CN103915605B - Sulfur-bearing negative pole and corresponding nonaqueous electrolytic solution secondary battery - Google Patents
Sulfur-bearing negative pole and corresponding nonaqueous electrolytic solution secondary battery Download PDFInfo
- Publication number
- CN103915605B CN103915605B CN201310006941.1A CN201310006941A CN103915605B CN 103915605 B CN103915605 B CN 103915605B CN 201310006941 A CN201310006941 A CN 201310006941A CN 103915605 B CN103915605 B CN 103915605B
- Authority
- CN
- China
- Prior art keywords
- battery
- negative pole
- electrolytic solution
- lithium
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims abstract description 29
- 230000000875 corresponding Effects 0.000 title description 3
- 239000000463 material Substances 0.000 claims abstract description 50
- -1 sulphur compound Chemical class 0.000 claims abstract description 43
- 239000011889 copper foil Substances 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000002905 metal composite material Substances 0.000 claims description 4
- 229910007552 Li2Sn Inorganic materials 0.000 claims description 3
- 239000011883 electrode binding agent Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims description 2
- 229910052609 olivine Inorganic materials 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims 1
- 150000003464 sulfur compounds Chemical class 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 23
- 235000001508 sulfur Nutrition 0.000 description 27
- 239000010408 film Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 18
- 238000007792 addition Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 210000004027 cells Anatomy 0.000 description 14
- 238000007599 discharging Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 150000008064 anhydrides Chemical class 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000004087 circulation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- VPAYJEUHKVESSD-UHFFFAOYSA-N Trifluoroiodomethane Chemical group FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910052803 cobalt Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GLUCAHCCJMJHGV-UHFFFAOYSA-N dilithium;dioxido(oxo)titanium Chemical compound [Li+].[Li+].[O-][Ti]([O-])=O GLUCAHCCJMJHGV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N Butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 210000001787 Dendrites Anatomy 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N Diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N Dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910013131 LiN Inorganic materials 0.000 description 2
- 229910014427 LiNi1/3Co1/3Mn1/3O2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N Lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 230000002441 reversible Effects 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 230000014233 sulfur utilization Effects 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UBMXMUDVGQEANW-UHFFFAOYSA-N 1,1,1,2,3,3,4,4-octafluoro-4-methoxy-2-(trifluoromethyl)butane Chemical compound COC(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F UBMXMUDVGQEANW-UHFFFAOYSA-N 0.000 description 1
- WMVAEJWSRBISBP-UHFFFAOYSA-N 1,1,1,2,3,3,4,4-octafluoro-4-propoxy-2-(trifluoromethyl)butane Chemical compound CCCOC(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F WMVAEJWSRBISBP-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- UJEGHEMJVNQWOJ-UHFFFAOYSA-N 1-heptoxyheptane Chemical compound CCCCCCCOCCCCCCC UJEGHEMJVNQWOJ-UHFFFAOYSA-N 0.000 description 1
- GTQXEQRIVGXSAE-UHFFFAOYSA-N 1-methoxyheptane Chemical compound CCCCCCCOC GTQXEQRIVGXSAE-UHFFFAOYSA-N 0.000 description 1
- DOYXDCAHTUMXDF-UHFFFAOYSA-N 1-propoxyheptane Chemical compound CCCCCCCOCCC DOYXDCAHTUMXDF-UHFFFAOYSA-N 0.000 description 1
- VCRNFKKHEIEHCS-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol;methoxymethane Chemical compound COC.OCCOCCOCCOCCO VCRNFKKHEIEHCS-UHFFFAOYSA-N 0.000 description 1
- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 description 1
- AURKDQJEOYBJSQ-UHFFFAOYSA-N 2-hydroxypropanoyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OC(=O)C(C)O AURKDQJEOYBJSQ-UHFFFAOYSA-N 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- FREZLSIGWNCSOQ-UHFFFAOYSA-N 3-methylbutanoyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OC(=O)CC(C)C FREZLSIGWNCSOQ-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 3H-pyran-2,6-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N Butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N Cobalt(II) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N Dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N Disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N Ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- YQHAJBWBAWASHP-UHFFFAOYSA-N FC(F)CCCCCOC Chemical compound FC(F)CCCCCOC YQHAJBWBAWASHP-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N Fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 229910008416 Li-Ti Inorganic materials 0.000 description 1
- 229910011469 Li4/3Ti5/3O4 Inorganic materials 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- 229910016124 LiNi1-x-y-zCox Inorganic materials 0.000 description 1
- 229910014411 LiNi1/2Mn1/2O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K Lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N Lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 229910013263 LiyM2O4 Inorganic materials 0.000 description 1
- 229910006861 Li—Ti Inorganic materials 0.000 description 1
- 229940017219 METHYL PROPIONATE Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- KKHUSADXXDNRPW-UHFFFAOYSA-N Malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 description 1
- YDSWCNNOKPMOTP-UHFFFAOYSA-N Mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910016483 Mn1/3Co1/3O2 Inorganic materials 0.000 description 1
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001225 Polyester resin Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N Propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 210000002356 Skeleton Anatomy 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 229920002397 Thermoplastic olefin Polymers 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N Triethylene glycol dimethyl ether Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N Trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- FXEDRSGUZBCDMO-HEEUSZRZSA-N [(E)-3-phenylprop-2-enoyl] (Z)-3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1/C=C/C(=O)OC(=O)\C=C/C1=CC=CC=C1 FXEDRSGUZBCDMO-HEEUSZRZSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910001884 aluminium oxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCUJFJGJUYOITH-UHFFFAOYSA-N lithium(1-);nickel;oxygen(2-) Chemical compound [Li-].[O-2].[O-2].[O-2].[O-2].[O-2].[Ni].[Ni].[Ni].[Ni] MCUJFJGJUYOITH-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BFASWJXWTSCDRR-UHFFFAOYSA-M prop-2-enyl carbonate Chemical compound [O-]C(=O)OC[C]=C BFASWJXWTSCDRR-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
It is an object of the invention to provide a kind of cheap and new type lithium ion battery negative material of high power capacity, and the nonaqueous electrolytic solution secondary battery with long-life, high power capacity using this negative pole is provided.This negative pole at least contains a kind of sulfur simple substance as negative electrode active material or sulphur compound and copper foil current collector；This nonaqueous electrolytic solution secondary battery possesses positive pole, above-mentioned negative pole, barrier film and nonaqueous electrolytic solution.
