CN107293701A - A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole - Google Patents
A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole Download PDFInfo
- Publication number
- CN107293701A CN107293701A CN201610204053.4A CN201610204053A CN107293701A CN 107293701 A CN107293701 A CN 107293701A CN 201610204053 A CN201610204053 A CN 201610204053A CN 107293701 A CN107293701 A CN 107293701A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- active material
- anode active
- carbon
- 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.)
- Pending
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- 239000006183 anode active material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 54
- 239000011258 core-shell material Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011257 shell material Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 16
- -1 polyethylene Polymers 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005275 alloying Methods 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011859 microparticle Substances 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000002296 pyrolytic carbon Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 235000013339 cereals Nutrition 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002210 silicon-based material Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 239000011883 electrode binding agent Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000011824 nuclear material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 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
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 229910013015 LiCoAlO2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011396 LiCoxNiyMnzO2 Inorganic materials 0.000 description 1
- 229910010747 LiFexM1-xPO4 Inorganic materials 0.000 description 1
- 229910010773 LiFexM1−xPO4 Inorganic materials 0.000 description 1
- 229910014971 LiMnCoO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013011 LiVPO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention proposes a kind of lithium ion battery anode active material and preparation method thereof and battery, and the negative active core-shell material is core shell structure, and the core includes Li-Si alloy particle, and the shell is carbon-coating；Core is used in the present invention for the negative active core-shell material of core shell structure that Li-Si alloy particle, shell are carbon-coating, the Volumetric expansion occurred when silicon is used as negative pole can effectively be alleviated, it is applied to battery, obtained battery can not only maintain higher capacity, meanwhile, also with good cycle performance.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole.
Background technology
In the prior art, as lithium ion battery anode active material, the actual capacity of graphite oneself close to the mAh/g of theoretical value 372, but it still can not meet high request of the electrokinetic cell to specific capacity and energy density；And the theoretical capacity of silicon is up to 4212 mAh/g, therefore it is received significant attention in field of lithium ion battery in recent years；The embedding lithium mechanism of silicon is alloying mechanism, and theoretical capacity calculates it in final embedding lithium state（Li22Si5）When volumetric expansion be original 400%, the problem of due to there is volumetric expansion, therefore, when being used as negative active core-shell material, the efflorescence of negative material can be seriously caused to crush, while negative terminal surface SEI films also can be destroyed and regenerated therewith, the expansion for eventually resulting in pole piece further increases, so as to cause electrode capacity significantly to be decayed, cycle performance of battery extreme difference.
In order to solve the system expansion issues of silicon, make the battery prepared that there is preferable cycle performance, prior art in carbon material mainly by adding a small amount of（3~10%）Silica flour, silicon monoxide powder or silicon alloy material, although the specific capacity of negative material can be brought up to 400 ~ 450mAh/g by this method, but the first charge-discharge efficiency of material can decline, and if the Capacity design of negative pole negative material is to more than 600mAh/g, then need the silicon of addition more than 20%, so not only substantially reduce material first charge-discharge efficiency, there is serious volumetric expansion in the substantial amounts of silicon materials of addition, the destruction and material that pole piece conductive network can be caused come off from collector, so as to cause cycle performance of battery poor, can not meet it is practical the need for.
The content of the invention
In order to solve the above-mentioned technical problem the application, proposes a kind of lithium ion battery anode active material, and the negative active core-shell material is core shell structure, and the core includes Li-Si alloy particle, and the shell is carbon-coating.
The present invention also provides a kind of preparation method of lithium ion battery anode active material, including：
(1) carbon source presoma, Li-Si alloy particle powder are mixed and disperseed with organic solvent, obtain slurries；
(2) removal organic solvent is dried in the slurries in step (1), obtains the presoma that carbon source presoma coats Li-Si alloy alloying pellet；
(3) presoma in step (2) is placed under inert atmosphere and be sintered, obtain the lithium ion battery anode active material that core is Li-Si alloy particle, shell is carbon-coating.
