TWI255060B - Electrolyte solvent for improving safety of battery and lithium secondary battery comprising the same - Google Patents
Electrolyte solvent for improving safety of battery and lithium secondary battery comprising the same Download PDFInfo
- Publication number
- TWI255060B TWI255060B TW093126793A TW93126793A TWI255060B TW I255060 B TWI255060 B TW I255060B TW 093126793 A TW093126793 A TW 093126793A TW 93126793 A TW93126793 A TW 93126793A TW I255060 B TWI255060 B TW I255060B
- Authority
- TW
- Taiwan
- Prior art keywords
- electrolyte
- carbonate
- battery
- solvent
- electrolyte solvent
- Prior art date
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- 239000002904 solvent Substances 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 11
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 25
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 dimethyl carbonate Anthracene Chemical compound 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000052 vinegar Substances 0.000 claims description 7
- 235000021419 vinegar Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- CRJXZTRTJWAKMU-UHFFFAOYSA-N 4,4,5-trifluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1(F)F CRJXZTRTJWAKMU-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 235000019000 fluorine Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- FOPMLNAHNAGHLC-UHFFFAOYSA-N [C].FC=C Chemical compound [C].FC=C FOPMLNAHNAGHLC-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical class [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011076 safety test Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MJIULRNAOLSIHL-UHFFFAOYSA-N carbonic acid;fluoroethene Chemical compound FC=C.OC(O)=O MJIULRNAOLSIHL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IKHLUODZAMLTAF-UHFFFAOYSA-N 1,1-difluoropropyl hydrogen carbonate Chemical compound CCC(F)(F)OC(O)=O IKHLUODZAMLTAF-UHFFFAOYSA-N 0.000 description 1