Description
Technical field
The present invention relates to electrochemical energy source domain, particularly relate to the sulfur-bearing negative pole of a kind of lithium ion battery, and use the height of this negative pole
Performance lithium ion battery.
Background technology
Lithium rechargeable battery is the electrical energy storage device of a kind of high efficiency, high-energy-density, be widely used in small-sized can
Mobile electronic device.As other battery systems, lithium ion battery mainly has positive electrode, negative material, barrier film and electrolysis
The big critical material of liquid four is constituted, and the character of material and the performance of lithium ion battery have very important relation.Lithium-ion electric at present
The widely used positive electrode in pond is mainly lithium ion can reversibly embed-lithium ion the transition metal oxide of deintercalation, as with cobalt acid
Lithium (LiCoO2), ternary material (LiNi1/3Co1/3Mn1/3O2) etc. for the layered metal oxide of representative, with LiMn2O4 (LiMn2O4)
For the spinel-type metal-oxide represented, with LiFePO4 (LiFePO4) it is the olivine-type metal-oxide etc. of representative；
Negative material is that lithium ion can reversibly embed-the compound of deintercalation, such as lamellar graphite.The application of these high performance materials, determines
Lithium ion battery today is as can not the shaking of power supply of small-sized portable type communication electronic equipment (such as mobile phone, hand-held computer etc.)
Dynamic status.But along with the further development (such as electric automobile requirement in terms of power source) of society, existing lithium ion battery
System all need to improve at price, safety, specific capacity and power-performance, the raw-material aspect such as plentiful.Develop higher property
Material and the corresponding lithium ion cell electrode of energy are important.
Elemental sulfur, as the positive electrode of battery, has high energy density, abundant natural resources, cheap and environment
The multiple advantages such as close friend.Sulfur as theoretical specific capacity 1675mAh/g of the positive electrode of battery it is considered to be under very good
Generation anode material for lithium ion battery；If negative pole uses lithium metal (theoretical specific capacity 3860mAh/g), the lithium sulfur of formation
Secondary cell theoretical energy density can reach 2680Wh/Kg, is preferable high-energy density secondary battery.But at lithium-sulfur cell
In, sulfur and discharging product thereof are all electronics and ion insulator, and it is molten that many lithium sulfides that reduction process produces are soluble in organic electrolyte
In agent, these cause, and Li-S secondary cell high rate performance is poor, active material utilization is low, capacity attenuation is rapid, thus limits
It develops (seeing documents and materials: 1) P.G.Bruce, S.A.Freunberger, L.J.Hardwick, and J-M.Tarascon,
Nat.Mater.,2012,11,19；2) A.Manthiram, Y.-Z.Fu, and Y.-S.Su., Acc.Chem.Res., ASAP；
3) X.Ji, K.T.Lee, and L.F. Nazar, Nat.Mater., 2009,8,500 etc.).
For improving the cycle characteristics of lithium-sulfur cell, it is proposed that various solutions, such as U.S. Patent No. 7250233 and
No. 7078124, though to battery performance, some improves these methods, but practical application effect is the most obvious.The master of the present invention
Want inventor once by vitochemical method sulfur be fixed on the C-C skeleton of organic molecule (Japanese Patent No. 3871306,
Japanese Patent No. 4208451, Japanese Patent No. 4297673, Japanese Patent No. 4674883, U.S. Patent No. 6709787
Number) greatly suppress the problems of dissolution of sulfur, but relative to elemental sulfur, the manufacturing cost of this material is higher, battery capacity has subtracted
Low.
Summary of the invention
It is an object of the present invention to provide a kind of new type lithium ion battery negative pole, this negative pole has good electric conductivity, high
Active material utilization, excellent cycle performance.The negative pole that the present invention provides, including metallic copper collector and at least one sulfenyl
Material.This negative pole is in preparation process, and in the battery charging and discharging activation process being assembled into described negative pole, with sulfenyl
Material and the reaction of metallic copper.
Negative pole of the present invention has following characteristics, and its composition contains: copper current collector, negative electrode active material and binding agent, institute
State negative electrode active material and include at least one sulfenyl material and appropriate conductive agent.
Sulfenyl material of the present invention (sulfur simple substance or sulphur compound) is selected from sulfur simple substance (S8)、Li2Sn(n >=1), organic sulfur chemical combination
One or more in thing, inorganic sulphide.From high power capacity and the angle of low price of negative pole, preferably sulfur simple substance (S8)
And Li2Sn(n >=8), wherein elemental sulfur (S8) low price, apply simple optimization.Containing of the element sulphur that described sulfenyl material contains
Amount, be not particularly limited, the element sulphur that described sulfenyl material contains account for described sulfenyl material, conductive agent and weight of binder it
During the 10-95% of sum, combination property is preferable, and the lowest, the negative material capacity as battery is relatively low, and time the highest, the circulation of battery is special
Property reduce.
