CN101286573A - Electrolyte and lithium ion secondary battery containing the electrolyte - Google Patents
Electrolyte and lithium ion secondary battery containing the electrolyte Download PDFInfo
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- CN101286573A CN101286573A CNA2007100905066A CN200710090506A CN101286573A CN 101286573 A CN101286573 A CN 101286573A CN A2007100905066 A CNA2007100905066 A CN A2007100905066A CN 200710090506 A CN200710090506 A CN 200710090506A CN 101286573 A CN101286573 A CN 101286573A
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- Prior art keywords
- electrolyte
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- weight
- battery
- lithium
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 130
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 45
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 36
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 33
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 20
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- -1 LiSiF 6 Inorganic materials 0.000 claims description 16
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- YHNYOPGEKPRPNL-UHFFFAOYSA-N ethene;sulfurous acid Chemical compound C=C.OS(O)=O YHNYOPGEKPRPNL-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 27
- 238000000034 method Methods 0.000 description 20
- 239000012046 mixed solvent Substances 0.000 description 18
- 230000004087 circulation Effects 0.000 description 14
- 238000011056 performance test Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 150000005676 cyclic carbonates Chemical class 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- YUKILTJWFRTXGB-UHFFFAOYSA-N 1-chloro-3-methoxybenzene Chemical compound COC1=CC=CC(Cl)=C1 YUKILTJWFRTXGB-UHFFFAOYSA-N 0.000 description 1
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 1
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical compound COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 description 1
- MFJNOXOAIFNSBX-UHFFFAOYSA-N 1-fluoro-3-methoxybenzene Chemical compound COC1=CC=CC(F)=C1 MFJNOXOAIFNSBX-UHFFFAOYSA-N 0.000 description 1
- VIPWUFMFHBIKQI-UHFFFAOYSA-N 1-fluoro-4-methoxybenzene Chemical compound COC1=CC=C(F)C=C1 VIPWUFMFHBIKQI-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte, comprising lithium salt and organic solvent, wherein, the lithium salt at least comprises lithium bis(oxalate) borate. The electrolyte is characterized in that: the electrolyte also comprises a compound A as shown in the formula (I). In the formula (I), R1 and R2 respectively represent an alkyl with one to six hydrogen atoms or carbon atoms. Adding compound A as shown in the formula (I) into the electrolyte and adopting the electrolyte with lithium bis(oxalate) borate to manufacture batteries, the electrolyte remarkably improves the cycle performance of the lithium ion secondary batteries. The batteries made by the electrolyte can well perform in every aspect and market prospect thereof is bright.
Description
Technical field
The invention relates to a kind of electrolyte and contain the battery of this electrolyte, especially about a kind of electrolyte and contain the lithium rechargeable battery of this electrolyte.
Background technology
Lithium rechargeable battery comprises positive pole, negative pole, barrier film and electrolyte.Described electrolyte comprises as electrolytical lithium salts, organic solvent and additive.Lithium rechargeable battery has high-energy-density, high voltage, pollution-free, characteristics such as containing metal lithium, cycle life height, memory-less effect, charging rate be not fast.Being widely used in 3C Product at present, also is in PC, mobile phone and the individual radio electronic equipment such as portable CD player, PDA.
Yet, more and more higher along with improving constantly of people's demand to the performance requirement of lithium ion battery, such as when the automobile driving power, require battery to have high power capacity, excellent cycle performance, heavy-current discharge performance etc.
US 2004062995A1 discloses a kind of nonaqueous electrolytic solution secondary battery that contains, this battery comprises positive pole, negative pole and nonaqueous electrolytic solution, negative electrode active material in the described negative pole is a material with carbon element, wherein, described nonaqueous electrolytic solution contains at least a saturated cyclic carbonate and the cyclic carbonate of carbon-carbon double bonds, and the content of the cyclic carbonate of described carbon-carbon double bonds is 1.0 * 10
-8-13.0 * 10
-5The capacity of negative plates of gram/1 MAH.The cyclic carbonate of described carbon-carbon double bonds is a vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, 4, at least a in 5-dibutyl vinylene carbonate, 4-ethyl-5-methyl carbonic acid vinylene, 4-methyl-5-propyl group vinylene carbonate and the vinylethylene carbonate.As electrolytical lithium salts in the described nonaqueous electrolytic solution is LiPF
6, LiBF
4, LiCF
3SO
3, LiN (C
LF
2L+1SO
2) (C
MF
2M+1SO
2) (wherein, L and M all are not less than 1), LiC (C
pF
2p+1SO
2) (C
qF
2q+1SO
2) (C
rF
2r+1SO
2) in (wherein, p, q and r all are not less than 1) one or more.This method adopts the heavy-current discharge performance of the battery of this electrolyte with raising by the amount of the cyclic carbonate of carbon-carbon double bonds in the control electrolyte.But, adopt the cycle performance of battery of this electrolyte relatively poor, battery life is shorter.