- RHKPJTFLRQNNGJ-UHFFFAOYSA-N 1,3-benzothiazole-2-carbaldehyde Chemical compound C1=CC=C2SC(C=O)=NC2=C1 RHKPJTFLRQNNGJ-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- HUXWZDFLYJUAHR-UHFFFAOYSA-N 1,3-dioxolan-2-one;hydrazine Chemical compound NN.O=C1OCCO1 HUXWZDFLYJUAHR-UHFFFAOYSA-N 0.000 description 1
- SFRVOKMRHPQYGE-UHFFFAOYSA-N 1-(9h-fluoren-9-yl)ethyl carbonochloridate Chemical group C1=CC=C2C(C(OC(Cl)=O)C)C3=CC=CC=C3C2=C1 SFRVOKMRHPQYGE-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 208000002874 Acne Vulgaris Diseases 0.000 description 1
- HFQWLFOTUOSIBY-UHFFFAOYSA-N C(O)(O)=O.CNNC Chemical compound C(O)(O)=O.CNNC HFQWLFOTUOSIBY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- PCQBZUXXNDBYCV-UHFFFAOYSA-N NN(CCCCCCCCCC)CC Chemical compound NN(CCCCCCCCCC)CC PCQBZUXXNDBYCV-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- JQPCKPIRMBWMIN-UHFFFAOYSA-N [Cl].O=C1OCCO1 Chemical compound [Cl].O=C1OCCO1 JQPCKPIRMBWMIN-UHFFFAOYSA-N 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical group [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- GOHKWOGFPSWROP-UHFFFAOYSA-N [S].C=C Chemical compound [S].C=C GOHKWOGFPSWROP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- PMGNOQUKCGLETL-TYYBGVCCSA-N carbonic acid;(e)-1,2-difluoroethene Chemical compound OC(O)=O.F\C=C\F PMGNOQUKCGLETL-TYYBGVCCSA-N 0.000 description 1
- DDXGMOVCPFHPIV-UHFFFAOYSA-N carbonic acid;chloroethene Chemical compound ClC=C.OC(O)=O DDXGMOVCPFHPIV-UHFFFAOYSA-N 0.000 description 1
- GOYLFROSCCAARR-UHFFFAOYSA-N carbonic acid;ethenoxyethene Chemical compound OC(O)=O.C=COC=C GOYLFROSCCAARR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- DXTVYXOAQBXYAU-UHFFFAOYSA-N chloro ethyl carbonate Chemical compound CCOC(=O)OCl DXTVYXOAQBXYAU-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PPPHYGCRGMTZNA-UHFFFAOYSA-N trifluoromethyl hydrogen sulfate Chemical compound OS(=O)(=O)OC(F)(F)F PPPHYGCRGMTZNA-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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
1255060 九、發明說明: 【發明所屬之技術領域】 本發明是關於一種電解液溶劑用以改善包含該等之 電池與鐘二次電池之安全性。 、 【先前技術】 10 15 當可攜式裝置,例如高效能筆記型電腦和手機,變的 ,越普及’具高能量密度的充電電池是極需要的。尤其 是鐘二次電池’儘管才被發明不久,但已被大量用在可# =子產品。於是,藉增加鐘二次電池之電容量而延長^ ί式裝置之運行時間的研究正積極進行中。然而增加了容 里部減少了電池的安全性。有多堂 的安全性。 〇方以在改善μ二次電'池 綜括至目前為止對鋰二次電池安全 池安全層面最大的是當充雷士 九心響电 ”古4… 性物質與電解液的埶稃