According to embodiment of the present invention, sulfur electrode of the present invention is used as negative pole, is coated on copper current collector by sulfenyl material
(in lithium-sulfur cell, usual sulfur is as positive pole, and aluminum is as collector), can be greatly improved the utilization rate of sulfur, i.e. improve electrode
Specific capacity.Copper current collector, in the charge and discharge process of the sulfur battery of the present invention, generates conductance with negative electrode active material element sulphur chemical combination
Rate is high, the compound of stable cycle performance, makes element sulphur be fixed, and improves sulfur materials circulation stability.
The preferred Copper Foil of copper current collector of the present invention, collector thickness and the material of Copper Foil, be not particularly limited.The thickness of Copper Foil
Degree is also not particularly limited, and optimization range is 1-30 μm, and 5-15 μm is most preferably.The material of Copper Foil can be fine copper or alloyed copper,
Fine copper or copper component alloyed copper more than 95% is preferably used from the angle of price and processability.
According to embodiment of the present invention, negative electrode active material is preferably properly added copper powder.Copper powder is in the battery charge and discharge of the present invention
Electric process generates with negative electrode active material element sulphur chemical combination electrical conductivity height, the compound of stable cycle performance, makes element sulphur obtain
Fixing, improve the specific capacity of material.Described copper powder includes pure copper powder, alloy copper powder, and partial oxidation or part sulfur
Change powder.Copper foil current collector and copper powder to a certain extent with negative electrode active material element sulphur chemical combination, generate that electrical conductivity is high, follow
The compound of ring stable performance, makes element sulphur be fixed, and improves the utilization rate of element sulphur, and makes prepared lithium sulfur electricity
Pond has the cycle performance of excellence.
Described conductive agent is selected from material with carbon element, and (acetylene black, Super P, Super S, 350G, carbon are fine in such as carbon black conductive agent
Dimension (VGCF), CNT (CNTs), Ketjen black (KetjenblackEC300J, KetjenblackEC600JD, Carbon
ECP, Carbon ECP600JD) etc.), graphite agent (KS-6, KS-15, SFG-6, SFG-15 etc.) carbon nanometer
A kind of conductive material in rod and Graphene etc. or the mixture of different materials.
Conductive agent can also be metal dust, as selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y,
At least one in Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Ta, W, Re, Os, Ir, Pt and Au
Metal dust or several metal alloy powders.Above-mentioned transition metal powders can be used alone can also be with above-mentioned Carbon Materials
It is used in mixed way.Particle diameters preferably is selected from micron level, more preferably from Nano grade.
The acting as of binding agent in the present invention, is adhered to described negative electrode active material on copper current collector, and strengthens the machine of negative pole
Tool globality, improves solid-solid interface and/or solid-liquid interface physical electrical contact, increases the electronics of whole negative pole and the conductivity of ion
Energy.Can select the different binding agent such as water system, oil system, this binding agent is selected from polyvinylidene fluoride (PVDF), polyvinyl alcohol
(PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), TPO (PP, PE etc.), butyronitrile
One in the polymer such as rubber (NBR), butadiene-styrene rubber (SBR), polyacrylonitrile (PAN), polyvinyl alcohol (PVA) or
Multiple.Dissolved with water, METHYLPYRROLIDONE (NMP) equal solvent and scattered (stick with paste containing cathode agent constituent, starch
Deng) and be applied to the one or two sides of copper foil current collector, then remove solvent, and form banding formed body (anode mixture layer)
After material.But the manufacture method of negative pole is not limited to foregoing illustrative method.
It is a further object to provide a kind of battery using negative pole noted earlier.The battery of the present invention is except using above institute
Stating outside negative pole, it also includes the required parts such as positive pole, barrier film and nonaqueous electrolytic solution in constituting.So the nonaqueous electrolytic solution of the present invention
Other elements, as long as having above-mentioned negative pole, are not particularly limited by secondary cell, can use known with existing
The element that nonaqueous electrolytic solution secondary battery is same.
The positive electrode that generally lithium ion battery uses can use in the present invention.The positive active material that positive pole relates to, can
To use the compound of reversibly occlusion-releasing (embedding and deintercalation) lithium ion, use Li for example, it is possible to enumeratexMO2Or
LiyM2O4The lithium-transition metal composite oxide that (in formula, M is transition metal, 0≤x≤1,0≤y≤2) represents, including spinelle
The lithium-transition metal composite oxide of shape, the lithium-transition metal composite oxide of layer structure, the lithium transition-metal of olivine structural
Composite oxides etc..
As its object lesson, LiCoO can be enumerated2Deng lithium and cobalt oxides, LiMn2O4Deng lithium manganese oxide, LiNiO2Deng
Lithium nickel oxide, Li4/3Ti5/3O4Deng Li-Ti oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides；Have
LiMPO4Materials of olivine-type crystalline texture such as (M=Fe, Mn, Ni) etc..
Lithium-contained composite oxide especially with layer structure or spinelle shape structure is preferred, LiCoO2、LiMn2O4、
LiNiO2、LiNi1/2Mn1/2O2Deng for the li-mn-ni compound oxide of representative, LiNil/3Mn1/3Co1/3O2、
LiNi0.6Mn0.2Co0.2O2Deng for the lithium manganese nickel cobalt composite oxides of representative or LiNi1-x-y-zCoxAlyMgzO2(in formula, 0≤x≤1,
0≤y≤0.1,0≤z≤0.1,0≤1-x-y-z≤1) etc. lithium-contained composite oxide.It addition, the composition in above-mentioned lithium-contained composite oxide
A part for element, by the addition element of Ge, Ti, Zr, Mg, Al, Mo, Sn etc. replaced containing lithium composite oxygen
Compounds etc. also comprise wherein.
These positive active materials, both can be used alone a kind, it is possible to two or more is also used.Such as, by using stratiform simultaneously
The lithium-contained composite oxide of structure and the lithium-contained composite oxide of spinel structure, can seek to take into account high capacity and safety
Improve.