In addition, US 20050026044A1 discloses a kind of electrolyte, and this electrolyte is by lithium salts, lactone and low viscous solvent composition, and wherein, described lithium salts contains biethyl diacid lithium borate.This method improves the dissolubility of biethyl diacid lithium borate in electrolyte solvent by using lactone and low viscous solvent as electrolyte solvent, to improve the heavy-current discharge performance of battery.Though this method has been improved the heavy-current discharge performance of battery,, adopt the cycle performance of battery of the electrolyte contain biethyl diacid lithium borate still good inadequately.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of lithium rechargeable battery cycle performance difference in the prior art, a kind of electrolyte of the cycle performance that can improve lithium rechargeable battery and the lithium rechargeable battery that adopts this electrolyte are provided.
The present inventor is surprised to find that, when cyclic carbonate that contains carbon-carbon double bonds in the electrolyte simultaneously and biethyl diacid lithium borate, this electrolyte not only can effectively improve the large-current discharge characteristics of the lithium rechargeable battery that adopts this electrolyte, and can effectively overcome the problem of the cycle performance difference of battery, make and adopt the lithium rechargeable battery of this electrolyte not only to have the large-current discharge characteristics of big excellence, but also have excellent cycle performance.
The invention provides a kind of electrolyte, this electrolyte contains lithium salts and organic solvent, and described lithium salts contains biethyl diacid lithium borate at least, it is characterized in that, described electrolyte also contains suc as formula the compd A shown in (I),
R in the formula (I)
1And R
2Representing hydrogen atom or carbon number respectively is the alkyl of 1-6.
The present invention also provides a kind of lithium rechargeable battery, comprise battery case, electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery case, described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, the electrolyte that makes for the present invention of described electrolyte.
Electrolyte provided by the invention is owing to contain suc as formula compd A and the biethyl diacid lithium borate shown in (I) simultaneously, thereby can improve the cycle performance of the lithium rechargeable battery that adopts this electrolyte greatly.For example, the normal temperature discharge capacitance after 400 times of the battery that the present invention the makes circulations is all more than 80%, the cycle performance of the battery that make in the prior art.In addition, the discharge capacitance that the high temperature after 400 circulations of the battery that the present invention makes is 45 ℃ also will be higher than the battery that makes in the prior art all more than 77%.
In addition, the present invention has effectively improved the cryogenic property of battery by adding suc as formula the compd B shown in (II) in electrolyte.Simultaneously, the battery that contains electrolyte of the present invention also has higher capacity.
In sum, the battery performance in every respect that adopts the electrolyte among the present invention to make is all good, has good market prospects.
Embodiment
Electrolyte provided by the invention contains suc as formula the compd A shown in (I),
R in the formula (I)
1And R
2Representing hydrogen atom or carbon number respectively is the alkyl of 1-6.Specifically, described compd A can be a vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, 4, one or more in 5-dibutyl vinylene carbonate, 4-ethyl-5-methyl carbonic acid vinylene and 4-methyl-5-propyl group vinylene carbonate.Total amount with electrolyte is a benchmark, and the content of described compd A is 0.1-10 weight %, is preferably 0.5-3 weight %.