疋度。有鑑於此,對於改善 …、I 手於發展具良好敎稃定产的二人電池的安全性,主要著 熱穩定度。’、,、“度的正極活性物質和改善電解液的 現今用作電解液的溶劑主 垣類,該等溶劑係為可直鍊狀的碳酸 境的溫度使電池溫度上升日士 ^氣池局部線路短路或環 的氧反應,尤其是正極:’〆谷劑易與活性物質降解生成 因此在溶劑中加人阻姆材生物貝’會造成燃燒或***。 阻燃材枓可改善電池安全性。 20 1255060 ^很多對阻燃劑的研究可被應用在鋰二次電池,此類研 究主要是將碳酸塩類上的氫以氟取代或改成含磷的溶劑, 此=溶劑比之前的碳酸塩類或酯類溶劑有較低的易燃性, 仁而用大里才可使電解液有阻燃性。此種阻燃劑對鋰塩的 5分解^比環狀碳酸塩差,且含氟或含碟比含氮的具較高的 原子里Μ吏電解液黏;帶性增力口。因此當阻燃劑對電解液之 比例提高,讀低了鐘離子的傳導性,而大大降地了電池效 能。 曰本專利早期公開專利平成1(Μ99567號揭露如果使 用如下、、構式1之二氟丙稀碳酸醋,被以占全部電解液溶 劑容量之60〜90%容量使用時,可以改善電池安全性。 結構式1 , Υ 然而,三氟丙烯碳酸酉旨黏滞度比一般常用的溶劑如乙 稀碳酸或㈣碳酸㈣兩倍。因此若依日本公開所敘述 之使用量,將會使電解液之離子的傳導性大幅下降,因^ 科避免的降地了電池效能。況且三氟丙稀碳_是將丙 坤石厌酸自日以μ取代氫,使内稀碳酸s|有了 —些缺點。如 20 1255060 5 10 15 20 25 ^ Electr〇chimicaActaVol.45,p.99>1999 ,^^^ ? /、使用於電解液溶劑中,在石 、 .^ . , ^ ^ 極與^解液接觸面所 =的包復層會有些不合適且會有電池充放電生命《的 美國料第6,5G6,524號揭露使用包含氟乙稀碳酸醋 和丙烯㈣旨做電解液溶劑時,會在石墨 的保護層。,然而若用此組成物作為電解液溶劑,離 二會=7mS/Cm,而使電池效能降低,因為氣乙婦碳酸 酉曰和丙烯碳酸醋雖有高介電常數卻有高黏滯性。 【發明内容】 / 、本發明發現若以氟乙烯碳酸西旨與直鍊酿溶劑結合 池之電解液溶劑使用,電池 會如同前案般的變差。 陸會改善,且電池編 因此,本發明的目的在提供一種電池用電解液溶劑, ,、包括氟乙烯碳酸自旨與直鍊龍劑,以及包含該等之鐘二 次電池。 ^ π面來α兒’本發明提供了 -種電池電解液溶劑包 括氟乙烯碳酸酯與直鍊酯溶劑。 另方面,本發明提供了一種鐘二次電池包括一正電 α"負^極和—電解液所組成,其中電解液包括敗乙烯 碳酸酯以及直鍊酯溶劑。 以下,係為本發明之詳細介紹。 ^本發明提供一種電池用電解液溶劑,#包括氟乙烯碳 I酉旨與直鍊酯溶劑當電解液。 1255060 、使用於本發明之氟乙烯碳酸酯係選^ 式2所代表之單氟乙稀碳酸酯(flec)、4 所代表之雙氟乙烯碳酸酯和其混和物中 結構式2 1包括由如下結構 f如下結構式3或 挑選出來的: 10
[FLEC] 結構式3
[trans-di-FEC] [反式雙氟乙烯碳酸酯] 15
結構式4 F F
[cis-di-FEC] [順式雙氟乙烯碳酸酉旨] I255〇6〇 當電池開始充電,氟乙烯碳酸酯在負電極產生—具高 熱穩定度的鑛膜,當將電池暴露在高溫’就乙稀碳酸酉旨: ,活化物質外面形成一鍍膜,如此既可抑制快速的放 1反應’於是便大大改善了電池安全性。尤其是氟乙稀碳 酸醋會在負電極形成穩定的、鍍膜而非氟乙稀碳酸醋不會因 ^此鐘―次電池中的氟乙稀碳酸§旨藉、由電解液氟乙稀碳酸 酉曰與鐘反應防止链的遺失,且可預防電解液的變質,因為 琶知液會在南電壓時氧化變質。 … 1〇 此外,不像日本早期公開平成10-199567使用的三氟 冰炭酸酯含有至少三個氟,氟乙烯碳酸醋只含一或兩個 氣。因此氟乙烯碳酸酯可預防如三氟乙婦碳酸醋所造成的 黏滯度增加的問題,亦可預防電池效能的衰退。另外,如 所知之先前技藝,如果使用日本專利公開之三氣乙稀碳酸 15酯,由三氟乙烯碳酸酯所生成的鍍膜的穩定性是不夠的, 遠有由於丙烯碳酸酯本身短缺所造成的電池充放電生命週 期的問題。相反的氟乙烯碳酸酯應用在現今的發明並不會 有此問題。 ’θ 藉由使用一直鍊酯化合物與氟乙烯碳酸酯,本發明不 20像習知技藝者,而可以改善電池安全性,也預防了電池效 能變差。表-顯示了氟乙蝉碳酸酯、三氟乙稀碳酸酷,碳酸 乙烯酯、碳酸丙烯酯、碳酸二甲酯、甲基乙基碳酸塩、碳 酸二乙基酯、乙酸乙酯、碳酸乙烯酯、丙酸甲酯等之物理 性質,其係為先前技藝所熟知之電解液溶劑。 表一:電解液溶劑之物理性質 25 1255060 溶劑 1占滯度(室溫) 介電常數 氟乙烯碳酸酯 4.1 78.4 106.1 ^ 反式雙氟乙 烯碳酸酯 2.5 37.1 124.0 ^ 三氟乙烯碳 酸醋 5.0 62.0 156 .y 〜 碳酸乙烯酯 2.5 89 88.1 ^ 碳酸丙稀酉旨 2.53 65 102.1 ^ 碳酸二乙基酯 0.59 3.1 ~90.1 ~^ 曱基乙基碳酸 塩 0.65 3.0 104.1 ^ 碳酸二乙基酯 0.75 2.8 118.1 ~ 乙酸乙酯 ^ 〇ΤΪ4 6.0 88.11 ^ 丙酸曱酯 0.43 6.2 88·ΐΤ〜 如表一所示,氟乙烯碳 毆_有很鬲的黏滯 獨使用時,會造成電池效能衰退 此外,環狀碳酸化合物比直鍊碳酸化合物有更高的黏滯 ^ 所以即使以氟乙烯碳酸酯與環狀碳酸化合物做電解 液會使電池效能降低。舉例來說,美國專利第6,5〇6,524 就闡逑*使用氟乙稀碳酸g|加環狀碳酸酯會因為離 性減少而使電池效能變差。 、、 本專利早期公開平成10-199567使用的三氟 厌酉夂酯比氟乙烯碳酸 ^ 人夂S日有更向的黏滯度。因此其結合直鍊 10 10 1255060 碳酸酯溶劑,其將很難防止電池效能變差。 依據本杳明,氟乙婦碳酸酯加直鍊酯溶劑用作電解 液,可改善電池安全性且不會降低電池效能。 同時,曰本專利早期公開平成10-199567曾使用氯 5乙烯碳酸酯加直鍊碳酸酯做電解液溶劑之例子。然而,如 同期刊P〇Wer S〇urce,81_82 (1999),p.20所述,若碳酸氯乙 ,旨加直鍊碳酸S旨用做電解液,負電極的碳酸氯乙稀酉旨會 ,原分解成氯化鐘。所生成的氯化㈣動至正電極生成氯 ⑺氯離子移動至負電極。這反應會—直重複著。用氯乙 坤碳酸酯加直鍊碳酸酯做電解液對電池效能會有不利的影 15 另一方面,氟化鋰是由氟乙烯碳酸酯(Fmc)反應而生成 被用作—種電解液的-種成分,其溶解度比氯化鐘差。 思指出上述的重複反應而使效能變差。因&,此發明的電 解液洛劑顯不比以氯乙稀碳酸§旨加直鍊碳酸_做電解液溶 劑者’可以減少電池效能降低。 簡而"之在本舍明中,氟乙稀碳酸酯結合直鍊酯溶 韻為電解液溶劑是與前述美國專利與日本公開者不同, 而可改善電池安全性,也不會降低電池效能。 〜可被用在本發明的直鍊s旨溶劑包括§旨類溶液和碳酸 每溶液,具體例子包括,但不限於:甲基乙基碳酸塩、二 甲基碳酸塩、二乙基碳酸盘、酷酸乙§旨和包含上述兩種或 以上的混合液。 的包含氣乙細碳酸酉旨 本發明的電池電解液溶劑較佳 20 1255060 =,量占全數電解液體積的2G〜⑽,若氟乙烯碳酸醋 二:、於2。%’即不會有足夠的安全性與電 ^容劑較佳的包4:: 的影響。同時直錄 的已3占全數電解液體積的40〜80%體積量。 ,另—方面,本發明的鋰二次電池是由正電極、負電 口"解液所組成,而電解液是由電解質溶液和鐘盘組成。 本發明的鐘二次電池可用已知的相同材料和方法來 造,但不包括本發明的電解液。舉例來說,本發明的鋰二 ίο 15 =池之電極結構是將多孔之隨插在正負電極間而製^ 的,再將此電極結構放入電池箱並到入發明的非水溶 液的電解液。 可被用在本發明絲的例子包括但不限於:六氣鱗酸 ,氮魏鐘、三敗甲基續酸銨經、雙過五氟乙基續酸銨 經、三氟曱基石黃酸甲基鐘、雙氧内醋删酸鐘、和包含上述 兩種或以上的混合液。
处,發明的電解液在室溫下,較佳的係為具有離子導電 月匕咼於7 mS/cm,更佳的是高於8 m§/cm。當離子導電 度少於7 mS/cm,電解液的離子就會移動的很慢,因此使 電池效能衰退。 斤在本發明中,用於正極的活性物質包含鋰與過渡金屬 的氧化物,非限定之例子包括uc〇2、UNi〇2、LiMh〇4、 ι^Μη〇2α&ίιΝΐιχ0〇χΜγ〇2(Μ=Α1、Τι Μ§4α〇< x < 1 ^ 0 < Υ < 0.2) , LiNixCoYMni.x.Y〇2 (〇 < X < 〇.5? 〇 < m5)’LiMxM’yMlWy)〇4(M,M,=V、〇、Fe、Co、 12 1255060
Nl 或^ UCoP〇4 等。 本發明中,負極的物質為可吸收、儲 子,非限定之例子包括# ^ 样放鋰離 離子的化合物。反夕和錫可吸收、儲存和釋放鐘 5 藉由電解液溶劑包含氟 月& 發明鐘二次電池可改善安全性,而不會降低電:广^ 【實施方式】 10 本發明在下文將舉例詳述之,然而 ,的,就是本發明沒有被侷限於子。n頁知 率備和測量離早導常痒 15 單氣乙烯碳酸酉旨和、甲基乙基碟酸塩依下表2之比例混 和來製備溶液,將六氟甲基磺酸鋰溶於各個製備的溶液調 =濃度為ο·8-1·2莫爾濃度之電解液。用瑞士萬通712電 導度計在任意溫度下測電解液的離子導電性。 實施例8 g 、,準備電解液和測量離子導電度的方法如同實施例工至 7,差別在於改以二甲基碳酸塩取代甲基乙基、碳酸塩,其混 20 和體積比例如下表2。 比較例 準備電解液和測量離子導電度的方法如同實施例丨至 7,差別在於用氟乙烯碳酸酯和甲基乙基碳酸塩或二f基碳 I酯而不用氟乙稀碳酸酯,其混和體積比例如下表2。 25 j匕較例5 13 1255060 、,準備甩解液和測量離子導電度的方法如同實施例1至 ' L差別在於用氣乙烯碳酸酯,乙烯碳酸酯和甲基乙基碳酸 塩,其混和體積比例如下表2。 _電池的 5 為了坪價電池安全性與效能,鋰二次電池結構如圖1 使用貫施例1至12與比較例1至7所配製的電解液來製造。 斗寸別地’負電極形成一以碳為鍍膜的負電極集電器 、(銅泊)當作負極活性物質。正電極形成一以鋰鈷氧化物 為f膜的正電極集電器(金箔)當作正極活性物質。還有 1〇以夕孔聚烯烴做分隔器纏繞於圓桶狀的膠狀物多次。然 後,§絶緣體被放置於圓桶狀的膠狀物上下端之間,最後的 圓桶狀的膠狀物放入直徑丨8毫米以及高65毫米圓桶狀的 私池罐,接下來將製備的電解液注入電池罐中,如此即完 成電池的製造。 15 生評估 直役18¾米以及高65毫米的電池被充飽電至4.2伏 斗寸或過充至4.3伏特,之後放入加熱速度每分鐘上升五度 的烤箱加熱至15〇度,測電池熱***的時間。結果如表三 和圖2至5。 20 一電解溶劑的組成物 ~~~-- LiPF6 (莫耳 濃度) FIEC (vol%) EC (vol%) PC (vol%) EMC (vol%) DMC (vol%) 貝施例1 ------ 0.8 25 75 14 1255060
實施例2 0.8 33 67 實施例3 0.8 40 60 實施例4 0.8 50 50 實施例5 0.8 60 40 實施例6 1.0 33 67 實施例7 1.2 33 67 實施例8 0.8 25 75 實施例9 0.8 33 67 實施例10 0.8 40 60 實施例11 0.8 50 50 實施例12 0.8 60 40 比較例1 0.8 10 90 比較例2 0.8 70 30 比較例3 0.8 33 67 比較例4 0.8 33 67 比較例5 0.8 23 10 67 比較例6 0.8 13 20 67 比較例7 0.8 50 50 表三:電池效能與安全性測試結果 室溫下 放電特性百分 充電伏 150°C下的維 的離子 比(電容量於 特數 持時間 傳導度 1C時/電容量 (mS/cm) 於 0·2 C) 15 1255〇6〇 超過90分鐘
不可測的,因 如上表三證據所顯示,电 灵施例之電池,豆白紅备 碳酸醋結合直鍊醋溶劑做為電解液溶劑,在離 安全性測試之結果都很出色。 a 16 1255060 較例3和4中,不含氣乙婦碳酸酯的安全性 Κ ^例1至12的雷砷#卵农,^ 日J文王r生 相對少量的氟乙烯碳酸二卜 加丙二s: 差。在比較例7中,用氣乙稀伽旨 Ή (¥狀碳酸酯)做電解液。其安全性與放電 貝不可測,因為高黏滞性電解液使電極未飽和。 ίο κ、同…圖4和5顯示電池過度充電至4.35伏特時安全 '生測試之結果。如圖4和5顯示,比較例丨的電池無法在 bO。。烘相中維持4〇分鐘(圖4)。實施例2的電池可在 150 C烘箱中維持其安全性超過2小時。、 免匕尤以上所述可以看出,依據本發明所提供,氟乙烯碳 酉文酉日結合直鍊酯溶劑做為電池之電解液溶劑,此可以防止 電池效能減低而改善電池之安全性。 15【圖式簡單說明】 圖1顯示一般圓桶電池結構。 圖2和圖3係為圖表顯示以比較例1和2所製造之電池在 飽和充私狀怨(4·2V)熱盒(h〇t-b〇x)測試之結果。 圖4和圖5係為圖表顯示以比較例1和2所製造之電池在 20過度充電狀態(4·35ν)熱盒(h〇t_b〇x)測試之結果。 【主要元件符號說明】 17 25
Claims (1)
- 95年2月修正頁 ^ ^ ^ ;; ' ' ..,.、、 \ 十、申請專利範圍: 1 · 一種用於雷、、★ α λ /之電解液溶劑,其包括氟乙烯碳酸酯 〇 且具有離子傳導度高於7mS/cm。 2 ·如申靖專利齡图每· 5 耗圍弟1項所述之電解液溶劑,其中該 5 鼠乙沐^^酸酉曰之體籍旦μ入Α 體積里占全部電解液溶劑體積的 20〜60%,且直鍊酯溶劑 、幻 4()~8()%。 4之體積里占全部電解液溶劑體積的 # 3:山如申請專利範圍第1項所述之電解液溶劑,其中該 鼠乙細石反酸醋係選自肖括|备 H)醋或其混和物。 Μ乙㈣酸酉旨、雙氣乙稀碳酸 4.如申請專利範圍第丨項所述之電解液溶劑,盆中该 直鍊醋溶劑係選自包括甲基乙基碳酸堪、二甲基碳酸垣、 二乙基碳酸塩、醋酸乙醋、或包含上述兩種或以上的混合 物。 / 口 15 5· -種鋰二次電池,包括一正電極、一負電極和一電 解液,其中該電解液包括一如申請專利範圍第丨至4項之 電解液溶劑,以及鋰盘。 、 18
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