For constituting the positive pole of nonaqueous electrolytic solution secondary battery, such as, above-mentioned positive active material is properly added white carbon black, second
The conductive auxiliary agents such as acetylene black, or the binding agent such as Kynoar, poly(ethylene oxide) etc., prepare anode mixture, by it with aluminium foil etc.
Current-collecting member uses as after coating on the banding molded body of core.But, the manufacture method of positive pole is not limited only to upper example.
According to embodiment of the present invention, wherein binding agent act as described positive electrode active material powder is adhered to described collection
On fluid, and strengthen the mechanical integrity of positive pole, improve solid-solid interface and/or solid-liquid interface physical electrical contact, increase whole just
The electronics of pole and the conductive performance of ion.Can select the different adhesive such as water system, oil system, this binding agent is selected from poly-inclined difluoro
Ethylene (PVDF), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), polyene
Hydro carbons (PP, PE etc.), nitrile rubber (NBR), butadiene-styrene rubber (SBR), polyacrylonitrile (PAN), polyvinyl alcohol (PVA)
Deng one or more in polymer.
In the nonaqueous electrolytic solution secondary battery that the present invention provides, it is not particularly limited for the barrier film that positive pole and negative pole are separated yet,
The various barrier films used in existing well-known nonaqueous electrolytic solution secondary battery can be used.
Owing to the effect of barrier film is to be separated by the both positive and negative polarity active substance of battery, it is to avoid any electron stream of positive and negative interpolar directly passes through,
Avoid battery short circuit；The ion out-of-date resistance of circulation is little as far as possible, so mostly selecting apertured polymeric film.Such as, employing is poly-
The polyolefin resin such as ethylene, polypropylene, or the pore barrier film that the polyester resin such as polybutylene terephthalate (PBT) is formed is
Preferably.It addition, these pore barrier films (pore film) also can overlapping use.Above-mentioned polymer microporous film is through material surface
The modified thin film obtained, the composite ceramics barrier film being coated on polyolefin such as ceramic powder (aluminium oxide, silicon oxide etc.) also may be used
To use.
The thickness of barrier film is not particularly limited yet, but considers safety and high capacity two aspect of battery, be preferably
5-30μm.It addition, the air permeability of barrier film (s/100mL) is not particularly limited yet, but preferably 10-1000(s/100mL),
More preferably 50-800(s/100mL), particularly preferably 90-700(s/100mL).
In the nonaqueous electrolytic solution secondary battery that the present invention provides, use nonaqueous solvent (organic solvent) is as nonaqueous electrolytic solution, wherein
The nonaqueous solvent of high-k is preferred.Owing to sulfide (the particularly inductor of elemental sulfur) is at the electrolyte of carbonates
In be difficult to solvation, in the electrolyte that this kind solvent is constituted, be generally difficult to discharge and recharge, so many ethers R (CH2CH2O) n-R'
(n=1-6;R and R' is methyl or ethyl etc.) it is preferred, particularly dimethyl ether tetraethylene glycol (TEG) (TEGDME), glycol dinitrate
Ether (DME), the one of 1,3-dioxolane (DOL) or combinations thereof etc. are it is furthermore preferred that these solvents are to many
Sulfide dissolubility is high, good stability.
It addition, a small amount of interpolation of carbonate-containing class is feasible.Wherein, it is recommended to use dielectric constant is the ester of more than 30.As
The ester of such high-k, for example, it is possible to enumerate ethylene carbonate, Allyl carbonate, butylene, gamma-butyrolacton,
Sulfur class ester (ethylene glycol sulfide etc.) etc..Wherein, preferably cyclic ester, ethylene carbonate, vinylene carbonate, propylene carbonate
The cyclic carbonate such as ester, butylene is particularly preferred.In addition to above-mentioned solvent, dimethyl carbonate, carbonic acid two can be used
Low viscous polarity linear carbonate that ethyl ester, Ethyl methyl carbonate etc. are representative, aliphatic branched chain type carbonats compound.Ring
Shape carbonic ester (particularly ethylene carbonate) is particularly preferred with the mixed solvent of linear carbonate.
It addition, in addition to above-mentioned nonaqueous solvent, the chain phosphoric acid such as chain-like alkyl esters, trimethyl phosphate such as methyl propionate can be used
Three esters；The nitrile solvents such as 3-methoxypropionitrile；The branched chain type compounds with ehter bond with dendrimer as representative etc. are non-aqueous
Solvent (organic solvent).
It addition, may be used without fluorine kind solvent.
As fluorine kind solvent, for example, it is possible to enumerate H (CF2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、
H(CF2)2OCH2CF3、H(CF2)2CH2O(CF2)2H etc. or CF3CHFCF2OCH3、CF3CHFCF2OCH2CH3
Etc. (perfluoroalkyl) alkyl ether of linear chain structure, i.e. 2-trifluoromethyl hexafluoro propyl methyl ether, 2-trifluoromethyl hexafluoro propyl group ether,
2-trifluoromethyl hexafluoro propyl group propyl ether, 3-trifluoromethyl octafluoro butyl methyl ether, 3-trifluoromethyl octafluoro butyl ether, 3-trifluoromethyl
Octafluoro butyl propyl ether, 4-trifluoromethyl ten fluorine amyl group methyl ether, 4-trifluoromethyl ten fluorine amyl group ether, 4-trifluoromethyl ten fluorine amyl group third
Ether, 5-trifluoromethyl ten difluoro hexyl methyl ether, 5-trifluoromethyl ten difluoro hexyl ether, 5-trifluoromethyl ten difluoro hexyl propyl ether,
6-trifluoromethyl ten tetrafluoro heptyl methyl ether, 6-trifluoromethyl ten tetrafluoro heptyl ether, 6-trifluoromethyl ten tetrafluoro heptyl propyl ether, 7-
Trifluoromethyl ten hexafluoro octyl group methyl ether, 7-trifluoromethyl ten hexafluoro octyl group ether, 7-trifluoromethyl ten hexafluoro octyl group propyl ether etc..