According to the present invention, contain biethyl diacid lithium borate (LiB (C in the described lithium salts at least
2O
4)
2, LiBOB).In the present invention, described biethyl diacid lithium borate plays conventional lithium salts on the one hand as electrolytical effect, and on the other hand, described biethyl diacid lithium borate also acts synergistically with compd A, plays the effect that improves cycle performance of battery.Therefore, when only containing biethyl diacid lithium borate in the electrolyte of the present invention as the lithium salts electrolyte, the content of described biethyl diacid lithium borate can be the electrolytical content of lithium salts in the conventional electrolysis liquid, that is to say, total amount with lithium salts is a benchmark, and the content maximum of described biethyl diacid lithium borate can be 100 weight %.But the consumption of biethyl diacid lithium borate is excessive, causes battery capacity to descend easily.Therefore, except biethyl diacid lithium borate, can also contain other conventional lithium salts that uses in the described lithium salts.For example, can be LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSiF
6, LiB (C
6H
5)
4, LiCl, LiBr, LiAlCl
4, LiCF
3SO
3, Li (CF
3SO
2)
3, Li (CF
3SO
2)
2N, LiCF
3CO
2, Li (CF
3CO
2)
2N and Li[(C
2O
4)
2B] in one or more.Although a spot of biethyl diacid lithium borate and above-claimed cpd A mating reaction can realize purpose of the present invention, under the preferable case, be benchmark with the content of described lithium salts, the content of described biethyl diacid lithium borate is 1-15 weight %.
The employed organic solvent of electrolyte among the present invention can be conventionally used as the organic solvent of electrolyte for those skilled in the art.For example, can be in vinyl carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, ethene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite and the oxolane one or more.
According to electrolyte provided by the invention, the content of described lithium salts and organic solvent can be the lithium salts and the organic solvent content of this area routine, for example, total amount with electrolyte is a benchmark, the content of described lithium salts can be 0.1-15 weight %, and the content of described organic solvent is 75-90 weight %, under the preferable case, the content of described lithium salts is 0.1-10 weight %, and the content of described organic solvent is 87-90 weight %.
The present inventor finds that further when also containing suc as formula the compd B shown in (II) in the electrolyte provided by the invention, this electrolyte can also further improve the low temperature performance of the battery that adopts this electrolyte.Therefore, under the preferable case, electrolyte of the present invention also contains suc as formula the compd B shown in (II),
Wherein, it is that alkyl or the carbon number of 1-6 is the alkoxyl of 1-6 that R represents hydrogen atom, carbon number, and X represents halogen.Specifically, described compd B can be one or more in fluorobenzene, chlorobenzene, bromobenzene, 2-fluoroanisole, 2-chloroanisole, 2-bromoanisole, 3-fluoroanisole, 3-chloroanisole, 3-bromoanisole, 4-fluoroanisole, 4-chloroanisole and the 4-bromoanisole.Although a spot of compd B can reach the effect that improves the battery low temperature discharge property, under the preferable case, be benchmark with the total amount of electrolyte, the content of described compd B is 0.1-8 weight %, is preferably 0.1-5 weight %.The present invention makes the battery that adopts this electrolyte when possessing the good high-temperature performance by add compd B in electrolyte, has excellent cryogenic property, has improved the combination property of battery greatly, makes battery have more market prospects.
According to lithium rechargeable battery provided by the invention, described positive pole can be to well known to a person skilled in the art various positive poles, generally includes collector body and coating and/or is filled in positive electrode on this collector body.Described collector body can be a various collector body known in those skilled in the art, and as aluminium foil, Copper Foil or nickel plated steel strip, the present invention selects for use aluminium foil to make collector body.Described positive electrode can be a various positive electrode known in those skilled in the art, the conductive agent that generally includes positive active material, adhesive and optionally contain.
Described positive active material can be the positive active material of the embedded removal lithium embedded ion of this area routine, one or several in the preferred following material: Li
xM
yMn
2-yO
4, wherein, 0.9≤x≤1.2,0≤y≤1.0, M is a kind of in the elements such as lithium, boron, magnesium, aluminium, iron, cobalt, nickel, copper, gallium, yttrium, fluorine, iodine, sulphur; Li
xNi
yCo
1-yO
2, wherein, 0.9≤x≤1.1,0≤y≤1.0; Li
aNi
xCo
yMn
zO
2, wherein, 0≤a≤1.2, x+y+z=1,0≤x≤0.5,0≤y≤0.5,0≤z≤0.5.
Described adhesive can adopt the conventional all types of adhesives that are used to prepare lithium ion secondary battery positive electrode that use in the prior art, for example, can be in polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), butadiene-styrene rubber (SBR) and butadiene-styrene rubber (SBR) latex one or more.Weight with the positive active material in the positive electrode is benchmark, and the content of described adhesive is 2-10 weight %, is preferably 2-8 weight %.
