. The nanostructured separator can be ing, or printing. The nanostructured separator can be depos groWn on a substrate, such as a ?rst electrode of a battery or ited as phase pure material or as a mixture With other electrochemical cell. For example, the nanostructured sepa ingredients in the form of composite material. Alternatively, rator can be groWn on an anode material. The substrate can be the nanostructured separator can include a MOM, CP or COF any solid support, for example, a porous, conductor, semi supported inside cavities or channels of a gel, a sol-gel, a conductor, magnetic, metallic, non-metallic, photoactive, porous inorganic support, or an organic polymer. polymer, or heat responsive material. The substrate can be conducting, semiconducting or insulating. The substrate can [0047] Examples of fabricating a nanostructured separator be quartz, diamond, silica, alumina, a metal oxide, a metal folloW. In one example, a thin ?lm of the nanostructured US 2013/0280611A1 Oct. 24, 2013

separator can be formed on a pressed pellet of manganese cross section of 80 microns (FIG. 12B). Referring to FIG. 13, oxide, which can be used as an electrode in battery or elec the X-ray powder diffraction pattern of the 2,5-thiophenedi trochemical cell. boronicacid COF ?lm grown on the MnO2 substrate. [0055] A number of embodiments of the invention have EXAMPLE 1 been described. Nevertheless, it will be understood that vari [0048] 180 mg of ?nely grinded MnO2 was pressed at ous modi?cations may be made without departing from the 15,000 lb/inch to prepare the solid support. A mixture of spirit and scope of the invention. Other embodiments are terephthalic acid (0.5 mmol, 83 mg) and Zn(NO3)2~6H2O (1 within the scope of the following claims. mmol, 297 mg) was prepared and dissolved in N,N'-diethyl What is claimed is: formamide (5 mL) and 1 mL of this mixture added to the 1. An electrode material comprising an electrode substrate support in a closed vial, heated at 1050 C. for 12 h to result in and a nanostructured separator on a surface of the electrode a homogenous coverage of the substrate by the MOF. substrate. [0049] FIGS. 3A and 3B represent photographs of MnO2 2. The electrode material of claim 1, wherein the nano press-pellet as substrate (FIG. 3A) and after coating by Zn structured separator includes a metal-organic material. terephthalate MOF (FIG. 3B). FIGS. 4A and 4B represent 3. The electrode material of claim 2, wherein the metal SEM images of the surface of the MnO2 support (FIG. 4A) organic material is a metal-organic framework. and after growth of the MOF ?lm on the support (FIG. 4B). 4. The electrode material of claim 2, wherein the metal FIGS. 5A and 5B represent SEM images showing the cross organic material is a metal-organic polyhedron. section of the MOF thin ?lm on top of the MnO2 substrate at 5. The electrode material of claim 2, wherein the metal two different magni?cations. The average cross section of the organic material is a coordination polymer. MOF thin ?lm was 60 microns. 6. The electrode material of claim 2, wherein the nano [0050] Referring to FIG. 6, the X-ray powder diffraction structured separator is a covalent-organic framework. 7. The electrode material of claim 1, wherein the nano pattern of the Zn-terephthalate MOF ?lm grown on the MnO2 substrate. FIG. 7 represents the X-ray single crystal structure structured separator includes a Zinc or lead coordination com of the Zn-terephthalate MOF ?lm grown on the MnO2 sub pound. strate. The disordered parts of the framework, hydrogen 8. The electrode material of claim 7, wherein the nano atoms and disordered guest solvent molecules are omitted for structured separator includes a Zinc terephthalate metal-or clarity. ganic framework. 9. The electrode material of claim 7, wherein the nano EXAMPLE 2 structured separator includes a lead-(4,4'-sulfonyldiben Zoate) metal-organic framework. [0051] 180 mg of ?nely grinded MnO2 was pressed at 10. The electrode material of claim 2, wherein the nano 15,000 lb/inch to prepare the solid support. A mixture of structured separator includes a 2,5-thiophenediboronicacid 4,4'-sulfonyldibenZoic acid (0.1 mmol, 30 mg) and Pb(NO3)2 covalent-organic framework. (0.1 mmol, 33 mg) was prepared and dissolved in N,N' 1 1. The electrode material of claim 1, wherein the electrode dimethylformamide (2 mL) and this mixture added to the substrate is a manganese oxide. support in a closed vial, heated at 1 150 C. for 12 h to result in 12. An electrochemical cell comprising an electrode sub a homogenous coverage of the substrate by the Pb-(4,4' strate, a nano structured separator on a surface of the electrode sulfonyldibenZoate) MOF. substrate and a second electrode in contact with the nano [0052] FIGS. 8A and 8B represent photographs of MnO2 structured separator. press-pellet as substrate (FIG. 8A) and after coating by Pb 13. The electrochemical cell of claim 12, wherein the nano (4,4'-sulfonyldibenZoate) MOF (FIG. 8). FIGS. 9A and 9B structured separator includes a metal-organic material. represent SEM images of the surface of the MnO2 support 14. The electrochemical cell of claim 13, wherein the (FIG. 9A) and after growth of the Pb-(4,4'-sulfonyldiben metal-organic material is a metal-organic framework. Zoate) MOF ?lm on the support (FIG. 9B). 15. The electrochemical cell of claim 13, wherein the [0053] Referring to FIG. 10, the X-ray powder diffraction metal-organic material is a metal-organic polyhedron. pattern of the Pb-(4,4'-sulfonyldibenZoate) MOF ?lm grown 16. The electrochemical cell of claim 13, wherein the on the MnO2 substrate. FIG. 11 represents the X-ray single metal-organic material is a coordination polymer. crystal structure of the Pb-(4,4'-sulfonyldibenZoate) MOF 17. The electrochemical cell of claim 12, wherein the nano ?lm grown on the MnO2 substrate. The disordered parts of the structured separator is a covalent-organic framework. framework, hydrogen atoms and disordered guest solvent 18. The electrochemical cell of claim 12, wherein the nano molecules are omitted for clarity structured separator includes a Zinc or lead coordination com pound. EXAMPLE 3 19. The electrochemical cell of claim 18, wherein the nano [0054] A solution of 2,5-thiophenediboronicacid (70 mg) structured separator includes a Zinc terephthalate metal-or in tetrahydrofuran (2 mL) and toluene (2 mL) was prepared ganic framework. and heated in closed vial at 1050 C. for 24 h. The resulting 20. The electrochemical cell of claim 18, wherein the nano ?nely crystalline solid was air dried and spread on the surface structured separator includes a lead-(4,4'-sulfonyldiben of gently pressed MnO2 powder (180 mg) inside the pellet Zoate) metal-organic framework. press. The solids were pressed together at 15,000 lb for 5 21. The electrochemical cell of claim 12, wherein the nano minutes to result in uniformly covered surface by the COP. structured separator includes a 2,5-thiophenediboronicacid FIGS. 12A and 12B represent SEM images of the surface of covalent-organic framework. the MnO2 support after pellet-press of microcrystalline COF 22. The electrochemical cell of claim 1, wherein the elec into a thin ?lm (FIG. 12A), and side view indicating average trode substrate is a manganese oxide. US 2013/0280611A1 Oct. 24, 2013

23. A method of forming an electrode material of claim 1, comprising forming the nano structured separator on a surface of the electrode support. 24. A method of forming an electrochemical cell of claim 12, comprising forming the nanostructured separator on a surface of the electrode support and contacting the nanostruc tured separator With the second electrode.

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