The present invention further provides a kind of negative electrode of lithium ion battery, the negative pole includes the lithium ion battery anode active material that the application is proposed.
The present invention proposes a kind of lithium ion battery, and the battery includes above-mentioned negative electrode of lithium ion battery.
In lithium ion battery, because the intercalation potential of the silicon as negative active core-shell material is higher than the intercalation potential of carbon material, therefore, in the charge and discharge process of battery, lithium ion can preferentially be embedded in silicon materials, so as to cause silicon to occur, when " full charge " occurs in silicon, silicon volumetric expansion is up to about 400%, seriously reduces the capacity and cycle performance of battery；Present inventor accidentally in find, use core for the negative active core-shell material of core shell structure that Li-Si alloy particle, shell are carbon-coating, can effectively prevent silicon materials from occurring serious Volumetric expansion caused by " full charge " when being used as negative pole；Speculate its reason, it is probably because in the Li-Si alloy particle that the application is provided, silicon materials have been " embedded " part lithium in itself, thus as cell negative electrode material in use, in the charge and discharge process of battery, the further embedded caused volumetric expansion of lithium is smaller, when de- lithium, lithium in original Li-Si alloy particle can also be deviate from the lump, to keep the high power capacity of battery, while can also alleviate the Volumetric expansion occurred when silicon is used as negative pole；In addition, the presence of Li-Si alloy particle surface carbon shell, Li-Si alloy particle and electrolyte can not only be separated, ensure its stability, topmost, the presence of the carbon shell, inner nuclear material can be coordinated to play more preferable electric conductivity, the part lithium being " embedded " in itself in Li-Si alloy particle simultaneously can maintain void structure one by one during deviating from the later stage, and the void structure can accommodate caused volumetric expansion during embedding lithium next time, therefore further alleviate the Volumetric expansion of negative pole；Negative active core-shell material proposed by the present invention is applied to battery, obtained battery can not only maintain higher capacity, simultaneously, negative active core-shell material described herein can also effectively avoid situations such as silicon during negative pole as occurring because of Volumetric expansion negative pole appearance " dropping off ", " cracking ", make obtained battery while higher capacity is maintained, also with good cycle performance.
Brief description of the drawings
Fig. 1 be the embodiment of the present application 1 in negative active core-shell material A1 field emission scanning electron microscope figure.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that embodiment described herein is merely to illustrate and explain the present invention, it is not intended to limit the invention.
The present invention provides a kind of lithium ion battery anode active material, and the negative active core-shell material is core shell structure, and the core includes Li-Si alloy particle, and the shell is carbon-coating；Preferably, the shell is pyrolytic carbon layer.
According to lithium ion battery anode active material proposed by the present invention, it is preferable that on the basis of the weight of the Li-Si alloy particle, the content of lithium is 10-45%；The Li-Si alloy particle surface is coated to the active material of the core shell structure of carbon-coating is used for negative pole, due in Li-Si alloy particle, silicon materials have been " embedded " part lithium in advance, effectively it can prevent in battery charge and discharge process, silicon materials are by the situation of excessive " insertion " lithium, effectively alleviate the Volumetric expansion that silicon is used to occur during negative pole, simultaneously, the lithium being " embedded " in advance is during the later stage deviates from, hole can be left, to accommodate embedding lithium next time, further alleviate volumetric expansion effectiveness, so that the capacity and cycle performance of battery obtain very big lifting.
According to lithium ion battery anode active material proposed by the present invention, it is preferable that the average grain diameter of the Li-Si alloy particle is 0.2 ~ 5 μm；It is further preferred that the average grain diameter of the Li-Si alloy particle is 0.5 ~ 2 μm；Inventors herein have recognized that, the size of Li-Si alloy particle is controlled, can be in the influence that effectively reduction negative material is produced because silicon occurs volumetric expansion, while obtained negative active core-shell material also has good processing characteristics.