It addition, (perfluoroalkyl) alkyl ether of above-mentioned different (perfluoroalkyl) alkyl ether and above-mentioned linear chain structure also can and be used.
As the electrolytic salt used in nonaqueous electrolytic solution, the preferably perchlorate of lithium, organic boron lithium salts, the lithium of fluorochemical
The lithium salts such as salt, lithium imide salts.
As the example of such electrolytic salt, for example, it is possible to enumerate LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、
LiCF3SO3、LiCF3CO2、LiC2F4(SO3)2, LiN(C2F5SO2)2, LiC(CF3SO2)3、LiCnF2n+1SO3(n≥2)、
LiN(RfOSO2)2(in formula, Rf is fluoroalkyl) etc..In these lithium salts, fluorine-containing organic lithium salt is particularly preferred.
Fluorine-containing organic lithium salt, owing to anionic property is big and easily separated one-tenth ion, soluble in nonaqueous electrolytic solution.
Electrolyte lithium salt concentration in nonaqueous electrolytic solution, such as, 0.3mol/L (mol/L) is above preferably, more preferably
More than 0.7mol/L, preferably below 1.7mol/L, more preferably below 1.2mol/L.When the concentration of electrolyte lithium salt is too low,
Ionic conduction is spent little, and when too high, worry may not necessarily be dissolved electrolytic salt completely and be separated out.
It addition, in nonaqueous electrolytic solution, it is also possible to add the various additives of the performance that can improve the battery using it, do not make spy
Do not limit.
Such as, use the nonaqueous electrolytic solution that with the addition of the compound that intramolecular has C=C unsaturated bond, sometimes can suppress to use
The reduction of its battery charging and discharging cycle characteristics.
There is the compound of C=C unsaturated bond as this intramolecular, for example, it is possible to enumerate C6H5C6H11(cyclohexylbenzene) etc.
Aromatic compound；H(CF2)4CH2OOCCH=CH2, F(CF2)8CH2CH2OOCCH=CH2Etc. being fluorinated
Aliphatic compound；Fluorine-containing aromatic compound etc..It addition, 1,3-third sultone, 1,2-PD sulfuric ester is main tool
There are the compound (such as, chain or cyclic sulfonic acid ester, chain or cyclic sulfates etc.) of element sulphur, vinylene carbonate base ester, second
Thiazolinyl ethylene carbonate, carbonic acid ethylene fluoride ester etc. can also use, the most highly effective.Particularly adopt when negative electrode active material
During with highly crystalline material, the combined effect such as vinylene carbonate base ester, vinyl ethylene carbonate, carbonic acid ethylene fluoride ester is more preferable.
The addition of these various additives, is preferred to nonaqueous electrolytic solution total amount for example, 0.05-5wt%.
Further, above-mentioned vinylene carbonate, vinyl ethylene carbonate, carbonic acid ethylene fluoride ester, use containing these compounds
The battery of nonaqueous electrolytic solution, by charging, forms protecting film in negative terminal surface, and suppression is connect with nonaqueous electrolytic solution by negative electrode active material
Touch the reaction that causes, there is the effect of the decomposition etc. of nonaqueous electrolytic solution preventing from being caused by this reaction.
Additionally, the improvement of the hot properties in order to realize nonaqueous electrolytic solution secondary battery, also can add in nonaqueous electrolytic solution anhydride,
One in lithium carbonate, lithium nitrate or combinations thereof.
Anhydride, the surface modifier as negative pole is relevant with at negative terminal surface formation composite membrane, has the storage of battery when making high temperature
The function that characteristic etc. more improve.It addition, by anhydride is added to nonaqueous electrolytic solution, owing to can make in nonaqueous electrolytic solution
Moisture reduce, it is possible to make the gas generating capacity in the battery of this nonaqueous electrolytic solution of employing reduce.
Add to the anhydride of nonaqueous electrolytic solution, be not particularly limited, both can be the intramolecular change with at least 1 acid anhydride structure
Compound, it is also possible to be the compound with multiple acid anhydride structure.
As the object lesson of anhydride, for example, it is possible to enumerate mellitic acid trianhydride, malonic anhydride, maleic anhydride, butyryl oxide., third
Anhydride, pulvinic acid acid anhydride, phthalone anhydride, phthalic anhydride, pyromellitic acid dianhydride, lactic anhydride, naphthalic anhydride, toluene anhydride,
Thiobenzoate acid anhydride, biphenyl anhydride, citraconic anhydride, diethylene glycol amide anhydride, acetic anhydride, succinic anhydrides, cinnamic anhydride, penta
Dicarboxylic anhydride, glutaconic anhydride, valeric anhydride, itaconic anhydride, different butyric acid anhydride, isovaleric anhydride, benzoyl oxide etc., these can make
With one kind or two or more.It addition, the addition of the anhydride in nonaqueous electrolytic solution, nonaqueous electrolytic solution total amount is 0.05-1wt%
It is preferred.
The preparation method of the nonaqueous electrolytic solution secondary battery that the present invention provides, such as, between aforementioned positive electrode and negative pole, before clamping
State after barrier film in addition overlapping, make electrode layer laminate, wound after making electrode coiling body, be filled in packaging body, just,
Negative pole is attached by lead body (lead wire) etc. with the positive and negative electrode terminal of packaging body, more aforementioned nonaqueous electrolytic solution is injected
After in packaging body, sealed package and make.