Described conductive agent can be the anodal conductive agent of this area routine, at least a such as in acetylene black, conductive carbon black and the electrically conductive graphite.Conductive agent in second coating can be selected from one or more in the conductive agent that described positive electrode coating limited.Weight with the positive active material in the positive electrode is benchmark, and the content of conductive agent described in the positive electrode coating is 0-20 weight %, is preferably 2-15 weight %.
The negative pole of lithium rechargeable battery of the present invention is conventionally known to one of skill in the art.In general, described negative pole comprises collector body and coating and/or is filled in negative material on the conducting base.Described collector body is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip or Punching steel strip.Described negative active core-shell material is conventionally known to one of skill in the art, and it comprises negative electrode active material, adhesive and the conductive agent that optionally contains.
Described negative electrode active material is not particularly limited, can be the negative electrode active material of the embedded removal lithium embedded of this area routine, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred electrographite.
The adhesive of described negative pole comprises one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).Weight with described negative electrode active material is benchmark, and the content of described adhesive is 0.1-10 weight %, is preferably 0.5-5 weight %.
The conductive agent of described negative pole is not particularly limited, and can be the cathode conductive agent of this area routine, for example, and can acetylene black, in conductive carbon black and the electrically conductive graphite one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 0-15 weight %, is preferably 2-10 weight %.
The solvent that is used to prepare anode sizing agent and cathode size of the present invention can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of solvent can be coated on the described collector body described slurry and gets final product.In general, be benchmark with the weight of negative electrode active material, the content of described solvent is 30-80 weight %, is preferably 35-60 weight %.
Described membrane layer has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described membrane layer can be the general various membrane layers in this area, such as by those skilled in the art in the modified poly ethylene felt of respectively producing the trade mark, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt or the nylon felt of known each manufacturer production and wettability microporous polyolefin film through welding or the bonding composite membrane that forms.
The preparation method of lithium rechargeable battery of the present invention comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and the barrier film between positive pole and negative pole are prepared into pole piece, then pole piece is placed battery case, inject electrolyte, the sealed cell shell.
The preparation method of described positive pole can adopt conventional preparation method.For example,, apply and/or be filled on the described collector body positive active material, conductive agent and adhesive and solvent, drying, pressing mold or pressing mold not can obtain described positive pole.
The preparation method of described negative pole can adopt conventional preparation method.For example,, apply and/or be filled on the described collector negative electrode active material, conductive agent and adhesive and solvent, drying, pressing mold or pressing mold not can obtain described negative pole.
The preparation method of lithium rechargeable battery of the present invention is except described electrolyte uses nonaqueous electrolytic solution provided by the invention, and other step is conventionally known to one of skill in the art.The preparation method of lithium rechargeable battery provided by the invention is included between described positive pole for preparing and the negative pole membrane layer is set, constitute the electrode group, this electrode group is contained in the battery case, injects electrolyte, then the battery case sealing can be made lithium rechargeable battery.
Below by embodiment the present invention is described in more detail.
Embodiment 1
Present embodiment illustrates electrolyte provided by the invention, contains the battery of this electrolyte and their preparation method.
(1) preparation of electrolyte
50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, in this mixed solvent, add 22.8 gram LiPF
6Electrolyte adds 3.6 biethyl diacid lithium borates that restrain again, mixes, and adds the vinylene carbonates of 3.6 grams then, mixes, and makes electrolyte.In this electrolyte, the content of vinylene carbonate is 2 weight %, and the content of lithium salts is 14.7 weight %, and in the lithium salts, the content of biethyl diacid lithium borate is 13.6 weight %.
