CN105576245B - 锂离子电池 - Google Patents
锂离子电池 Download PDFInfo
- Publication number
- CN105576245B CN105576245B CN201410552824.XA CN201410552824A CN105576245B CN 105576245 B CN105576245 B CN 105576245B CN 201410552824 A CN201410552824 A CN 201410552824A CN 105576245 B CN105576245 B CN 105576245B
- Authority
- CN
- China
- Prior art keywords
- maleimide
- bismaleimide
- monomer
- lithium ion
- ion battery
- 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.)
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 50
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 39
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000004985 diamines Chemical class 0.000 claims abstract description 25
- 239000011883 electrode binding agent Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- -1 acyl Imines Chemical class 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- VPTHKCDQSIYZFV-UHFFFAOYSA-N 1-[2-(aminomethyl)phenyl]pyrrole-2,5-dione Chemical compound NCC1=CC=CC=C1N1C(=O)C=CC1=O VPTHKCDQSIYZFV-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- BIZYEXNGCULMQU-UHFFFAOYSA-N 3-ethenylpyrrole-2,5-dione Chemical compound C=CC1=CC(=O)NC1=O BIZYEXNGCULMQU-UHFFFAOYSA-N 0.000 claims description 2
- BHPSIKROCCEKQR-UHFFFAOYSA-N 3-sulfanylpyrrole-2,5-dione Chemical compound SC1=CC(=O)NC1=O BHPSIKROCCEKQR-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- DQBIPBSPUYNBJO-UHFFFAOYSA-N 6-iminocyclohexa-2,4-dien-1-ol Chemical compound OC1C=CC=CC1=N DQBIPBSPUYNBJO-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910003849 O-Si Inorganic materials 0.000 claims description 2
- 229910003872 O—Si Inorganic materials 0.000 claims description 2
- UMKZXSOQFHBKCO-UHFFFAOYSA-N bicyclo[4.2.0]octa-1,3,5-trien-7-imine Chemical compound C1=CC=C2C(=N)CC2=C1 UMKZXSOQFHBKCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 2
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 claims 1
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 claims 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 239000010439 graphite Substances 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 229910001290 LiPF6 Inorganic materials 0.000 description 9
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 9