According to lithium ion battery anode active material proposed by the present invention, it is preferable that the porosity of the carbon-coating is less than 5%；The present inventor has found that the carbon shell for being less than 5% using porosity can be good at coordinating the charge-discharge performance of nuclear material Li-Si alloy so that negative material has the cycle performance of higher capacity and Geng Gao in an experiment.
According to lithium ion battery anode active material proposed by the present invention, the thickness of the carbon-coating is 5-10 μm；The presence of carbon shell, the discharge and recharge of nuclear material Li-Si alloy particle can not only be coordinated, make it have more preferable charge-discharge performance and cycle performance, simultaneously, the presence of the carbon shell can also reduce electrolyte and be contacted with the direct of Li-Si alloy particle, not only inhibit SEI films being concatenated to form on silicon materials surface, moreover it is possible to maintain the stabilization of inner nuclear material Li-Si alloy particle, the battery prepared also has good cycle performance while charge/discharge capacity is kept；And the thickness of carbon shell is defined to 5-10 μm, the negative active core-shell material of obtained core shell structure has optimal equalization performance.
According to lithium ion battery anode active material proposed by the present invention, the mass ratio of the Li-Si alloy particle and carbon-coating is 1：1~1：5；The mass ratio of Li-Si alloy particle and carbon-coating is controlled in above range value, carbon-coating can be made to form uniform and stable clad in Li-Si alloy particle surface.
According to lithium ion battery anode active material proposed by the present invention, it is characterised in that the carbon-coating also contains additive, the additive is the one or more in carbon black, CNT, carbon fiber, graphene, graphite microparticles；The presence of additive can improve the uniform and stable property of clad carbon-coating, while the electric conductivity of whole negative material can also be improved.
According to lithium ion battery anode active material proposed by the present invention, on the basis of the gross mass of the carbon-coating, the content of the additive is 1-20%.
The invention also provides a kind of preparation method of lithium ion battery anode active material, including：
(1) carbon source presoma, Li-Si alloy particle powder are mixed and disperseed with organic solvent, obtain slurries；
(2) removal organic solvent is dried in the slurries in step (1), obtains the presoma that carbon source presoma coats Li-Si alloy alloying pellet.
(3) presoma in step (2) is placed under inert atmosphere and be sintered, obtain the lithium ion battery anode active material that core is Li-Si alloy particle, shell is carbon-coating.
Preferably, in the step (1), the mass ratio of the carbon source presoma and Li-Si alloy particle powder is 5:1~20:1.The mass ratio of carbon source presoma and Li-Si alloy particle is controlled, and then can control to be coated on the carbon shell thickness of Li-Si alloy particle surface.
In above-mentioned steps (1), one or more of the carbon source presoma in glucose, polyethylene, polypropylene, polybutene, polyacrylonitrile, polyvinyl chloride, pitch, phenolic resin, sulphurated siliastic, paraffin, inclined tetrafluoroethene；The organic solvent is selected from the one or more in hexane, thiacyclohexane, heptane, octane, decane, ethylene carbonate, dimethyl ether, diethyl ether, phenylate, toluene, dimethylbenzene, tetrahydrofuran, oxinane, dimethyl sulfoxide, dimethylformamide, 1-METHYLPYRROLIDONE；The process for dispersing can be dispersed with stirring, it is preferred to use ultrasonic disperse；It is specifically as follows and carbon source presoma is first dissolved in organic solvent, then adds Li-Si alloy particle, dispersed with stirring or ultrasonic disperse, obtain dispersed slurries.
Drying means in above-mentioned steps (2) for example can remove organic solvent using the conventional method for removing organic solvent in this area using sol-gal process, spray drying process, fluid-bed drying or freeze-drying.
Sintering temperature in above-mentioned steps (3) is 400 ~ 1000 DEG C, and sintering time is 6 ~ 12h, is specially the product that will be obtained in step (2) in being incubated 6 ~ 12 hours in 400 ~ 1000 DEG C under inert gas shielding, furnace cooling；Wherein inert gas is protective gas commonly used in the art, such as nitrogen, argon gas.