(2) Zheng Ji preparation
(Atuofeina Corp 761#PVDF) is dissolved in 1350 gram N-N-methyl-2-2-pyrrolidone N-(NMP) solvents and makes binder solution, then with 2895 gram LiCoO with 90 gram polyvinylidene fluoride
2(FMC Corp.'s production) joins in the above-mentioned solution, fully mixes and makes anode sizing agent, and this anode sizing agent is coated on the aluminium foil equably, makes long 70 millimeters, wide 19 millimeters, thick 125 microns positive pole through 125 ℃ of oven dry 1 hour, roll-in, cut-parts.The amount that applies makes every positive pole contain 6.2 gram LiCoO
2
(3) preparation of negative pole
(Jiangmen quantum Gao Ke company produces with 30 gram CMC CMC, model is CMC1500) and 75 gram butadiene-styrene rubber (SBR) latex (Nantong Shen Hua chemical company commodity, the trade mark is TAIPOL1500E) be dissolved in the 1875 gram water, make binder solution, with 1395 gram graphite (SODIFF company commodity, the trade mark is DAG84) join in this binder solution, mix and make the graphite cathode slurry, this cathode size is coated on the Copper Foil equably, through 125 ℃ of oven dry 1 hour, roll-in, cut-parts make long 70 millimeters, wide 19 millimeters, thick 125 microns negative pole.The amount that applies makes every negative pole contain 3.1 gram graphite.
(4) preparation of battery
The polypropylene screen of above-mentioned positive and negative plate and 20 micron thickness is wound into the pole piece of a rectangular lithium ion battery, pack in the battery case and weld, the electrolyte that manual implantation step (1) makes in ar gas environment in glove box is about 2.8 milliliters subsequently, lithium rechargeable battery A1 is made in sealing.The model of this lithium rechargeable battery is LP 053450, and design capacity is 1150 MAHs.
Comparative Examples 1
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add 22.8 gram LiPF in this mixed solvent
6Electrolyte mixes, the electrolyte that makes.In this electrolyte, the content of lithium salts is 13.2 weight %.Finally make reference cell D1.
Comparative Examples 2
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add 22.8 gram LiPF in this mixed solvent
6Electrolyte mixes, and adds the vinylene carbonate of 3.6 grams then, mixes the electrolyte that makes.In this electrolyte, the content of vinylene carbonate is 2 weight %, and the content of lithium salts is 12.9 weight %.Finally make reference cell D2.
Comparative Examples 3
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add 22.8 gram LiPF in this mixed solvent
6And the biethyl diacid lithium borate of 3.6 grams, mix the electrolyte that makes.In this electrolyte, the content of lithium salts is 15.0 weight %, and in the lithium salts, the content of biethyl diacid lithium borate is 13.6 weight %.Finally make reference cell D3.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add 22.8 gram LiPF in this mixed solvent
6Electrolyte adds 1 biethyl diacid lithium borate that restrains again, mixes, and adds 4 of 1 gram then, and 5-dimethyl vinylene carbonate mixes, the electrolyte that makes.In this electrolyte, 4, the content of 5-dimethyl vinylene carbonate is 0.6 weight %, and the content of lithium salts is 13.6 weight %, and in the lithium salts, the content of biethyl diacid lithium borate is 4.2 weight %.Finally make battery A2.
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add 14.6 gram LiPF in this mixed solvent
6Electrolyte adds 8.0 biethyl diacid lithium borates that restrain again, mixes, and adds the 4-ethyl-5-methyl carbonic acid vinylenes of 5.0 grams then, mixes the electrolyte that makes.In this electrolyte, the content of 4-ethyl-5-methyl carbonic acid vinylene is 2.8 weight %, and the content of lithium salts is 12.7 weight %, and in the lithium salts, the content of biethyl diacid lithium borate is 35.4 weight %.Finally make battery A3.
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, in this mixed solvent, add 18.7 gram biethyl diacid lithium borates, mix, add the vinylene carbonate of 2.5 grams then, mix the electrolyte that makes.In this electrolyte, the content of vinylene carbonate is 1.5 weight %, and the content of lithium salts is 11.0 weight %, and in the lithium salts, the content of biethyl diacid lithium borate is 100 weight %.Finally make battery A4.
Embodiment 5
Method according to embodiment 1 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add the LiPF of 22.8 grams in this mixed solvent
6Electrolyte adds 3.6 biethyl diacid lithium borates that restrain again, mixes, and adds the fluorobenzene of 3.6 grams and the vinylene carbonates of 3.6 grams then, mixes the electrolyte that makes.In this electrolyte, the content of fluorobenzene is 2 weight %, and the content of vinylene carbonate is 2 weight %, and the content of lithium salts is 14.4 weight %, and in the lithium salts, the content of biethyl diacid lithium borate is 13.6 weight %.Finally make battery A5.