- 239000005030 aluminium foil Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical class CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- JQQCMCDVLAZJHZ-UHFFFAOYSA-N lithium;methanesulfonic acid Chemical compound [Li].CS(O)(=O)=O JQQCMCDVLAZJHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
本发明涉及一种锂离子电池,包括正极、负极、隔膜及电解质溶液,该正极包括正极活性物质、导电剂及正极粘结剂,该正极粘结剂是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物,该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。
Description
技术领域
本发明涉及一种的锂离子电池。
背景技术
随着便携式电子产品的快速发展和普遍化,锂离子电池的市场需求与日俱增。与传统二次电池相比,锂离子电池具有能量密度高、循环寿命长、无记忆效应和环境污染小等优点。然而,近年来用于手机、笔记本电脑中的锂电池爆炸伤人事件屡屡发生,锂离子电池的安全问题已引起人们的广泛关注。锂离子电池在过度充放电、短路以及大电流长时间工作的情形下会释放出大量的热,可能发生热失控引起电池燃烧或爆炸,而电动汽车等应用领域对电池有更加严苛的安全要求。因此,锂离子电池的安全性研究具有重要意义。
发明内容
有鉴于此,确有必要提供一种能够提高安全性能的锂离子电池。
一种锂离子电池,包括正极、负极、隔膜及电解质溶液,该正极包括正极活性物质、导电剂及正极粘结剂,该正极粘结剂是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物,该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种,该有机二胺类化合物的分子通式由式(3)或式(4)表示,其中R3与R4为二价有机取代基,
(3);
(4)。
本发明采用由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物作为正极粘结剂应用于锂离子电池,能够具有较好的粘结力,且对锂离子电池充放电循环性能影响较小,并能够提高锂离子电池的热稳定性,起到过充保护的作用。
附图说明
图1为本发明实施例2和对比例1的锂离子电池的倍率性能曲线。
图2为本发明实施例3~6的锂离子电池的循环性能曲线。
图3为本发明实施例7的锂离子电池的过充电时电池的电压及温度随时间变化曲线。
图4为本发明比较例2的锂离子电池的过充电时电池的电压及温度随时间变化曲线。
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例对本发明提供的锂离子电池作进一步的详细说明。
本发明实施方式提供一种正极粘结剂,是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物。
该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。
该马来酰亚胺单体的分子通式可以由式(1)表示。
(1)
R1为单价有机取代基,具体地,可以为-R, -RNH2R, -C(O)CH3,-CH2OCH3, -CH2S(O)CH3, 单价形式的环脂族基团,单价形式的取代芳香族基团,或单价形式的未取代芳香族基团,如-C6H5, -C6H4C6H5,或-CH2(C6H4)CH3。R为1~6个碳的烃基,优选为烷基。所述取代优选是以卤素,1~6个碳的烷基或1~6个碳的硅烷基进行取代。该未取代芳香族基团优选为苯基、甲基苯基或二甲基苯基。该芳香族的苯环的数量优选为1~2个。
具体地,该马来酰亚胺单体可以选自N-苯基马来酰亚胺、N-(邻甲基苯基)-马来酰亚胺、N-(间甲基苯基)-马来酰亚胺、N-(对甲基苯基)-马来酰亚胺、N-环己烷基马来酰亚胺、马来酰亚胺、马来酰亚胺基酚、马来酰亚胺基苯并环丁烯、二甲苯基马来酰亚胺、N-甲基马来酰亚胺、乙烯基马来酰亚胺、硫代马来酰亚胺、马来酰亚胺酮、亚甲基马来酰亚胺、马来酰亚胺甲醚、马来酰亚胺基乙二醇及4-马来酰亚胺苯砜中的一种或多种。
该双马来酰亚胺单体的分子通式可以由式(2)表示。
(2)
R2为二价有机取代基,具体地,可以为-R-,-RNH2R-,-C(O)CH2-,-CH2OCH2-,-C(O)-,-O-,-O-O-,-S-,-S-S-,-S(O)-,-CH2S(O)CH2-,-(O)S(O)-, -R-Si(CH3)2-O-Si(CH3)2-R-,二价形式的环脂族基团,二价形式的取代芳香族基团,或二价形式的未取代芳香族基团,如伸苯基(-C6H4-),伸联苯基(-C6H4C6H4-),取代的伸苯基,取代的伸联苯基,-(C6H4)-R5-(C6H4)-,-CH2(C6H4)CH2-,或-CH2(C6H4)(O)-。R5为-CH2-,-C(O)-,-C(CH3)2-,-O-,-O-O-,-S-,-S-S-,-S(O)-,或-(O)S(O)-。R为1~6个碳的烃基,优选为烷基。所述取代优选是以卤素,1~6个碳的烷基或1~6个碳的硅烷基进行取代。该芳香族的苯环的数量优选为1~2个。
