# US 10,770,721 B2 · Lithium metal secondary battery containing anode-protecting polymer layer and manufacturing method

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- Number: US 10,770,721 B2
- Document ID: US10770721B2
- Status: Granted
- Kind: B2
- Application number: 15/483,348
- Filed: 2017-04-10
- Published: 2018-10-11
- Granted: 2020-09-08
- Earliest claimed: 2017-04-10
- Assignees: Global Graphene Group, Inc.
- Applicants: Nanotek Instruments, Inc.
- Inventors: Aruna Zhamu; Bor Z. Jang
- Web page: https://patentgrep.com/patent/US10770721B2

## CPC

- H01M 4/366: {as layered products}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/405: {Alloys based on lithium}
- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 10/052: Li-accumulators
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- H01M 4/625: {Carbon or graphite}
- H01M 12/08: composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- H01M 50/46: Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M 2300/0082: Organic polymers
- H01M 2300/0085: Immobilising or gelification of electrolyte
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided is lithium secondary battery comprising a cathode, an anode, and an electrolyte or separator-electrolyte assembly disposed between the cathode and the anode, wherein the anode comprises: (a) a foil or coating of lithium or lithium alloy as an anode active material; and (b) a thin layer of a high-elasticity polymer having a recoverable tensile strain no less than 5%, a lithium ion conductivity no less than 10−6 S/cm at room temperature, and a thickness from 1 nm to 10 μm, wherein the high-elasticity polymer contains an ultrahigh molecular weight polymer having a molecular weight from 0.5×106 to 9×106 g/mole and is disposed between the lithium or lithium alloy and the electrolyte or separator-electrolyte assembly.

## Claims

### Claim 1

A lithium secondary battery comprising a cathode, an anode, and an electrolyte or separator-electrolyte assembly disposed between said cathode and said anode, wherein said anode comprises:
a) a foil or coating of lithium or lithium alloy as an anode active material; and
b) a layer of polymer having a recoverable tensile strain no less than 5%, a lithium ion conductivity no less than 10−6 S/cm at room temperature, and a thickness from 1 nm to 10 μm, wherein said polymer contains an ultrahigh molecular weight polymer having a molecular weight from 0.5×106 to 9×106 grams/mole and is disposed between said lithium or lithium alloy and said electrolyte or separator-electrolyte assembly, wherein said ultrahigh molecular weight polymer is a thermoplastic and is selected from polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyethylene glycol, polyvinyl alcohol, polyacrylamide, poly(methyl methacrylate), poly(methyl ether acrylate), a copolymer thereof, a sulfonated derivative thereof, a chemical derivative thereof, or a combination thereof.

### Claim 2 (depends on 1)

The lithium secondary battery of claim 1, wherein said molecular weight is from 0.5×106 to less than 5×106 grams/mole.

### Claim 3 (depends on 1)

The lithium secondary battery of claim 1, wherein said molecular weight is from 1×106 to less than 3×106 grams/mole.

### Claim 4 (depends on 1)

The lithium secondary battery of claim 1, wherein said thickness is from 1 nm to 1 μm.

### Claim 5 (depends on 1)

The lithium secondary battery of claim 1, wherein said thickness is less than 100 nm.

### Claim 6 (depends on 1)

The lithium secondary battery of claim 1, wherein said thickness is less than 10 nm.

### Claim 7 (depends on 1)

The lithium secondary battery of claim 1, wherein said lithium ion conductivity is from 10−4 S/cm to 10−2 S/cm.

### Claim 8 (depends on 1)

The lithium secondary battery of claim 1, wherein said polymer is a neat polymer having no additive or filler dispersed therein.

### Claim 9 (depends on 1)

The lithium secondary battery of claim 1, wherein said ultra-high molecular weight polymer contains from 0.1% to 50% by weight of a lithium ion-conducting additive dispersed therein, or contains therein from 0.1% by weight to 10% by weight of a reinforcement nano filament selected from carbon nanotube, carbon nano-fiber, graphene, and combinations thereof.

### Claim 10 (depends on 1)

The lithium secondary battery of claim 1, wherein said ultra-high molecular weight polymer is mixed with a lithium ion-conducting additive to form a composite wherein said lithium ion-conducting additive is dispersed in said high-elasticity polymer and is selected from Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, and combinations thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1 and 1≤y≤4.

### Claim 11 (depends on 1)

The lithium secondary battery of claim 1, wherein said ultra-high molecular weight polymer is mixed with an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof to form a blend, co-polymer, or semi-interpenetrating network.

### Claim 12 (depends on 1)

The lithium secondary battery of claim 1, wherein the ultra-high molecular weight polymer forms a mixture, blend, copolymer, or semi-interpenetrating network with a lithium ion-conducting polymer and is selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, and combinations thereof.

### Claim 13 (depends on 1)

The lithium secondary battery of claim 1, which is a lithium-sulfur battery, wherein said cathode comprises sulfur, a sulfur-containing molecule, a sulfur-containing compound, a metal sulfide, a sulfur-carbon polymer, a lithium polysulfide, a sulfur/carbon hybrid or composite, a sulfur/graphite hybrid or composite, a sulfur/graphene hybrid or composite, a sulfur-polymer compound, and combinations thereof.

### Claim 14 (depends on 1)

The lithium battery of claim 1, which is a lithium metal battery, lithium-sulfur battery, lithium-selenium battery, or lithium-air battery.

### Claim 15 (depends on 1)

The lithium secondary battery of claim 1, wherein said ultrahigh molecular weight polymer contains a lithium salt and/or a liquid solvent dispersed between chains of said ultrahigh molecular weight polymer.

### Claim 16 (depends on 15)

The lithium secondary battery of claim 15, wherein said liquid solvent is selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, an ionic liquid solvent, and combinations thereof.

### Claim 17 (depends on 15)

The lithium secondary battery of claim 15, wherein said lithium salt is selected from lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphates, lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, and combinations thereof.

### Claim 18 (depends on 1)

The lithium secondary battery of claim 1, wherein said ultrahigh molecular weight polymer contains an electrically conductive material dispersed therein.

### Claim 19 (depends on 18)

The lithium secondary battery of claim 18, wherein said electrically conducting material is selected from an electron-conducting polymer, a metal particle or wire, a graphene sheet, a carbon fiber, a graphite fiber, a carbon nano-fiber, a graphite nano-fiber, a carbon nanotube, a graphite particle, an expanded graphite flake, an acetylene black particle, and combinations thereof.

### Claim 20 (depends on 19)

The lithium secondary battery of claim 19, wherein said electrically conducting material has a thickness or diameter less than 100 nm.

### Claim 21 (depends on 1)

The lithium secondary battery of claim 1, wherein said polymer further comprises a conductive additive is-selected from a graphite, graphene, or carbon, and combinations thereof.

### Claim 22 (depends on 21)

The lithium secondary battery of claim 21, wherein said graphite or carbon is selected from polymeric carbon, amorphous carbon, chemical vapor deposition carbon, coal tar pitch, petroleum pitch, meso-phase pitch, carbon black, coke, acetylene black, activated carbon, fine expanded graphite particle with a dimension smaller than 100 nm, artificial graphite particle, natural graphite particle, and combinations thereof.

### Claim 23 (depends on 1)

The lithium secondary battery of claim 1, further including a cathode active material that is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn, all having a thickness or diameter from 0.5 nm to 100 nm.

### Claim 24 (depends on 23)

The lithium secondary battery of claim 23, wherein said nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn is coated with or embraced by a conductive protective coating selected from a carbon material, graphene, electronically conductive polymer, conductive metal oxide, or conductive metal coating.

### Claim 25 (depends on 1)

The lithium secondary battery of claim 1, further including a cathode active material that is selected from an inorganic material, an organic material, a polymeric material, or a combination thereof, and said inorganic material does not include sulfur or alkali metal poly sulfide.

### Claim 26 (depends on 25)

The lithium secondary battery of claim 25, wherein said inorganic material is selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, lithium metal silicide, and combinations thereof.

### Claim 27 (depends on 25)

The lithium secondary battery of claim 25, wherein said inorganic material is selected from a metal fluoride or metal chloride including the group consisting of CoF3, MnF3, FeF3, VF3, VOF3, TiF3, BiF3, NiF2, FeF2, CuF2, CuF, SnF2, AgF, CuCl2, FeCl3, MnCl2, and combinations thereof.

### Claim 28 (depends on 25)

The lithium secondary battery of claim 25, wherein said inorganic material is selected from a lithium transition metal silicate, denoted as Li2MSiO4 or Li2MaxMbySiO4, wherein M and Ma are selected from Fe, Mn, Co, Ni, V, or VO; Mb is selected from Fe, Mn, Co, Ni, V, Ti, Al, B, Sn, or Bi; and x+y≤1.

### Claim 29 (depends on 25)

The lithium secondary battery of claim 25, wherein said inorganic material is selected from a transition metal dichalcogenide, a transition metal trichalcogenide, and combinations thereof.

### Claim 30 (depends on 25)

The lithium secondary battery of claim 25, wherein said inorganic material is selected from TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, an iron oxide, a vanadium oxide, and combinations thereof.

### Claim 31 (depends on 25)

The lithium secondary battery of claim 25, wherein said organic material contains a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, and combinations thereof.

### Claim 32 (depends on 25)

The lithium secondary battery of claim 25, wherein said organic material or polymeric material is selected from poly(anthraquinonyl sulfide) (PAQS), a lithium oxocarbon, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, quino(triazene), redox-active organic material, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE), 2,3,6,7,10,11-hexamethoxytriphenylene (HMTP), poly(5-amino-1,4-dyhydroxy anthraquinone) (PADAQ), phosphazene disulfide polymer ([(NPS2)3]n), lithiated 1,4,5,8-naphthalenetetraol formaldehyde polymer, hexaazatrinaphtylene (HATN), hexaazatriphenylene hexacarbonitrile (HAT(CN)6), 5-benzylidene hydantoin, isatine lithium salt, pyromellitic diimide lithium salt, tetrahydroxy-p-benzoquinone derivatives (THQLi4), N,N′-diphenyl-2,3,5,6-tetraketopiperazine (PHP), N,N′-diallyl-2,3,5,6-tetraketopiperazine (AP), N,N′-dipropyl-2,3,5,6-tetraketopiperazine (PRP), a thioether polymer, a quinone compound, 1,4-benzoquinone, 5,7,12,14-pentacenetetrone (PT), 5-amino-2,3-dihydro-1,4-dyhydroxy anthraquinone (ADDAQ), 5-amino-1,4-dyhydroxy anthraquinone (ADAQ), calixquinone, Li4C6O6, Li2C6O6, Li6C6O6, and combinations thereof.

### Claim 33 (depends on 32)

The lithium secondary battery of claim 32, wherein said thioether polymer is selected from poly[methanetetryl-tetra(thiomethylene)] (PMTTM), poly(2,4-dithiopentanylene) (PDTP), a polymer containing poly(ethene-1,1,2,2-tetrathiol) (PETT) as a main-chain thioether polymers, a side-chain thioether polymer having a main-chain consisting of conjugating aromatic moieties, and having a thioether side chain as a pendant, poly(2-phenyl-1,3-dithiolane) (PPDT), poly(1,4-di(1,3-dithiolan-2-yl)benzene) (PDDTB), poly(tetrahydrobenzodithiophene) (PTHBDT), poly[1,2,4,5-tetrakis(propylthio)benzene] (PTKPTB), or poly[3,4(ethylenedithio)thiophene] (PEDTT).

### Claim 34 (depends on 25)

The lithium secondary battery of claim 25, wherein said inorganic material is selected from a metal oxide, metal phosphate, metal silicide, metal selenide, transition metal sulfide, and combinations thereof.

### Claim 35 (depends on 34)

The lithium secondary battery of claim 34, wherein said metal oxide contains a vanadium oxide selected from the group consisting of VO2, LixVO2, V2O5, LixV2O5, V3O8, LixV3O8, LixV3O7, V4O9, LixV4O9, V6O13, LixV6O13, their doped versions, their derivatives, and combinations thereof, wherein 0.1<x<5.

### Claim 36 (depends on 34)

The lithium secondary battery of claim 34, wherein said metal oxide or metal phosphate is selected from a layered compound (LiMO2), spinel compound (LiM2O4), olivine compound (LiMPO4), silicate compound (Li2MSiO4), tavorite compound (LiMPO4F), borate compound (LiMBO3), or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.

### Claim 37 (depends on 34)

The lithium secondary battery of claim 34, wherein said inorganic material is selected from the group consisting of: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, and (e) combinations thereof.