JP4757861B2 - 安全性及び性能が向上されたリチウム二次電池 - Google Patents
安全性及び性能が向上されたリチウム二次電池 Download PDFInfo
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- JP4757861B2 JP4757861B2 JP2007502739A JP2007502739A JP4757861B2 JP 4757861 B2 JP4757861 B2 JP 4757861B2 JP 2007502739 A JP2007502739 A JP 2007502739A JP 2007502739 A JP2007502739 A JP 2007502739A JP 4757861 B2 JP4757861 B2 JP 4757861B2
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- 229910052744 lithium Inorganic materials 0.000 title claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 43
- 229910001416 lithium ion Inorganic materials 0.000 claims description 41
- 239000010954 inorganic particle Substances 0.000 claims description 33
- 238000012546 transfer Methods 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 230000005540 biological transmission Effects 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 5
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 3
- 229910020346 SiS 2 Inorganic materials 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 3
- 229910010116 LiAlTiP Inorganic materials 0.000 claims description 2
- PPVYRCKAOVCGRJ-UHFFFAOYSA-K P(=S)([O-])([O-])[O-].[Ge+2].[Li+] Chemical compound P(=S)([O-])([O-])[O-].[Ge+2].[Li+] PPVYRCKAOVCGRJ-UHFFFAOYSA-K 0.000 claims description 2
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 12
- -1 lithium nitrides Chemical class 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910012465 LiTi Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/58—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
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
e growth)及びこれによる分離膜の破壊、急激な発熱反応、爆発などのような電池の安全性が欠如する問題点が発生する。
1)従来素子の安全性を高めるために電極の製造時に添加された一般の無機物粒子は前記無機物粒子の無反応性(inert)によって素子内のリチウムイオン伝導度が根本的に減少されて素子の性能低下が必須的に引き起こされた。これに対し、本発明の電極は電極添加剤として使われた無機物粒子のリチウムイオン伝達能力のため素子内のリチウムイオン伝導度の減少を最小化させて性能低下を防止することができる。
2)また、前記無機物粒子を添加して製造された電極は充電された電極の表面と接触する電解液の量を相対的に減少させることにより、一般的に素子の熱的安全性の欠如を起こす電極活物質と電解液との間の発熱反応を抑制して素子の安全性を高めることができる。特に、前記無機物粒子は一般的に200℃以上の高温になっても物理的な性質が変わらない特性、すなわち耐熱性を有するので高温、過充電などの過度な条件でも電極の安全性低下が全然発生しなくなる。
電極内に含まれるリチウムイオン伝達能力を有する無機物粒子の含量は特に制限されることはないが、電極活物質100重量部当たり0.01ないし10重量部が好ましい。前記無機物粒子の含量が0.01重量部未満である場合には、リチウムイオン伝達能力を有する無機物粒子の添加による電池の安全性の向上効果が僅かであり、無機物粒子の含量が10重量部超過である場合には、電池の容量及び性能低下が引き起こされる。
以下、本発明への理解を助けるために好適な実施例を挙げるが、後述する実施例は本発明を例示するものに過ぎず、本発明の範囲が以下の実施例に限定されることはない。
1−1.正極の製造
正極活物質としてLiCoO2 89重量%、リチウムイオン伝達能力を有する無機物粒子としてリチウムチタンフォスフェート(LiTi2(PO4)3)粉末3重量%、導電剤としてカーボンブラック(carbon black)4重量%、結合剤としてPVdF4重量%を、溶剤であるN-メチル-2ピロリドン(NMP)に加えて、正極混合物スラリーを製造した。前記正極混合物スラリーを厚さが20μmであるアルミニウム(Al)薄膜に塗布し乾燥することで正極を製造した後、ロールプレス(roll press)を施した。
負極活物質として炭素粉末、結合剤としてポリビニリデンフルオライド(PVdF)、導電剤としてカーボンブラック(carbon black)それぞれ96重量%、3重量%、1重量%を、溶剤であるN-メチル-2ピロリドン(NMP)に加えて、負極混合物スラリーを製造した。前記負極混合物スラリーを厚さが10μmである銅(Cu)薄膜に塗布し乾燥することで負極を製造した後、ロールプレス(roll press)を施した。
前記実施例1−1及び1−2で製造された両電極の間にポリプロピレン/ポリエチレン/ポリプロピレン(PP/PE/PP)分離膜を介在させた後、1モールのリチウムヘキサフルオロフォスフェート(LiPF6)が溶解されたエチレンカーボネート/プロピレンカーボネート/ジエチレンカーボネート(EC:PC:DEC=30:20:50重量%)の混合溶液である電解液を注入して電池を完成した。
リチウムチタンフォスフェート(LiTi2(PO4)3))粉末を使わないで正極活物質であるLiCoO2 92重量%を使って製造された正極を使用した以外は、前記実施例1の方法と同様にしてリチウム二次電池を製造した。
本発明によってリチウムイオン伝達能力を有する無機物粒子を含む電極スラリーから製造された電極を備えたリチウム二次電池の安全性を評価するために、下記のような実験を施した。
本発明はリチウムイオン伝達能力を有する無機物粒子を電極添加剤として用いることによって電気化学素子の安全性を高めると共に添加剤の添加による素子の性能低下を最小化させることができる。
Claims (6)
- (a)リチウムを吸蔵及び放出することができる正極活物質と、
前記正極活物質が、リチウムマンガン酸化物、リチウムコバルト酸化物、リチウムニッケル酸化物、リチウム鉄酸化物又はこれらの複合酸化物からなる群から選択されてなり、
(b)リチウムイオン伝達能力を有する一種以上の無機物粒子と、
前記無機物粒子が、リチウムフォスフェート(Li 3 PO 4 )、リチウムチタンフォスフェート〔Li x Ti y (PO 4 ) 3 、0<x<2、0<y<3〕、リチウムアルミニウムチタンフォスフェート〔Li x Al y Ti z (PO 4 ) 3 、0<x<2、0<y<1、0<z<3〕、〔(LiAlTiP) x O y 系ガラス(0<x<4、0<y<13)〕、リチウムランタンチタネート(Li x La y TiO 3 、0<x<2、0<y<3)、リチウムゲルマニウムチオフォスフェート(Li x Ge y P z S w 、0<x<4、0<y<1、0<z<1、0<w<5)、リチウムナイトライド(Li x N y 、0<x<4、0<y<2)、SiS 2 (Li x Si y S z 、0<x<3、0<y<2、0<z<4)系ガラス及びP 2 S 5 (Li x P y S z 、0<x<3、0<y<3、0<z<7)系ガラスからなる群より選択されてなり、
(c)導電剤と、及び
(d)バインダーとからなり、
前記リチウムイオン伝達能力を有する無機物粒子が、前記正極活物質100重量部当たり0.01ないし10重量部の量で存在してなり、
前記正極活物質の粒子が相互に連結し、かつ、前記バインダーにより結合されてなり、
正極において、前記正極活物質の粒子と、前記リチウムイオン伝達能力を有する無機物粒子がお互いに均一に混合されてなるものである、正極。 - 前記リチウムイオン伝達能力を有する無機物粒子が、リチウム元素を含んでなるが、リチウムイオンを保存せずにリチウムイオンを移動させる機能を有するものである、請求項1に記載の正極。
- 前記リチウムイオン伝達能力を有する無機物粒子が、結晶系または非晶質系である、請求項1に記載の正極。
- 前記結晶系リチウムイオン伝達能力を有する無機物粒子は、格子構造内にリチウムイオンを保存せずに、前記格子構造内に存在する欠陷によってリチウムイオンを伝達及び移動させることができるものである、請求項3に記載の正極。
- 電気化学素子であって、
正極と、負極と、両電極との間に介在された分離膜と、及び電解質を備えてなり、
前記正極が請求項1〜4のうちいずれかに一項に記載のものである、電気化学素子。 - 前記電気化学素子が、リチウム二次電池である請求項5に記載の電気化学素子。
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KR100805005B1 (ko) | 2008-02-20 |
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JP2007527603A (ja) | 2007-09-27 |
TW200614574A (en) | 2006-05-01 |
CA2574628A1 (en) | 2006-02-23 |
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