As the packaging body of battery, the packaging bodies such as square, cylindrical shape that metal makes can be used, or be laminated by metal (aluminum etc.)
The layered product packaging body that film is formed, such as aluminum plastic film etc..
Further, the manufacture method of nonaqueous electrolytic solution secondary battery and the structure of battery, it is not particularly limited, arranges in packaging body
After positive pole, negative pole, barrier film and nonaqueous electrolytic solution, before battery fully seals, it is excellent for arranging the open formation process being charged
Choosing.So, in the charging initial stage produces gas or battery, the moisture of residual is removable to outside battery.
After carrying out above-mentioned open formation process remove electricity pool gas method, be not particularly limited, can use nature remove or
Any one that vacuum removes.It addition, before battery fully seals, it is possible to use the suitable forming battery such as extruding.
The nonaqueous electrolytic solution secondary battery that the present invention provides, due to high power capacity, battery behavior is the best, it is possible to use such spy
Property, can be used as the removable information-based instrument such as mobile phone, notebook computer drives the secondary cell of power supply, and, make
Extensively utilize for the power supply of the various machine such as electric automobile or hybrid electric vehicle.
Present inventor finds with unremitting effort through studying intensively, and finds that metallic copper can improve the utilization rate of elemental sulfur, finds simultaneously
The radius size of copper ion is the most close with lithium ion.By the electrode material constituted at sulfenyl materials such as elemental sulfurs is applied to copper
On paper tinsel, form pole piece with Copper Foil as collector, and this electrode plates is used for the negative pole of lithium-sulfur cell, and (usual elemental sulfur is always
Be considered as positive electrode) substantially increase the cycle life of the sulfenyl materials such as elemental sulfur, and by this negative pole with at lithium ion battery
In widely used positive pole, barrier film, nonaqueous electrolytic solution etc. constitute high performance lithium ion battery, achieve the achievement of the present invention.
Being further discovered that part in adding elemental sulfur and add copper powder, the effect of battery is more preferable.Described positive electrode includes that lithium ion can
Reversibly embedding-deintercalation lithium ion transition metal oxide, as with cobalt acid lithium (LiCoO2), ternary material (as
LiNi1/3Co1/3Mn1/3O2) etc. for representative stratiform metal-oxide, with LiMn2O4 (LiMn2O4) it is the spinelle of representative
The metal-oxide of type, with LiFePO4 (LiFePO4) it is the metal-oxide etc. of the olivine-type of representative.
In the present invention, the sulfur-bearing negative pole formed using Copper Foil as collector is in charge and discharge process, and the copper reaction of sulfur and collector is raw
Become the new compound insoluble in electrolyte.Copper, while the electric conductivity of the activity and active substance mixture that improve sulfur-sulfide linkage, enters
And the utilization rate of sulfur materials can be improved, and sulfur has been fixed on electrode, thus fundamentally solve the intrinsic of lithium-sulfur cell
Technical problem so that the performance of sulfur battery is greatly improved.In the electrode system or battery of the present invention, elemental sulfur
Utilization rate almost can arrive 100%, and capacity can be existing lithium ion close to or up the theoretical capacity (1670mAh/g) of sulfur
More than 4 times of negative electrode battery material graphite.The battery of the present invention has the cycle performance of excellence, can be with existing lithium-ion electric
Pond is suitable.
The current potential of the negative pole sulfenyl material that the present invention provides is about 1.7V (relative to lithium metal current potential).Use the electricity of this negative pole
Pond, during charge and discharge cycles, will not produce Li dendrite in negative terminal surface, be possible to prevent the internal short-circuit caused because of Li dendrite
Phenomenon.So use compared with the lithium metal of low potential or the conventional lithium ion battery of graphite with negative material, the battery of the present invention
Safer.On the other hand, the negative pole sulfenyl material of the present invention and employing spinel type lithium titanate (Li4Ti5O12: current potential 1.5V,
Actual capacity about 150mAh/g), running voltage close, but the theoretical capacity of the material of the present invention is more than 10 times of the latter.
Hold so utilizing the battery of the negative electrode active material of the present invention, the lithium titanate series lithium ion battery higher than same safety to compare battery
Measure higher.
The negative pole that the present invention provides has that the performance similar with lithium titanate, i.e. discharge curve be smooth, good conductivity, cyclical stability
Good.It addition, it also has the advantages such as wide material sources are cheap, preparation is easy, specific capacity is high.
Accompanying drawing explanation
Fig. 1 is the electrode charge and discharge curve of embodiment 1 negative pole.
Fig. 2 is the electrode charge and discharge curve of embodiment 1 positive pole.
Fig. 3 is the charging and discharging curve of embodiment 1 battery.
Fig. 4 is LiMn2O4/ Li battery and LiMn2O4/Cu-S8The cycle characteristics correlation curve of battery.
Detailed description of the invention
By embodiment, the present invention will be further described below in conjunction with the accompanying drawings.It is understood, however, that embodiment and comparative example are
For explaining embodiment of the present invention, in the range of without departing from present subject matter, scope is not by described enforcement
The restriction of example.
Other purpose of the present invention and advantage will be set forth in part in the description which follows, partly aobvious and easy from described explanation
See, or understood by the enforcement of the present invention.
Further, in the following description, what " % " was not specifically noted is quality criteria.
Embodiment 1
Prepared by negative pole: 60g sulfur powder and 30g conductive agent acetylene black are mixed, and being then added to 125 grams of solid contents is the PVDF of 8%
After solution (solvent: METHYLPYRROLIDONE (NMP)) is uniformly mixed, adjust slurry viscosity with NMP, preparation
Become powdery pulp；Being coated in the copper foil current collector of thickness 10 μm by above-mentioned cathode size, the electrode plates after coating is at 60 DEG C
Vacuum drying oven in be dried 12h remove solvent, then pole piece is struck out the disk of diameter 12mm, for negative pole material after weighing
Material.Sulfur content 1.1mg in this negative plate.Electrode discharge curve and discharge capacity are shown in Fig. 1.