Comparative Examples 4
Method according to embodiment 5 prepares lithium rechargeable battery, different is, described electrolyte prepares as follows: 50 gram vinyl carbonic esters (EC), 50 gram Methylethyl carbonic esters (EMC) and 50 gram diethyl carbonate (DEC) are mixed into mixed solvent, add the LiPF of 22.8 grams in this mixed solvent
6Electrolyte adds 3.6 fluorobenzene that restrain again, mixes, and in this electrolyte, the content of fluorobenzene is 2 weight %, and the content of lithium salts is 12.9 weight %.Finally make reference cell D4.
Embodiment 6
Method according to embodiment 5 prepares lithium rechargeable battery, and different is, the 2-chloroanisoles of 2.0 grams that add in the described electrolyte replace fluorobenzene, and the content of 2-chloroanisole is 1.1 weight % in this electrolyte.Finally make battery A6.
Embodiment 7
Method according to embodiment 5 prepares lithium rechargeable battery, and different is, the 3-bromoanisoles of 8.0 grams that add in the described electrolyte replace fluorobenzene, and the content of 2-chloroanisole is 4.3 weight % in this electrolyte.Finally make battery A7.
Embodiment 8
The performance of the battery A1 that the present embodiment explanation embodiment of the invention 1 makes.
(1) normal-temperature circulating performance test
Use BS-9300R secondary cell device for detecting performance that battery A1 is tested, test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
After 1C constant voltage charge to 4.2 volt, 20 milliamperes of charging cut-off currents.After shelving 5 minutes, be discharged to 3.0 volts, measure the initial discharge capacity that obtains battery with 1C.Repetition lies prostrate with 1C constant voltage charge to 4.2; Be discharged to 3.0 volts charge and discharge process again with 1C, the discharge capacity after the each circulation of record is calculated the discharge capacitance after the circulation the 400th time according to following formula then.The result is as shown in table 1.
Discharge capacitance=400th time circulation back discharge capacity/initial discharge capacity * 100%
In the above-mentioned cyclic process, with the thickness of the battery after cell thickness before the vernier caliper measurement circulation and the 400th circulation, obtain the cell thickness changing value after the circulation the 400th time simultaneously.The result is as shown in table 1.
(2) high temperature cyclic performance test
Method according to performance test (1) is tested battery A1, and different is that described test is to carry out under 45 ℃ in ambient temperature.Measure the 400th time after the circulation discharge capacitance and the thickness of battery after the 400th circulation, the result is as shown in table 1.
(3) high-temperature storage performance test
Battery A1 with 1C constant-current constant-voltage charging to 4.2 volt, is measured initial internal resistance R1, place battery 85 ± 2 ℃ to store 48 hours down afterwards, placed 24 hours down at 25 ℃ then, measure the recovery thickness and the internal resistance R2 of battery, and then be discharged to 3.2 volts, the initial capacity of record battery with 1C.Again battery is full of electricity and shelves current discharge to 3.2 volt of using 1C after 5 minutes, circulate continuously three times, write down the capacity (promptly recovering capacity) of each circulation.According to the storage internal resistance rate of change and the capacity restoration rate of following formula counting cell, the result is as shown in table 2.
Store internal resistance rate of change (%)=(R2-R1)/R1 * 100%
Recovery capacity/initial capacity * 100% of capacity restoration rate (%)=the 3rd circulation
(4) normal temperature discharge capacity test
Totally 5 of power taking pond A1 use BS-9300R secondary cell device for detecting performance to carry out the discharge capacity test.Test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
With 1C current charges to 4.2 volt, then with 1C current discharge to 3.0 volt, 5 discharge capacity value of record gained are averaged as discharge capacity.The result is as shown in table 3.
(5) low temperature performance test
Use BS-9300R secondary cell device for detecting performance that battery A1 is carried out the low temperature discharge volume test.
In temperature is that 25 ℃, relative humidity are under 30% the environment, and battery with 1C current charges to 4.2 volt, with 1C current discharge to 3 volt, is recorded initial discharge capacity then.Then, with this battery A1 with 1C current charges to 4.2 volt, in temperature be for-10 ℃, relative humidity after placing 90 minutes under 30% the environment with 1C current discharge to 2.75 volt, and the discharge capacity value of record when being discharged to 3 volts and 2.75 volts.