According to the preparation method of lithium ion battery anode active material proposed by the present invention, preferably, also include adding additive, one or more of the additive in carbon black, CNT, carbon fiber, graphene, graphite microparticles in the step (1).
Present invention further proposes a kind of negative electrode of lithium ion battery, the negative pole includes the lithium ion battery anode active material that the application is proposed.
The invention also provides a kind of lithium ion battery, the battery includes above-mentioned negative pole.
In the present invention, the positive pole of battery, barrier film and nonaqueous electrolyte liquid are had no particular limits, can be with various types of positive poles, barrier film and nonaqueous electrolytic solution commonly used in the art, as long as the negative pole that the battery is used contains the negative active core-shell material of core shell structure provided by the present invention.The preparation method of the negative pole can use various methods commonly used in the art, for example negative active core-shell material proposed by the present invention, negative pole can be bonded and mixed with negative pole organic solvent, be coated on negative electrode collector, negative electrode material layer is formed on negative current collector surface, dry, obtain the negative pole.Preferably, in the negative electrode material layer of the battery, the content for the negative active core-shell material that the present invention is provided is 80-100wt%；The species and content of the negative pole bonding agent can be the conventional selection of this area.For example, the negative pole bonding agent can be selected from carboxymethyl cellulose（CMC）, Kynoar（PVDF）, polytetrafluoroethylene (PTFE)（PTFE）, polyvinyl alcohol（PVA）, polyacrylic acid（PAA）, chitosan, sodium alginate, polyimides, butadiene-styrene rubber（SBR）At least one of with the various modifications such as TPO emulsion or non-modified bonding agent.Preferably, on the basis of the gross weight of negative active core-shell material, the content of the negative pole bonding agent is 0.01%-10%, preferably 0.02%-8%；The negative electrode material layer can optionally contain cathode conductive agent, and the cathode conductive agent is selected from least one of carbon black, nickel powder and copper powder, and to increase negative conductive, the consumption of cathode conductive agent is known to the skilled person.
The positive pole is known to those skilled in the art.The positive pole includes plus plate current-collecting body and coating and/or the positive electrode being filled on plus plate current-collecting body, and the positive electrode includes positive active material, positive conductive agent and positive electrode binder.
The preparation method of the positive pole is various methods commonly used in the art, for example, positive active material, positive conductive agent and positive electrode binder can be mixed with positive pole organic solvent, be coated on positive electrode collector, be dried to obtain the positive pole.
According to the present invention, the various positive active materials that the positive active material can be known in the art for example can be LiCoO2、LiVPO4、LiCoAlO2、LiMnCoO2、LiCoxNiyMnzO2（x+y+z=1）、LiMn2O4、LiNiO2And LiFexM1-xPO4（M is Co, Ni, Mn, 0.8≤x≤1）In one or more, wherein the consumption of the positive active material be this area conventional amount used.
The present invention is not particularly limited for the positive conductive agent in positive pole, can be the conventional positive conductive agent in this area, for example can be selected from least one of carbon black, graphite, acetylene black, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder, the consumption of positive conductive agent can be the conventional amount used of ability.Generally on the basis of the gross weight of positive active material, the content of positive conductive agent can be 0.5%-15%, preferably 1%-10%.
According to the present invention, the positive electrode binder can be various positive electrode binders commonly used in the art, for example can selected from polyvinylidene fluoride, polytetrafluoroethylene (PTFE),（It is fluorine-containing）Polyacrylate,（It is fluorine-containing）Polyurethane,（It is fluorine-containing）Epoxy resin, polyacrylic acid（PAA）, chitosan, sodium alginate, polyimides, butadiene-styrene rubber, poly- methylcellulose, poly- sodium carboxymethylcellulose pyce, hydroxypropyl methyl cellulose, POLYPROPYLENE GLYCOL and butadiene-styrene rubber（SBR）In one or more.Further, on the basis of the gross weight of positive active material, the content of the positive electrode binder is 0.01%-10%, preferably 0.02%-7%.