具体地,该双马来酰亚胺单体可以选自N,N’-双马来酰亚胺-4,4’-二苯基代甲烷、1,1’-(亚甲基双-4,1-亚苯基)双马来酰亚胺、N,N’-(1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-(4-甲基-1,3-亚苯基)双马来酰亚胺、1,1’-(3,3’-二甲基-1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-乙烯基双马来酰亚胺、N,N’-丁烯基双马来酰亚胺、N,N’-(1,2-亚苯基)双马来酰亚胺、N,N’-(1,3-亚苯基)双马来酰亚胺、N,N’-双马来酰亚胺硫、N,N’-双马来酰亚胺二硫、N,N’-双马来酰亚胺亚胺酮、N,N’-亚甲基双马来酰亚胺、双马来酰亚胺甲醚、1,2-双马来酰亚胺基-1,2-乙二醇、N,N’-4,4’-二苯醚-双马来酰亚胺及4,4’-双马来酰亚胺-二苯砜中的一种或多种。
该马来酰亚胺类衍生物单体可通过将上述马来酰亚胺单体、双马来酰亚胺单体或多马来酰亚胺单体中马来酰亚胺基团中的H原子以卤素原子取代。
该有机二胺类化合物的分子通式可以由式(3)或式(4)表示。
(3)
(4)
其中R3与R4为二价有机取代基。
具体地,R3可以为-(CH2)n-,-CH2-O-CH2-,-CH(NH)-(CH2)n-,二价形式的环脂族基团,二价形式的取代芳香族基团,或二价形式的未取代芳香族基团,如伸苯基(-C6H4-),伸联苯基(-C6H4C6H4-),取代的伸苯基或取代的伸联苯基。R4可以为-(CH2)n-,-O-,-S-,-S-S-,-CH2-O-CH2-,-CH(NH)-(CH2)n-或-CH(CN)(CH2)n-。n=1~12。所述取代优选是以卤素,1~6个碳的烷基或1~6个碳的硅烷基进行取代。该芳香族的苯环的数量优选为1~2个。
作为正极粘结剂的聚合物应的分子量可以为1000~50000。
具体地,该有机二胺类化合物可以包括但不限于乙二胺、苯二胺、二氨基二苯甲烷及二氨基二苯醚中的至少一种。
在一实施例中,当该马来酰亚胺单体为双马来酰亚胺,有机二胺类化合物为二氨基二苯甲烷,该添加剂可以由式(5)表示。
(5)
该聚合物的制备方法可以包括以下步骤:
将有机二胺类化合物在有机溶剂中溶解形成二胺溶液;
将马来酰亚胺类单体与有机溶剂混合并预加热,形成马来酰亚胺类单体的溶液;以及
将二胺溶液加入预加热的马来酰亚胺类单体的溶液中,保持预加热温度混合搅拌使反应充分进行,得到所述聚合物。
该马来酰亚胺类单体与该有机二胺类化合物的摩尔比可以为1:10~10:1,优选为1:1~6:1。该马来酰亚胺类单体的溶液中马来酰亚胺类单体与有机溶剂的质量比可以为1:100~1:1,优选为1:10~1:2。该马来酰亚胺类单体的溶液的预加热温度可以为80℃~180℃,优选为80℃~150℃。该二胺溶液中有机二胺类化合物与有机溶剂的质量比可以为1:100~1:1,优选为1:10~1:2。该有机二胺类化合物的溶液可以通过输送泵以一定速率输送至马来酰亚胺类单体的溶液中,输送完毕后持续搅拌一定时间,使反应充分进行,该混合搅拌的时间大于6小时,优选为12小时~48小时。该溶剂为能够溶解该马来酰亚胺类单体与该有机二胺类化合物的有机溶剂,例如γ-丁内酯、碳酸丙烯酯及N-甲基吡咯烷酮(NMP)。可以理解,为了使该聚合物具有合适的粘度需要保证该预加热温度在80℃~180℃区间,且反应时间较长,从而提高聚合物的支化度。
本发明实施方式提供一种正极材料,包括正极活性物质、导电剂及上述正极粘结剂,该正极粘结剂是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物。该正极粘结剂可以与该正极活性物质及导电剂均匀混合。该正极粘结剂在该正极材料中的质量百分含量可以为0.01%~50%,优选为1%~20%。
该正极活性物质可以为层状结构的锂-过渡金属氧化物,尖晶石型结构的锂-过渡金属氧化物以及橄榄石型结构的锂-过渡金属氧化物中的至少一种,例如,橄榄石型磷酸铁锂、层状结构钴酸锂、层状结构锰酸锂、尖晶石型锰酸锂、锂镍锰氧化物及锂镍钴锰氧化物。
该导电剂可以为碳素材料,如碳黑、导电聚合物、乙炔黑、碳纤维、碳纳米管及石墨中的一种或多种。
本发明实施例进一步提供一种锂离子电池,包括正极、负极、隔膜及电解质溶液。该正极与负极通过所述隔膜相互间隔。所述正极可进一步包括一正极集流体及设置在该正极集流体表面的所述正极材料。所述负极可进一步包括一负极集流体及设置在该负极集流体表面的负极材料。该负极材料与上述正极材料相对且通过所述隔膜间隔设置。