Positive pole preparation is at the spinel lithium manganate (LiMn of 90 mass parts2O4, positive active material, actual capacity 106.3mAh/g)
In, mix the white carbon black as conductive agent of 5 mass parts, add polyvinylidene fluoride 5 mass parts in the mixture and be dissolved in NMP
Solution, mixing and make positive pole and close serosity so that it is by 70 eye mesh screens, remove the part that particle diameter is big.By equal for this anode sizing agent
On the one side of the aluminium foil being coated on thickness 15 μm, the electrode plates after coating is dried 12h in the vacuum drying oven of 80 DEG C evenly
After removing solvent, pole piece is struck out diameter 11mm disk, weighs, for the positive pole of battery.Active substance in positive pole
Content according to the ratio of positive electrode capacity anticathode capacity be 100 than 120(i.e. negative pole excess) design, coating preparation.Electrode discharge
Curve is shown in Fig. 2.
Battery preparation forms button cell with above-mentioned sulfur negative pole and above-mentioned spinel lithium manganese oxide anode pole piece and carries out battery
Evaluate.The preparation method of battery is as follows: in the glove box of argon gas atmosphere, according to cathode pole piece, three layers of porous septum
(PP/PE/PP), the laminated structure of bibulous paper, anode pole piece, aluminium backing, add electrolyte be assembled into the full battery of button, and
Testing the performance of battery in battery test system, discharge and recharge blanking voltage is 1.0V～2.6V.Battery discharge curve and battery
Discharge capacity (due to negative pole excess, be the most also positive discharge capacity) is shown in Fig. 3 and Biao 1.
Electrode capacity confirms:
The electrode slice of preparation, diameter are bigger 1mm than electrode slice, thickness is the metallic lithium foil of 0.1mm, electrolyte (the two (three of 1M
Methyl fluoride sulfonic acid) imine lithium (LiTFSI)-DOL/DME(3/7 volume ratio)), and barrier film (PP/PE/PP), filling
The glove box of full argon assembles button half-cell.After placing an evening, utilize charge and discharge device that battery behavior is evaluated.
The occasion of negative pole, discharging condition: with 0.5mA/cm2Discharge current half-cell determined electric current terminate to after 1.0V；Charging bar
Part: with 0.5mA/cm2Charging and discharging currents half-cell is charged to 3.0V；The occasion of positive pole, charge condition: with 0.5mA/cm2
Charging and discharging currents half-cell is charged to 4.3V；Discharging condition: with 0.5mA/cm2Discharge current half-cell determined electric current arrive
Terminate after 3.0V.
The evaluation of battery charging and discharging performance:
The most first battery is charged, fully charged after carry out constant-current discharge again, repeated multiple times under similarity condition afterwards
Circulation.Charge condition: after battery being charged to certain voltage with the charging and discharging currents of 0.5C, then continuation charging reaches under this voltage
Total charging time is (now for full charge) till 2.5 hours；Discharging condition: with the discharge current of 1C, battery is determined electric current and arrive
Terminate after certain voltage.Capability retention after 100 times of battery circulations is the capacity after 100 cycle charge-discharges of battery and the
The ratio (%) of the capacity after cycle charge-discharge.
Fig. 4 is LiMn2O4/ Li battery and LiMn2O4/Cu-S8The cycle characteristics of battery compares, it can be seen that LiMn2O4/
Cu-S8Battery and LiMn2O4The cycle characteristics of/Li battery is basically identical, and through the circulation in 30 cycles, capability retention is
More than 95%, Cu-S is described8Negative material has charge/discharge cycle characteristics well.
Comparative example 1
In the negative pole preparation process of embodiment 1, in addition to Copper Foil is substituted by the aluminium foil that thickness is 15 μm, same with embodiment 1
Sample is prepared for LiMn2O4/S8Button cell, test the results are shown in Table 1.
Comparative example 2
In the negative pole preparation process of embodiment 1, in addition to substituting Copper Foil with the nickel foil of thickness 20 μm, same with embodiment 1
Sample is prepared for LiMn2O4/S8Button cell, test the results are shown in Table 1.
Table 1LiMn2O4/S8The composition of battery and battery behavior
As it can be seen from table 1 compared with aluminum foil current collector and nickel foil collector, Copper Foil is as LiMn2O4/S8The negative pole of battery
Collector substantially increase negative electrode active material elemental sulfur utilization rate while, also improve LiMn2O4/S8The appearance of battery
Amount and circulating battery characteristic.
Table 1 is implemented positive active material LiMn in 12O4Actual capacity be 106.3mAh/g, and and S8Negative pole is constituted
The specific discharge capacity of battery, for being all higher than 100mAh/g, illustrates to utilize the elemental sulfur (S being coated on Copper Foil8) negative material is at electricity
Pond plays positive electrode capacity well, and its reversible capacity is relatively low.
Embodiment 2～7
In the negative pole preparation process of embodiment 1, in negative pole, with the addition of the pure copper powder of 5000 mesh according to the composition amounts of table 2, mixed
After closing slurrying, painting compress is on Copper Foil, is prepared for the negative pole of elemental sulfur.In addition, embodiment 3～7 is made similarly to Example 1
For LiMn2O4/Cu-S8) button cell, test the results are shown in Table 2.The charging/discharging voltage scope of battery is 1.0V～2.6V.
That tests the results are shown in Table 2.
Table 2LiMn2O4/S8The composition of battery and battery behavior
It is not difficult to find out from table 2, compared with Example 1, in negative pole, adds copper powder, improve LiMn2O4/S8Following of battery
Ring property.