And then be that 25 ℃, relative humidity are under 30% the environment in temperature with battery A1, lie prostrate with 1C current charges to 4.2, after under temperature for-20 ℃, relative humidity is 30% environment, placing 90 minutes then with 1C current discharge to 2.75 volt, and the discharge capacity value of record when being discharged to 3 volts and 2.75 volts.Calculate the low temperature discharge ratio according to following formula then.The result is as shown in table 4.
Low temperature discharge ratio=low temperature discharge capacity/initial discharge capacity * 100%
Comparative Examples 5-7
Method according to embodiment 5 is carried out normal-temperature circulating performance test, high temperature cyclic performance test, the test of high-temperature storage performance, the test of normal temperature discharge capacity to battery D1-D4.The result is shown in table 1-3.
Embodiment 9-11
Method according to embodiment 8 is carried out normal-temperature circulating performance test, high temperature cyclic performance test, the test of high-temperature storage performance, the test of normal temperature discharge capacity to battery A2-A4.The result is shown in table 1-3.
Embodiment 12-14
Method according to embodiment 8 is carried out the low temperature performance test to battery A5-A7.The result is as shown in table 4.
Comparative Examples 8
Method according to embodiment 8 is carried out the low temperature performance test to battery D4.The result is as shown in table 4.
Table 1
As can be seen from Table 1, in the normal-temperature circulating performance test, 400 circulation back discharge capacitances of the battery A1-A4 that the present invention makes are all more than 80%, and do not add biethyl diacid lithium borate and compd A in the electrolyte of reference cell D1, discharge capacitance only is 63%, has only added biethyl diacid lithium borate in the electrolyte of reference cell D2, and discharge capacitance only is 72%, only added compd A in the electrolyte of reference cell D3, discharge capacitance only is 73%.Therefore, the cycle performance of battery that adopts electrolyte of the present invention to make will be apparently higher than reference cell D1-D3.In addition, in 45 ℃ high temperature cyclic performance test, the cycle performance of battery that adopts electrolyte of the present invention to make also will be higher than reference cell D1-D3.
In addition, the battery A1-A4 that makes of the present invention changes less with respect to the reference cell D1-D3 that Comparative Examples makes at 400 circulation back cell thickness.
Table 2
| The battery source | The battery numbering | Initial capacity (MAH) | Recover thickness (millimeter) | Store internal resistance rate of change (%) | Capacity restoration rate (%) |
| Embodiment 1 | A1 | 1205 | 6.32 | 10.23 | 86.89 |
| Comparative example 1 | D1 | 1184 | 6.61 | 18.91 | 75.03 |
| Comparative example 2 | D2 | 1189 | 7.09 | 20.34 | 72.44 |
| Comparative example 3 | D3 | 1187 | 6.99 | 21.47 | 71.85 |
| Embodiment 2 | A2 | 1197 | 6.38 | 11.11 | 85.46 |
| Embodiment 3 | A3 | 1180 | 6.45 | 12.66 | 83.56 |
| Embodiment 4 | A4 | 1135 | 6.28 | 10.59 | 88.57 |
As can be seen from Table 2, the battery A1-A4 that embodiment of the invention 1-4 makes compares with the reference cell D1-D3 that Comparative Examples 1-3 makes, and after storing under 85 ± 2 ℃, stores the internal resistance rate of change and will hang down more than 6%, and it is high more than 7% that the capacity restoration rate is wanted.In addition, initial discharge capacity after the high-temperature storage of battery A1-A3 is also higher, it is also little than reference cell D1-D3 to recover thickness, and battery A3 that embodiment 3 and embodiment 4 make and A4 are lower on initial capacity, its reason is that the lithium salts in the electrolyte of this battery is a biethyl diacid lithium borate all, makes battery capacity reduce.Therefore, among the present invention, be benchmark with the total amount of lithium salts, the content of described biethyl diacid lithium borate is preferably 1-15 weight %.
Table 3
As can be seen from Table 3, the normal temperature discharge capacity of the battery A1-A3 that makes of embodiment of the invention 1-3 exceeds more than 10 MAHs than the reference cell D1-D3 that Comparative Examples 1-3 makes.In addition, battery A3 that embodiment 3 and embodiment 4 make and the normal temperature discharge capacity of A4 are relatively low, and its reason is that the lithium salts in the electrolyte of this battery is a biethyl diacid lithium borate all, make battery capacity reduce.Therefore, among the present invention, be benchmark with the total amount of lithium salts, the content of described biethyl diacid lithium borate is preferably 1-15 weight %.
Table 4
As can be seen from Table 4, the battery A5-A7 that embodiment of the invention 5-7 makes has added compd B in electrolyte, making the cryogenic property of battery compare battery A1 is improved largely, and compare and in electrolyte, only add the reference cell D4 that compd B makes, it is high that the low temperature discharge ratio of battery A1-A3 is also obviously wanted.Therefore, the present invention preferably adds compd B in electrolyte.
Claims (9)
1, a kind of electrolyte, this electrolyte contains lithium salts and organic solvent, and described lithium salts contains biethyl diacid lithium borate at least, it is characterized in that, and described electrolyte also contains suc as formula the compd A shown in (I),
R in the formula (I)
1And R
2Representing hydrogen atom or carbon number respectively is the alkyl of 1-6.
2, electrolyte according to claim 1 wherein, is benchmark with the total amount of electrolyte, and the content of described compd A is 0.1-10 weight %, and the content of described lithium salts is 0.1-15 weight %, and the content of described organic solvent is 75-90 weight %.
3, electrolyte according to claim 2 wherein, is benchmark with the total amount of electrolyte, and the content of described compd A is 0.5-3 weight %, and the content of described lithium salts is 0.1-10 weight %, and the content of described organic solvent is 87-90 weight %.
4, electrolyte according to claim 1, wherein, described compd A is a vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, 4, one or more in 5-dibutyl vinylene carbonate, 4-ethyl-5-methyl carbonic acid vinylene and 4-methyl-5-propyl group vinylene carbonate.
5, electrolyte according to claim 1, wherein, described lithium salts also contains LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSiF
6, LiB (C
6H
5)
4, LiCl, LiBr, LiAlCl
4, LiCF
3SO
3, Li (CF
3SO
2)
3, Li (CF
3SO
2)
2N, LiCF
3CO
2And Li (CF
3CO
2)
2Among the N one or more are benchmark with the content of described lithium salts, and the content of biethyl diacid lithium borate is 1-15 weight %.
6, according to any described electrolyte among the claim 1-3, wherein, described organic solvent is one or more in vinyl carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, methyl formate, methyl acrylate, methyl butyrate, ethyl acetate, ethene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite and the oxolane.
7, electrolyte according to claim 1, wherein, this electrolyte also contains suc as formula the compd B shown in (II),
Wherein to represent hydrogen atom, carbon number be that alkyl or the carbon number of 1-6 is the alkoxyl of 1-6 to R, and X represents halogen.
8, electrolyte according to claim 7 wherein, is benchmark with the total amount of electrolyte, and the content of described compd B is 0.1-8 weight %.
9, a kind of lithium rechargeable battery, comprise battery case, electrode group and electrolyte, described electrode group and electrolyte are sealed in the battery case, described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that described electrolyte is any described electrolyte among the claim 1-9.
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|---|---|---|---|
| CNA2007100905066A CN101286573A (en) | 2007-04-09 | 2007-04-09 | Electrolyte and lithium ion secondary battery containing the electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100905066A CN101286573A (en) | 2007-04-09 | 2007-04-09 | Electrolyte and lithium ion secondary battery containing the electrolyte |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206796A (en) * | 2012-02-29 | 2015-12-30 | 新神户电机株式会社 | Lithium ion battery |
| WO2018006565A1 (en) * | 2016-07-08 | 2018-01-11 | 深圳新宙邦科技股份有限公司 | Lithium ion battery using non-aqueous electrolyte |
| CN111048839A (en) * | 2019-12-25 | 2020-04-21 | 湖州昆仑动力电池材料有限公司 | Lithium ion battery electrolyte with good low-temperature discharge characteristic and lithium ion battery |
-
2007
- 2007-04-09 CN CNA2007100905066A patent/CN101286573A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206796A (en) * | 2012-02-29 | 2015-12-30 | 新神户电机株式会社 | Lithium ion battery |
| WO2018006565A1 (en) * | 2016-07-08 | 2018-01-11 | 深圳新宙邦科技股份有限公司 | Lithium ion battery using non-aqueous electrolyte |
| CN111048839A (en) * | 2019-12-25 | 2020-04-21 | 湖州昆仑动力电池材料有限公司 | Lithium ion battery electrolyte with good low-temperature discharge characteristic and lithium ion battery |
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