该负极材料可包括负极活性物质,并可进一步包括导电剂及粘结剂。该负极活性物质可以为钛酸锂、石墨、相碳微球(MCMB)、乙炔黑、微珠碳、碳纤维、碳纳米管及裂解碳中的至少一种。该导电剂可以为碳素材料,如碳黑、导电聚合物、乙炔黑、碳纤维、碳纳米管及石墨中的一种或多种。该粘结剂可以是聚偏氟乙烯(PVDF)、聚偏(二)氟乙烯、聚四氟乙烯(PTFE)、氟类橡胶、三元乙丙橡胶及丁苯橡胶(SBR)中的一种或多种。
所述隔膜可以为聚烯烃多孔膜、改性聚丙烯毡、聚乙烯毡、玻璃纤维毡、超细玻璃纤维纸维尼纶毡或尼龙毡与可湿性聚烯烃微孔膜经焊接或粘接而成的复合膜。
该电解质溶液包括锂盐及非水溶剂。该非水溶剂可包括环状碳酸酯、链状碳酸酯、环状醚类、链状醚类、腈类及酰胺类中的一种或多种,如碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸丙烯酯(PC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、碳酸二丙酯、N-甲基吡咯烷酮(NMP)、N-甲基甲酰胺、N-甲基乙酰胺、二甲基甲酰胺、二乙基甲酰胺、二乙醚、乙腈、丙腈、苯甲醚、丁二腈、己二腈、戊二腈、二甲亚砜、亚硫酸二甲酯、碳酸亚乙烯酯、碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、氟代碳酸乙烯酯、氯代碳酸丙烯酯、酸酐、环丁砜、甲氧基甲基砜、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丙酸乙酯、丙酸甲酯、二甲基甲酰胺、1,3-二氧戊烷、1,2-二乙氧基乙烷、1,2-二甲氧基乙烷、或1,2-二丁氧基中的一种或几种的组合。
该锂盐可包括氯化锂(LiCl)、六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)、甲磺酸锂(LiCH3SO3)、三氟甲磺酸锂(LiCF3SO3)、六氟砷酸锂(LiAsF6)、六氟锑酸锂(LiSbF6)、高氯酸锂(LiClO4)、Li[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3]及双草酸硼酸锂(LiBOB)中的一种或多种。
实施例1
将4g双马来酰亚胺(BMI)及2.207g二氨基二苯甲烷分别溶解在γ-丁内酯中,去除溶液中的氧气,将双马来酰亚胺溶液升温至130℃,然后以5 rpm/min的速率将二氨基二苯甲烷溶液滴加入双马来酰亚胺溶液中,滴完后保持130℃24小时,冷却后用甲醇沉淀,洗涤烘干,得到的正极粘结剂,由式(5)表示。
实施例2
按质量百分比,将80%的LiNi1/3Co1/3Mn1/3O2、10%的实施例1的正极粘结剂和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。以锂片作为对电极,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,组装成2032扣式电池,进行充放电性能测试。
实施例3
按质量百分比,将85%的LiNi1/3Co1/3Mn1/3O2、5%的实施例1的正极粘结剂和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。以锂片作为对电极,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,组装成2032扣式电池,进行充放电性能测试。
实施例4
按质量百分比,将85%的LiNi1/3Co1/3Mn1/3O2、4.5%的实施例1的正极粘结剂、0.5%的PVDF和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。以锂片作为对电极,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,组装成2032扣式电池,进行充放电性能测试。
实施例5
按质量百分比,将85%的LiNi1/3Co1/3Mn1/3O2、4%的实施例1的正极粘结剂、1%的PVDF和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。以锂片作为对电极,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,组装成2032扣式电池,进行充放电性能测试。
实施例6
按质量百分比,将85%的LiNi1/3Co1/3Mn1/3O2、3%的实施例1的正极粘结剂、2%的PVDF和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。以锂片作为对电极,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,组装成2032扣式电池,进行充放电性能测试。
实施例7
全电池的组装:按质量百分比,将94%的LiNi1/3Co1/3Mn1/3O2、3%的实施例1的正极粘结剂和3%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥,压缩并裁剪制成电池正极。
按质量百分比,将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铜箔上,于100℃真空干燥,压缩并裁剪制成电池负极。将正负极匹配,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,采用卷绕工艺制成63.5mm*51.5mm*4.0mm的软包电池。
比较例1
按质量百分比,将80%的LiNi1/3Co1/3Mn1/3O2、10%的PVDF和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。以锂片作为对电极,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,组装成2032扣式电池,进行充放电性能测试。
比较例2
全电池的组装:按质量百分比,将94%的LiNi1/3Co1/3Mn1/3O2、3%的PVDF和3%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥,压缩并裁剪制成电池正极。
按质量百分比,将94%的石墨负极、3.5%的PVDF和2.5%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铜箔上,于100℃真空干燥,压缩并裁剪制成电池负极。将正负极匹配,电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中,采用卷绕工艺制成63.5mm*51.5mm*4.0mm的软包电池。
比较例3
将双马来酰亚胺(BMI)单体与巴比土酸按摩尔比为2:1在NMP中混合溶解,在130°C搅拌加热反应24小时,冷却后用甲醇沉淀,洗涤烘干,得到聚合物。
比较例4
按质量百分比,将80%的LiNi1/3Co1/3Mn1/3O2、10%的比较例3的聚合物和10%的导电石墨混合,用N-甲基吡咯烷酮分散,将此浆料涂布于铝箔上,于120℃真空干燥12小时,制成正极极片。
溶解度测试
将实施例1和比较例3的聚合物分别用不同的有机溶剂溶解,结果如表1所示,实施例1的聚合物在乙酸乙酯,四氢呋喃,丙酮有机溶剂中基本不溶解,而比较例3能微溶或部分溶解在乙酸乙酯,四氢呋喃,丙酮有机溶剂中。另外,实施例1和比较例3均能完全溶解在强极性溶解,如N-甲基吡咯烷酮中。
表1
乙酸乙酯 | 四氢呋喃 | 丙酮 | N-甲基吡咯烷酮 | N,N-二甲基甲酰胺 | |
实施例1 | × | × | × | ○ | ○ |
比较例3 | + | + | ++ | ○ | ○ |
×—不溶,+—微溶,++—部分溶解,○—完全溶解
粘结力测试
分别对实施例2、比较例1和比较例4的正极极片进行粘结力测试。使用的胶粘带宽度为20mm±1mm,先撕去外面的3~5层的胶粘带,然后再取150mm以上的胶粘带(胶粘带粘合面不能接触手或其他物质)。一端与正极极片表面粘结,长度100mm,另一端接夹持器,然后用压辊在自重下以约300mm/min的速度在正极极片上来回滚压三次,在试验环境下停放20min~40min后进行试验。将正极极片自由端对折180º,并从正极极片上剥开粘合面15mm。把正极极片自由端和试验板分别夹在上、下夹持器上。使剥离面与试验机力线保持一致。试验机以300mm/min±10mm/min下降速度连续剥离,并有自动记录仪绘出剥离曲线,实验结果如表2所示。从表2中可以看出,虽然没有传统的PVDF(比较例1)粘结力强,但实施例2的正极极片能够具有一定的粘结力,可以满足在锂离子电池电极中粘结正极活性材料的要求。而比较例4的正极极片则几乎没有粘结力。
表2
试样名称 | 试样厚度μm | 试样宽度mm | 最大负荷N |
实施例2 | 68±2 | 20 | 3.2 |
比较例1 | 68±2 | 20 | 5.5 |
比较例4 | 68±2 | 20 | 0 |
吸液率测试
将实施例2和比较例1的正极极片先称重,放入电解液中浸泡48小时后,取出用滤纸擦干表面电解液,称重。计算公式(浸泡后的极片质量-浸泡前的极片质量)/浸泡前的极片质量*100%的值,实施例2的正极极片为13.7%,比较例1的负极极片为15.2%。说明虽然没有传统的PVDF(比较例1)吸液率高,但实施例2的正极极片能够具有一定的吸液率,可以满足在锂离子电池电极正极粘结剂的要求。
电化学性能测试
请参阅图1,对实施例2和比较例1的锂离子电池进行倍率性能测试,测试条件为:在2.8~4.3V范围内,分别以0.2C、0.5C和1C电流倍率恒流充放电循环10次;然后在2.8~4.5V范围内,以1C倍率充放电循环10次。从图中可以看出,在0.2C倍率下,实施例2前几次循环容量不断增加,最终和比较例1保持相同水平;但在0.5C和1C倍率下,实施例2的容量略低于比较例1。
请参阅图2,对实施例3、4、5和6的锂离子电池进行循环性能测试,测试条件为:在2.8~4.3V范围内,以0.2C电流倍率恒流充放电循环30次。从图中可以看出,实施例3的循环性能最稳定,而采用不同配比的复合组分粘结剂的电池,随PVDF组分增加,容量反而略有下降。
电池过充测试
将实施例7和比较例2的全电池均以1C倍率,过充至10V,观察电池现象。请参阅图3及图4,实施例7在过充电过程中最高温度小于100℃,电池不燃烧爆炸。比较例2过充至5V左右电池发生燃烧,温度迅速上升最终达到350℃以上。
本发明实施例采用由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物能够作为正极粘结剂应用于锂离子电池,且对锂离子电池充放电循环性能影响较小,并能够提高锂离子电池的热稳定性,起到过充保护的作用。
另外,本领域技术人员还可在本发明精神内做其他变化,当然,这些依据本发明精神所做的变化,都应包含在本发明所要求保护的范围之内。
Claims (10)
1.一种锂离子电池,包括正极、负极、隔膜及电解质溶液,该正极包括正极活性物质、导电剂及正极粘结剂,该正极粘结剂是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物,该聚合物为体型聚合物,该聚合物的分子量为1000~50000,该聚合物的制备方法包括以下步骤:
将有机二胺类化合物在有机溶剂中溶解形成二胺溶液;
将马来酰亚胺类单体与有机溶剂混合并预加热,该预加热的温度为80℃~180℃,形成马来酰亚胺类单体的溶液;以及
将二胺溶液加入预加热的马来酰亚胺类单体的溶液中,保持所述预加热的温度混合搅拌使反应充分进行,得到所述聚合物,其中混合搅拌的时间大于6小时,
该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种,该有机二胺类化合物的分子通式由式(3)或式(4)表示,其中R3与R4为二价有机取代基,
H2N-R3-NH2
(3);
2.如权利要求1所述的锂离子电池,其特征在于,R3为-(CH2)n-,-CH2-O-CH2-,-CH(NH)-(CH2)n-,伸苯基,伸联苯基,取代的伸苯基,取代的伸联苯基,二价形式的环脂族基团,R4为-(CH2)n-,-O-,-S-,-S-S-,-CH2-O-CH2-,-CH(NH)-(CH2)n-或-CH(CN)(CH2)n-,n=1~12。
3.如权利要求1所述的锂离子电池,其特征在于,该有机二胺类化合物包括乙二胺、苯二胺、二氨基二苯甲烷及二氨基二苯醚中的至少一种。
4.如权利要求1所述的锂离子电池,其特征在于,该马来酰亚胺单体的分子通式由式(1)表示,其中R1为单价有机取代基:
5.如权利要求4所述的锂离子电池,其特征在于,R1为-R,-RNH2R,-C(O)CH3,-CH2OCH3,-CH2S(O)CH3,-C6H5,-C6H4C6H5,-CH2(C6H4)CH3,或单价形式的环脂族基团;R为1-6个碳的烃基。
6.如权利要求1所述的锂离子电池,其特征在于,该马来酰亚胺单体选自N-苯基马来酰亚胺、N-(邻甲基苯基)-马来酰亚胺、N-(间甲基苯基)-马来酰亚胺、N-(对甲基苯基)-马来酰亚胺、N-环己烷基马来酰亚胺、马来酰亚胺、马来酰亚胺基酚、马来酰亚胺基苯并环丁烯、二甲苯基马来酰亚胺、N-甲基马来酰亚胺、乙烯基马来酰亚胺、硫代马来酰亚胺、马来酰亚胺酮、亚甲基马来酰亚胺、马来酰亚胺甲醚、马来酰亚胺基乙二醇及4-马来酰亚胺苯砜中的一种或多种。
7.如权利要求1所述的锂离子电池,其特征在于,该双马来酰亚胺单体的分子通式由式(2)表示,其中R2为二价有机取代基:
8.如权利要求7所述的锂离子电池,其特征在于,R2为-R-,-RNH2R-,-C(O)CH2-,-CH2OCH2-,-C(O)-,-O-,-O-O-,-S-,-S-S-,-S(O)-,-CH2S(O)CH2-,-(O)S(O)-,-CH2(C6H4)CH2-,-CH2(C6H4)(O)-,-R-Si(CH3)2-O-Si(CH3)2-R-,-C6H4-,-C6H4C6H4-,二价形式的环脂族基团,或-(C6H4)-R5-(C6H4)-,R5为-CH2-,-C(O)-,-C(CH3)2-,-O-,-O-O-,-S-,-S-S-,-S(O)-,或-(O)S(O)-,R为1~6个碳的烃基。
9.如权利要求1所述的锂离子电池,其特征在于,该双马来酰亚胺单体选自N,N’-双马来酰亚胺-4,4’-二苯基代甲烷、1,1’-(亚甲基双-4,1-亚苯基)双马来酰亚胺、N,N’-(1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-(4-甲基-1,3-亚苯基)双马来酰亚胺、1,1’-(3,3’-二甲基-1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-乙烯基双马来酰亚胺、N,N’-丁烯基双马来酰亚胺、N,N’-(1,2-亚苯基)双马来酰亚胺、N,N’-(1,3-亚苯基)双马来酰亚胺、N,N’-双马来酰亚胺硫、N,N’-双马来酰亚胺二硫、N,N’-双马来酰亚胺亚胺酮、N,N’-亚甲基双马来酰亚胺、双马来酰亚胺甲醚、1,2-双马来酰亚胺基-1,2-乙二醇、N,N’-4,4’-二苯醚-双马来酰亚胺及4,4’-双马来酰亚胺-二苯砜中的一种或多种。
10.如权利要求1所述的锂离子电池,其特征在于,该马来酰亚胺类单体与该有机二胺类化合物的摩尔比为1∶1~6∶1。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410552824.XA CN105576245B (zh) | 2014-10-17 | 2014-10-17 | 锂离子电池 |
PCT/CN2015/091982 WO2016058542A1 (zh) | 2014-10-17 | 2015-10-15 | 锂离子电池 |
US15/481,996 US20170214048A1 (en) | 2014-10-17 | 2017-04-07 | Lithium ion battery |
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US9362546B1 (en) | 2013-01-07 | 2016-06-07 | Quantumscape Corporation | Thin film lithium conducting powder material deposition from flux |
CN105683127B (zh) | 2013-10-07 | 2020-08-28 | 昆腾斯科普公司 | 用于锂二次电池的石榴石材料和制造和使用石榴石材料的方法 |
WO2016063813A1 (ja) * | 2014-10-21 | 2016-04-28 | 日本電気株式会社 | 二次電池用電極およびこれを用いた二次電池 |
KR102609408B1 (ko) | 2015-04-16 | 2023-12-04 | 퀀텀스케이프 배터리, 인코포레이티드 | 고체 전해질 제조를 위한 세터 플레이트 및 그를 사용하여 치밀한 고체 전해질을 제조하는 방법 |
US9966630B2 (en) | 2016-01-27 | 2018-05-08 | Quantumscape Corporation | Annealed garnet electrolyte separators |
US20170331092A1 (en) | 2016-05-13 | 2017-11-16 | Quantumscape Corporation | Solid electrolyte separator bonding agent |
WO2018027200A1 (en) | 2016-08-05 | 2018-02-08 | Quantumscape Corporation | Translucent and transparent separators |
WO2018075809A1 (en) | 2016-10-21 | 2018-04-26 | Quantumscape Corporation | Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same |
WO2018236394A1 (en) | 2017-06-23 | 2018-12-27 | Quantumscape Corporation | LITHIUM-FILLED GRENATE ELECTROLYTES WITH SECONDARY PHASE INCLUSIONS |
US10347937B2 (en) | 2017-06-23 | 2019-07-09 | Quantumscape Corporation | Lithium-stuffed garnet electrolytes with secondary phase inclusions |
US11600850B2 (en) | 2017-11-06 | 2023-03-07 | Quantumscape Battery, Inc. | Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets |
TWI658068B (zh) * | 2018-02-26 | 2019-05-01 | 臺灣塑膠工業股份有限公司 | 鋰電池用聚合物的製造方法、鋰電池電解液和鋰電池 |
CN112567547A (zh) * | 2018-04-27 | 2021-03-26 | 陶氏环球技术有限责任公司 | 用于锂离子电池组生产的溶剂系统 |
CN110311138B (zh) * | 2019-07-11 | 2022-05-31 | 安普瑞斯(无锡)有限公司 | 一种具有热动保护功能的锂离子二次电池 |
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CN103700860B (zh) * | 2012-09-27 | 2016-04-06 | 比亚迪股份有限公司 | 一种锂离子电池 |
TWI473321B (zh) * | 2012-12-12 | 2015-02-11 | Ind Tech Res Inst | 鋰電池與其形成方法 |
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