Embodiment 8 ~ 11
In the negative pole preparation process of embodiment 1, in addition to substituting spinel lithium manganate with the positive active material of table 3, real
Execute example 8～11 and use identical negative pole preparation condition in embodiment 6.In charge-discharge test, the battery of iron phosphate lithium positive pole
Charging/discharging voltage scope is 1.0V～2.0V.The battery charging and discharging voltage range of other materials positive pole is 1.0V～2.6V.Test
The results are shown in Table 3.
The positive pole of table 3 sulfur battery is constituted and battery behavior
From table 3 it can be seen that the performance utilizing the sulfur negative material of copper powder and Copper Foil to play all kinds of positive electrode well (is held
Amount), the battery of composition, reversible capacity is low, and cycle characteristics is good.
Although the present invention being described in detail with reference to preferred embodiment, but, those skilled in the art should manage
Solve, the present invention can be made multiple amendment or replacement, and without departing from the basis illustrated in appended claims or its equivalent
The spirit and scope of invention.
Claims (10)
1. a battery cathode, it is characterised in that this negative pole includes copper current collector, negative electrode active material and binding agent, described negative electrode active material
Including at least one sulfenyl material and conductive agent, the element sulphur that described sulfenyl material contains account for described sulfenyl material, conductive agent and weight of binder it
The 10-95% of sum.
Battery cathode the most according to claim 1, it is characterised in that described sulfenyl material is sulfur simple substance, organosulfur compound or inorganic sulfur
Compound.
Battery cathode the most according to claim 1, it is characterised in that described sulfenyl material is Li2Sn, wherein n >=1.
Battery cathode the most according to claim 1, it is characterised in that described negative electrode active material also includes metallic copper powder.
Battery cathode the most according to claim 2, it is characterised in that described sulfenyl material is elemental sulfur, described copper current collector is Copper Foil.
Battery cathode the most according to claim 5, it is characterised in that described copper thickness is 1-30 μm.
Battery cathode the most according to claim 5, it is characterised in that described copper thickness is 5-15 μm.
8. a battery, including positive pole, porous septum and nonaqueous electrolytic solution, it is characterised in that also include claim 1-7 any claim institute
The negative pole stated.
Battery the most according to claim 8, it is characterised in that described positive pole possesses the lithium transition-metal of bedded structure again including at least a kind of
Close oxide, or a kind of lithium-transition metal composite oxide possessing spinelle shape, or a kind of lithium transition-metal possessing olivine structural is combined
Oxide.
Battery the most according to claim 8, it is characterised in that the solvent of described nonaqueous electrolytic solution be molecular formula be R (CH2CH2O)n-R'
Many ethers, wherein, n=1-6, R and R' are methyl or ethyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310006941.1A CN103915605B (en) | 2013-01-09 | Sulfur-bearing negative pole and corresponding nonaqueous electrolytic solution secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310006941.1A CN103915605B (en) | 2013-01-09 | Sulfur-bearing negative pole and corresponding nonaqueous electrolytic solution secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103915605A CN103915605A (en) | 2014-07-09 |
| CN103915605B true CN103915605B (en) | 2016-11-30 |
Family
ID=
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505184A (en) * | 2002-10-25 | 2004-06-16 | ����Sdi��ʽ���� | Lithium battery negative pole and lithium battery comprising the negative pole |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1505184A (en) * | 2002-10-25 | 2004-06-16 | ����Sdi��ʽ���� | Lithium battery negative pole and lithium battery comprising the negative pole |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104321912B (en) | Comprise the lithium secondary battery of multilayer active material layer | |
| JP6156939B2 (en) | Lithium ion secondary battery | |
| KR101772754B1 (en) | Method for producing positive electrode active material layer for lithium ion battery, and positive electrode active material layer for lithium ion battery | |
| JP4834030B2 (en) | Positive electrode for lithium secondary battery and lithium secondary battery using the same | |
| WO2014134967A1 (en) | Positive electrode film of lithium ion battery and preparation and application therefor | |
| CN111193071A (en) | Electrolyte of high-voltage quick-charging lithium ion battery and lithium ion battery | |
| CN104835961A (en) | Transition metal sulfide coated with carbon, preparation method and application | |
| WO2010148842A1 (en) | Lithium ion battery | |
| CN103311500A (en) | Lithium-ion battery negative pole piece and production method | |
| JP2012022794A (en) | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery | |
| WO2015161400A1 (en) | Sulphur-based transition metal composite cathode active material, corresponding cathode and corresponding battery | |
| JP6304746B2 (en) | Lithium ion secondary battery | |
| CN109841425B (en) | Capacitor battery and preparation method thereof | |
| CN102361095A (en) | Lithium ion battery with high specific power and preparation method for same | |
| CN103915602A (en) | New lithium sulfur battery positive electrode and lithium sulfur battery comprising new lithium sulfur battery positive electrode | |
| CN103915622A (en) | Transition metal sulfide negative electrode active material, corresponding negative electrode and corresponding cell | |
| JP6428243B2 (en) | Non-aqueous lithium secondary battery and manufacturing method thereof | |
| CN1819321A (en) | Lithium ion battery with high multiplying factor | |
| JP2011192561A (en) | Manufacturing method for nonaqueous electrolyte secondary battery | |
| CN110875476A (en) | Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery | |
| CN103762350A (en) | Titanium-containing anode material for lithium electrode and preparation method thereof | |
| CN106129314B (en) | A kind of power lithium-ion battery | |
| CN109935905B (en) | Electrolyte and lithium ion battery | |
| JP2018097935A (en) | Carbonaceous material, lithium secondary battery, and method of producing carbonaceous material | |
| JP6392566B2 (en) | Nonaqueous electrolyte secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |