JP2016521444A - リチウムバッテリ用正電極 - Google Patents
リチウムバッテリ用正電極 Download PDFInfo
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- JP2016521444A JP2016521444A JP2016509529A JP2016509529A JP2016521444A JP 2016521444 A JP2016521444 A JP 2016521444A JP 2016509529 A JP2016509529 A JP 2016509529A JP 2016509529 A JP2016509529 A JP 2016509529A JP 2016521444 A JP2016521444 A JP 2016521444A
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- positive electrode
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 159000000002 lithium salts Chemical class 0.000 claims description 44
- 229910003002 lithium salt Inorganic materials 0.000 claims description 43
- 239000007774 positive electrode material Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- -1 LiCF 3 SO 3 Inorganic materials 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- DOYSIZKQWJYULQ-UHFFFAOYSA-N 1,1,2,2,2-pentafluoro-n-(1,1,2,2,2-pentafluoroethylsulfonyl)ethanesulfonamide Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)C(F)(F)F DOYSIZKQWJYULQ-UHFFFAOYSA-N 0.000 claims description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229920000767 polyaniline Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WUOUBJDINSHIPE-UHFFFAOYSA-N 3-(4-fluorophenyl)thiophene Chemical class C1=CC(F)=CC=C1C1=CSC=C1 WUOUBJDINSHIPE-UHFFFAOYSA-N 0.000 description 1
- 206010000117 Abnormal behaviour Diseases 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Crystallography & Structural Chemistry (AREA)
Abstract
Description
前記正電極は、
a)複合材料の電気活性層と、ここで、前記複合材料は、
前記バッテリの作動電位窓内で導電性である一方、1.5V対Li/Li+より下でかつ/又は4.8V対Li/Li+より上の電位で絶縁性の高分子から選択された少なくとも1つの高分子P1と、
ハロゲン化高分子から選択された少なくとも1つの高分子P2と、を含み、
b)集電体と、
c)複合正電極材料の層と、ここで、前記複合正電極材料は、
少なくとも1つの活性正電極材料と、
電子伝導性を付与する少なくとも1つの作用物質と、
少なくとも1つのバインダと、
少なくとも1つのリチウム塩と、を含み、
前記電気活性層は、前記集電体と前記複合正電極材料の層との間に挟まれている。
0.54gのポリアニリン(PAni)、0.054gのポリビニリデンフルオライド(PVdF)及び0.387gのリチウム塩(LiTFSI)を157mlの溶剤NMP中に懸濁させた。この溶液を4時間磁気撹拌にかけ、次に被覆台を利用して炭素含有アルミニウムシートから成る集電体に付着させた。
LMPバッテリの性能に対する電気活性層内のリチウム塩の存在の影響の実証
前述のように、バッテリが組み立てられるときとその動作中に複合正電極材料層及び/又は電解質層内に存在するリチウム塩が電気活性層内に拡散することがあるので、電気活性層内のリチウム塩の存在は必須ではない。
−0.25mol/lのLiTFSI(B1と示す)
−0.5mol/lのLiTFSI(B2と示す)
−3mol/lのLiTFSI(B3と示す)
−リチウム塩なし(B4と示す)。
−比較バッテリBC0:電気活性層を含まないこと以外、本発明によるバッテリB1〜B4のものと全く同一の正電極。
−比較バッテリBC1:電気活性層がPVdFを含まないこと以外、バッテリB1と全く同一。
−バッテリB1は、黒い四角で表わされ、
−バッテリB2は、白い三角形で表わされ、
−バッテリB3は、白い円で表わされ、
−バッテリB4は、黒い菱形で表わされ、
−比較バッテリBC0は、黒い円で表わされ、
−比較バッテリBC1は、白い四角で表わされる。
−電気活性層(BC0)のない比較バッテリ:約3.56Vの平均酸化電位が観察される。このバッテリは、過充電又は過放電のための安全装置がない一方、酸化ピークの電位の観点から「理想的」な挙動を示す。
−電位が2.9V対Li+/Li0以下の場合、システムの抵抗率が高い(>10000Ω/cm2)。この結果から、低電位での電気活性層内にある導電性高分子の絶縁特性が分かる。
この実施例において、本発明により、また前に実施例2で作成されたようなバッテリB2のサイクルを実行した。
−充電:最初に3.5Vにプラトがある。
−放電:最初に3.35Vにプラトがある。
2:集電体
3:電気活性層
4:複合正電極材料層
5:電解質層
6:負電極層
7:集電体
Claims (16)
- 少なくとも1つの活性正電極材料と、少なくとも1つのバインダと、電子伝導性を付与する少なくとも1つの作用物質と、少なくとも1つの集電体とを備えた、リチウムバッテリ、詳細にはリチウム金属高分子バッテリ用の正電極であって、
前記正電極は、
a)複合材料の電気活性層と、ここで、前記複合材料は、
前記バッテリの作動電位窓内で導電性である一方、1.5V対Li/Li+より下でかつ/又は4.8V対Li/Li+より上の電位で絶縁性の高分子から選択された少なくとも1つの高分子P1と、
ハロゲン化高分子から選択された少なくとも1つの高分子P2と、を含み、
b)集電体と、
c)複合正電極材料の層と、ここで、前記複合正電極材料は、
少なくとも1つの活性正電極材料と、
電子伝導性を付与する少なくとも1つの作用物質と、
少なくとも1つのバインダと、
少なくとも1つのリチウム塩と、を含み、
前記電気活性層は、前記集電体と前記複合正電極材料の層との間に挟まれている、正電極。 - 前記高分子P1は、2.8V未満でかつ3.6Vを超える電位で絶縁性の高分子から選択された、請求項に記載の正電極。
- 前記高分子P1は、ポリアニン類、ポリチオフェン類、ポリピロール類及びポリ3,4−エチレンジオキシチオフェン類から選択された、請求項1に記載の正電極。
- 前記ハロゲン化高分子P2は、塩化ビニル、フッ化ビニリデン、塩化ビニリデン、テトラフロオルエチレン、クロロトリフルオロエチレンのホモポリマーとコポリマー、フッ化ビニリデンとヘキサフルオロプロピレンのコポリマー、及びこれらのホモポリマーとコポリマーの混合物から選択されたフッ素重合体である、請求項1〜3のうちいずれか一項に記載の正電極。
- 前記高分子P2は、ポリビニリデンフルオライドである、請求項4に記載の正電極。
- 前記高分子P2は、前記高分子P1の質量に対して1〜20質量%である、請求項1〜5のうちいずれか一項に記載の正電極。
- 前記電気活性層は、更に少なくとも1つのリチウム塩を含む、請求項1〜6のうちいずれか一項に記載の正電極。
- リチウム塩類は、LiBF4、LiPF6、リチウムビス(トリフルオロメチルスルホニル)イミド、リチウムビス(フルオロスルホニル)イミド(LiFSI)、ビス(ペンタフルオロエチルスルホニル)イミド、LiAsF6、LiCF3SO3、LiSbF6、LiSbCl6、Li2TiCl6、Li2SeCl6、Li2B10Cl10、Li2B12Cl12、及びリチウムビス(オキサラト)ボレートから選択された、請求項7に記載の正電極。
- 前記リチウム塩は、0.1M〜5Mのモル濃度で存在する、請求項7又はと請求項8に記載の正電極。
- 前記活性正電極材料は、リン酸鉄を主成分とする材料である、請求項1〜9のうちいずれか一項に記載の正電極。
- 前記活性正電極材料は、炭素含有被覆を含む露出粒子の形のLiFePO4である、請求項10に記載の正電極。
- 電子伝導性を付与する作用物質は、カーボンブラック、カーボンナノチューブ、グラファイト、及びこれらの材料の混合物から選択された炭素である、請求項1〜11のうちいずれか一項に記載の正電極。
- 複合正電極材料層が20〜100μmの範囲の厚さを有する場合に、前記電気活性層が1〜15μmの範囲の厚さを有する、請求項1〜12のうちいずれか一項に記載の正電極。
- リチウムバッテリを生産するための請求項1〜13のうちいずれかに一項に記載された正電極の使用法。
- 前記リチウムバッテリは、リチウム金属高分子バッテリである、請求項14に記載の使用法。
- 少なくとも正電極と、負電極と、電解質と、前記正電極用の集電体とを備えるリチウムバッテリであって、前記正電極は、請求項1〜13のうちいずれか一項に記載された正電極である、リチウムバッテリ。
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PCT/FR2014/050983 WO2014174212A1 (fr) | 2013-04-24 | 2014-04-23 | Electrode positive pour batterie lithium |
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US10038183B2 (en) | 2018-07-31 |
KR20160003680A (ko) | 2016-01-11 |
WO2014174212A1 (fr) | 2014-10-30 |
CN105164832A (zh) | 2015-12-16 |
KR102044220B1 (ko) | 2019-11-13 |
JP6402174B2 (ja) | 2018-10-10 |
HK1215757A1 (zh) | 2016-09-09 |
FR3005207A1 (fr) | 2014-10-31 |
CA2908675A1 (fr) | 2014-10-30 |
EP2989670B1 (fr) | 2019-12-11 |
FR3005207B1 (fr) | 2016-06-24 |
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US20160285078A1 (en) | 2016-09-29 |
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