According to the present invention, the positive pole organic solvent and negative pole organic solvent can be conventional use of various organic solvents in this area, for example, can be the one or more in 1-METHYLPYRROLIDONE, dimethylformamide, diethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran and water and alcohol series solvent.
The both positive and negative polarity collector that the plus plate current-collecting body negative current collector is known to the skilled person, for example, can be one kind in aluminium foil, copper foil, Punching steel strip.
The barrier film is located between positive pole and negative pole.The barrier film is not particularly limited in the present invention, can be conventional use of various barrier films, such as polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper in lithium ion battery.
The nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and there is no particular limitation as to it, the nonaqueous electrolytic solution that this area can be used conventional.Such as electrolyte lithium salt can be selected from lithium hexafluoro phosphate（LiPF6）, lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, at least one of chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.Nonaqueous solvents can select chain acid esters and ring-type acid esters mixed solution, and wherein chain acid esters can be selected from dimethyl carbonate（DMC）, diethyl carbonate（DEC）, methyl ethyl carbonate（EMC）, methyl propyl carbonate（MPC）, dipropyl carbonate（DPC）And at least one of other fluorine-containing, sulfur-bearings or the chain organosilane ester containing unsaturated bond, ring-type acid esters can be selected from ethylene carbonate（EC）, propene carbonate（PC）, vinylene carbonate（VC）, gamma-butyrolacton（γ-BL）, sultone and at least one of other fluorine-containing, sulfur-bearings or the ring-type organosilane ester containing unsaturated bond.Generally, in nonaqueous electrolytic solution, the concentration of lithium salts is 0.1-2.0mol/L.
According to the present invention, other constructions and preparation method of the battery are known to the skilled person, and therefore not to repeat here.
Because above-mentioned battery employs the negative active core-shell material for the core shell structure that the present invention is provided, it can preferably alleviate the volumetric expansion problem of silicium cathode material, so that the battery of gained has preferable cycle performance while high power capacity is ensured.
Below by way of specific embodiment, the present invention is described in detail.
Wherein, in the application, the porosity of carbon shell is measured by BET, mercury injection method；The thickness of carbon shell is measured by TG-DSC, TEM.
Embodiment
1
(1) 10g polyacrylonitrile is taken to be dissolved in 100ml dimethylformamide, form 100g/L solution, the Li-Si alloy particle powder that 2g average grain diameters are 1000nm is taken (in Li-Si alloy particle powder, 44%) the weight ratio of lithium is, under electromagnetic agitation, Li-Si alloy particle powder is put into above-mentioned solution, ultrasonic disperse after stirring obtains slurries；
(2) slurries in step (1) are placed under argon atmosphere and be spray-dried under 80 DEG C of environment, obtain the presoma that carbon source presoma coats Li-Si alloy alloying pellet；
(3) presoma in step (2) is placed in the dry crucible of graphite, in being incubated 6h at 800 DEG C under argon atmosphere, the lithium ion battery anode active material A1 that core is Li-Si alloy particle, shell is carbon-coating is obtained after cooling；Negative active core-shell material A1 Flied emission electron-microscope scanning figure is as shown in Figure 1；
(4) negative active core-shell material that will be prepared by quality proportioning in step (3)：Acetylene black：CMC：SBR=100：2：1.5：Tabletting after 2.5 ratio is well mixed, 120 DEG C of vacuum drying 24h obtain testing pole piece；Using metal lithium sheet as to electrode, celgard2400 polypropylene porous films are barrier film, 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC)（Weight ratio is=1：1）Mixed solution assembled in the glove box full of argon gas for electrolyte, so as to prepare battery S1.
Embodiment
2
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, step (1) substitutes polyacrylonitrile by adding 10g polyvinyl alcohol, prepares negative active core-shell material A2 and battery S2.
Embodiment
3
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 20g, the average grain diameter of the Li-Si alloy particle powder of addition is 500nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A3 and battery S3.
Embodiment
4
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 10g, the average grain diameter of the Li-Si alloy particle powder of addition is 800nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A4 and battery S4.
