# US 7,745,048 B2 · Rechargeable lithium polymer battery

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- Number: US 7,745,048 B2
- Document ID: US7745048B2
- Status: Granted
- Kind: B2
- Application number: 10/970,824
- Filed: 2004-10-21
- Published: 2005-04-28
- Granted: 2010-06-29
- Earliest claimed: 2003-10-23
- Assignees: Samsung SDI Co., Ltd.
- Inventors: Duck-Chul Hwang; Yun-Suk Choi; Chung-Kun Cho; Sang-Mock Lee
- Web page: https://patentgrep.com/patent/US7745048B2

## CPC

- H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/5815: {Sulfides}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/667: {in the form of layers, e.g. coatings}
- H01M 4/668: {Composites of electroconductive material and synthetic resins}
- H01M 10/052: Li-accumulators
- H01M 10/0562: Solid materials
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 50/461: {with adhesive layers between electrodes and separators}
- H01M 2004/027: {Negative electrodes}
- H01M 2300/004: Three solvents
- H01M 2300/0068: inorganic
- H01M 2300/0085: Immobilising or gelification of electrolyte
- H01M 2300/0094: in the form of layered products, e.g. coatings
- 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

Disclosed is a rechargeable lithium polymer battery comprising a negative electrode including a negative active material layer deposited on a substrate, a positive electrode including a positive active material; and a polymer electrolyte including a lithium salt, an organic solvent, and a polymer.

## Claims

### Claim 1

A rechargeable lithium polymer battery comprising:
a negative electrode comprising a negative active material layer deposited on a substrate, wherein the substrate comprises a negative current collector deposited on a supporting polymer film, and the negative active material is selected from the group consisting of lithium metal, an alloy of lithium metal and a material which is capable of reversibly forming a compound with lithium;
a positive electrode comprising a positive active material; and
a polymer electrolyte comprising a lithium salt, an organic solvent, and a polymer, wherein the polymer electrolyte is prepared by assembling a battery using an electrolyte precursor solution obtained from addition of a polymer-forming compound and an initiator to an electrolytic solution comprising a non-aqueous organic solvent and a lithium salt; and polymerizing the battery at a temperature at which it starts polymerization, wherein the polymer-forming compound is selected from the group consisting of compounds represented by formulas 16 to 18 and combinations thereof:
where Ra to Rf are identically or independently selected from one represented by formulas 16a or 16b:
where R5 is H or CH3, n is from 1 to 100,000, and R6 is H or CH3.

### Claim 2 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the current collector is selected from the group consisting of Ni, Ti, Cu, Ag, Au, Pt, Fe, Co, Cr, W, Mo, Al, Mg, K, Na, Ca, Sr, Ba, Si, Ge, Sb, Pb, In, Zn and combinations thereof.

### Claim 3 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the current collector has a thickness of 60 Å to 30,000 Å.

### Claim 4 (depends on 3)

The rechargeable lithium polymer battery of claim 3, wherein the current collector has a thickness of 75 Å to 10,000 Å.

### Claim 5 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the supporting polymer film has a melting point of 80° C. or more.

### Claim 6 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the supporting polymer film comprises a polymer selected from the group consisting of polyethylene terephthalate, polyimide, polytetrafluoroethylene, polyethylene naphthalate, polypropylene, polyethylene, polyester, polyvinylidene fluoride, and polysulfone.

### Claim 7 (depends on 1)

The rechargeable lithium polymer battery of claim 1, further comprising a silicon-included releasing layer.

### Claim 8 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the supporting polymer film has a thickness of 1 to 200 μm.

### Claim 9 (depends on 8)

The rechargeable lithium polymer battery of claim 8, wherein the supporting polymer film has a thickness of 2 to 100 μm.

### Claim 10 (depends on 9)

The rechargeable lithium polymer battery of claim 9, wherein the supporting polymer film has a thickness of 3 to 50 μm.

### Claim 11 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the negative active material layer has a thickness of 1 to 100 μm.

### Claim 12 (depends on 11)

The rechargeable lithium polymer battery of claim 11, wherein the negative active material layer has a thickness of 2 to 90 μm.

### Claim 13 (depends on 12)

The rechargeable lithium polymer battery of claim 12, wherein the negative active material layer has a thickness of 3 to 80 μm.

### Claim 14 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the negative active material is selected from the group consisting of Al, Mg, K, Na, Ca, Sr, Ba, Si, Ge, Sb, Pb, In, and Zn.

### Claim 15 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the negative active material layer further comprises a protection layer on a surface thereof.

### Claim 16 (depends on 15)

The rechargeable lithium polymer battery of claim 15, wherein the protection layer is a polymer material, an inorganic material or a mixture thereof.

### Claim 17 (depends on 16)

The rechargeable lithium polymer battery of claim 16, wherein the protection layer comprises an inorganic material selected from the group consisting of LiPON, Li2CO3, Li3N, Li3PO4, and Li5PO4.

### Claim 18 (depends on 16)

The rechargeable lithium polymer battery of claim 16, wherein the protection layer comprises an inorganic material with a thickness of 10 to 20,000 Å.

### Claim 19 (depends on 16)

The rechargeable lithium polymer battery of claim 16, wherein the protection layer comprises a polymer layer comprising a polymer selected from the group consisting of polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and hexafluoropropylene, poly(vinyl acetate), poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate), poly(methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinyl alcohol, poly(1-vinylpyrrolidone-co-vinyl acetate), cellulose acetate, polyvinyl pyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene-styrene, sulfonated styrene/ethylene-butylene/styrene triblock polymer, polyethylene oxide and combinations thereof.

### Claim 20 (depends on 16)

The rechargeable lithium polymer battery of claim 16, wherein the protection layer comprises a polymer material with a thickness of 100 Å to 10 μm.

### Claim 21 (depends on 15)

The rechargeable lithium polymer battery of claim 15, wherein the protection layer is provided as a single layer or as multiple layers.

### Claim 22 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the positive active material is a compound which is capable of reversibly intercalating or deintercalating lithium ions.

### Claim 23 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the positive active material is selected from the group consisting of compounds represented by formulas 2 to 15,
LiAO2
(2)
LiMn2O4
(3)
LiaNibBcMdO2 where 0.95 ≦ a ≦ 1.1, 0 ≦ b ≦ 0.9, 0 ≦ c ≦ 0.5,
(4)
and 0.001 ≦ d ≦ 0.1
LiaNibCocMndMeO2 where 0.95 ≦ a ≦ 1.1, 0 ≦ b ≦ 0.9,
(5)
0 ≦ c ≦ 0.5, 0 ≦ d ≦ 0.5, and 0.001 ≦ e ≦ 0.1
LiaAMbO2 where 0.95 ≦ a ≦ 1.1, and 0.001 ≦ b ≦ 0.1
(6)
LiaMn2MbO4 where 0.95 ≦ a ≦ 1.1, and 0.001 ≦ b ≦ 0.1
(7)
DS2
(8)
LiDS2
(9)
V2O5
(10)
LiV2O5
(11)
LiEO2
(12)
LiNiVO4
(13)
Li(3−x)F2(PO4)3 where 0 ≦ x ≦ 3
(14)
Li(3−x)Fe2(PO4)3 where 0 ≦ x ≦ 2
(15)
where A is selected from the group consisting of Co, No, or Mn; B is Co or Mn; D is Ti or Mo; B is selected from the group consisting of Cr, V, Fe, Sc, and Y; F is selected from the group consisting of V, Cr, M, Co, Ni, and Cu; and M is selected from the group consisting of transition metals, Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and combinations thereof.

### Claim 24 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the positive active material is selected from the group consisting of inorganic sulfur (S8), Li2Sn where n≧1 and carbon-sulfur polymers of the form (C2Sx)n, where x is from 2.5 to 50 and n≧2.

### Claim 25 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the initiator decomposes to generate nitrogen (N2) or carbon dioxide (CO2).

### Claim 26 (depends on 25)

The rechargeable lithium polymer battery of claim 25, wherein the initiator is selected from the group consisting of diacyl peroxides selected from the group consisting of dibenzoyl peroxide, succinic peroxide, dilauroyl peroxide, and didecanoyl peroxide; dialkyl peroxides selected from the group consisting of dicumyl peroxide, di-t-butyl peroxide and 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane; peroxy esters selected from the group consisting of α-cumyl peroxy-neodecanoate, 1,1-dimethyl-3-hydroxybutyl peroxy-2-ethylhexanoate, and t-butyl peroxy pivalate; tertiary alkyl hydroperoxides selected from the group consisting of 2,5-dihydroperoxy-2,5-dimethylhexane, cumene hydroperoxide, and t-butyl hydroperoxide; peroxy ketals selected from the group consisting of 2,2-di-(t-butylperoxy)butane and ethyl 3,3-di-(t-butylperoxy) butylate; peroxydicarbonates selected from the group consisting of di(n-propyl)peroxy dicarbonate, di(sec-butyl)peroxy dicarbonate, and di(2-ethylhexyl)peroxy dicarbonate; and azos comprising azobisisobutyronitrile.

### Claim 27 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the organic solvent is selected from the group consisting of benzene, toluene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene, 1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4-trichlorotoluene, iodotoluene, 1,2-diiodotoluene, 1,3-diiodotoluene, 1,4-diiodotoluene, 1,2,3-triiodotolune, 1,2,4-triiodotoluene, R—CN where R is a C2-C50 linear, branched, or cyclic hydrocarbon, and may include double bonds, aromatic rings, or ether bonds, dimethoxyformamide, methylacetate, xylene, cyclohexane, tetrahydrofurane, 2-methyltetrahydrofurane, cyclohexanone, ethanol, isopropyl alcohol, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, methylpropyl carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxyethane, 1,3-dioxolane, diglyme, tetraglyme, ethylene carbonate, propylene carbonate, γ-butyrolactone, valerolactone, decanolide, mevalolactone, sulfolane and mixtures thereof.

### Claim 28 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the lithium salt is selected from the group consisting of LiPF6, LiBP4, LiAsF6, LiClO4, LiCP3SO3, Li(CF3SO2)2N, LiN(SO2C2F5)2, LiSbF6, LiN(CF3SO2)3, LiC4F9SO3, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CxF2y+1SO2) where x and y are natural numbers, LiCl, LiI and mixtures thereof.

### Claim 29 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the polymer-forming compound and the electrolyte are provided in a weight ratio from 1:1 to 1:1,000.

### Claim 30 (depends on 29)

The rechargeable lithium polymer battery of claim 29, wherein the polymer-forming compound and the electrolyte are provided in a weight ratio from 1:5 to 1:200.

### Claim 31 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the polymer-forming compound and the initiator are provided in a weight ratio from 1:0.0001 to 1:0.5.

### Claim 32 (depends on 31)

The rechargeable lithium polymer battery of claim 31, wherein the polymer-forming compound and the electrolyte are provided in a weight ratio from 1:0.001 to 1:0.2.

### Claim 33 (depends on 1)

The rechargeable lithium polymer battery of claim 1, wherein the current collector has a thickness of 50 Å to 30,000 Å.