Embodiment
5
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 20g, the average grain diameter of the Li-Si alloy particle powder of addition is 1000nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A5 and battery S5.
Embodiment
6
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 10g, the average grain diameter of the Li-Si alloy particle powder of addition is 1500nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A6 and battery S6.
Embodiment
7
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, the amount of the polyacrylonitrile added in step (1) is 20g, the average grain diameter of the Li-Si alloy particle powder of addition is 2000nm, the quality of the Li-Si alloy powder particle of addition is 2g, prepares negative active core-shell material A7 and battery S7.
Embodiment
8
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, also include adding additive in step (1), additive is 0.5g graphene and 0.5g carbon ink, prepares negative active core-shell material A8 and battery S8.
Embodiment
9
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, also include adding additive in step (1), additive is 0.5g CNT and 0.5g graphite microparticles, prepares negative active core-shell material A9 and battery S9.
Comparative example
1
Lithium ion battery anode active material nuclear battery is prepared using method same as Example 1, unlike, Li-Si alloy powder is replaced using Si powder in step (1), negative active core-shell material DA1 and battery DS1 is prepared.
Comparative example
2
Battery is prepared using method same as Example 1, unlike, the Li-Si alloy powder particle for being 1000nm with average grain diameter in step (4) directly replaces the negative active core-shell material prepared in step (3), the Li-Si alloy powder particle is directly designated as DA2, and the battery prepared is designated as DS2.
Performance test
1st, charge-discharge performance is tested
Battery S1-S9, DS1-DS2 are subjected to electrochemical property test under room temperature environment, charging and discharging currents are 0.2C, and blanking voltage is 0.005 ~ 0.8V, and test result is shown in Table 1.
2nd, cycle performance is tested
Battery S1-S9 and DS1-DS2 are subjected to charge-discharge performance test, test condition is：First with 0.5C constant-current discharges to 0.005V, then with 0.2C constant-current discharges to 0.005V, shelve 5 minutes；0.8V is charged to 0.5C, is shelved 5 minutes；Circulation 50 times, after circulation terminates, by the 50th capacity divided by circulation volume produces capability retention first, test result is shown in Table 1.
Table 1
。
Wherein, efficiency refers to efficiency for charge-discharge, is the percentage of de- lithium capacity and embedding lithium capacity.Capability retention refers to take off lithium specific discharge capacity after circulating 50 times with taking off the percentage of lithium specific discharge capacity first.
As shown in Table 1, the negative active core-shell material of the core shell structure provided using the application is used for negative pole, and lithium capacity is taken off first and is far longer than embedding lithium capacity first, and this is due to during de- lithium, the lithium being " embedded " in advance is also deviate from the lump, therefore de- lithium amount is far longer than lithium-inserting amount first first；It can thus be seen that the negative active core-shell material that the application is provided, effectively can prevent silicon materials from occurring serious Volumetric expansion because being excessively embedded lithium in battery charge and discharge process；The battery S1-S9 that the negative active core-shell material of the core shell structure provided simultaneously using the present invention is made takes off the minimum 363.5mAh/g of lithium specific capacity after circulating 50 times, it is far longer than 216.4 mAh/g in 132.7 mAh/g and the DS2 in DS1, capability retention reaches as high as 83.5% after circulating 50 times, it is therefore seen that, the battery that negative active core-shell material provided by the present invention is prepared, with good cycle performance.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the range of the technology design of the present invention; a variety of simple variants can be carried out to technical scheme, these simple variants belong to protection scope of the present invention.
Claims (17)
1. a kind of lithium ion battery anode active material, it is characterised in that the negative active core-shell material is core shell structure, the core includes Li-Si alloy particle, and the shell is carbon-coating.
2. lithium ion battery anode active material according to claim 1, it is characterised in that on the basis of the weight of the Li-Si alloy particle, the content of lithium is 10-45%.
3. lithium ion battery anode active material according to claim 1, it is characterised in that the average grain diameter of the Li-Si alloy particle is 0.2 ~ 5 μm.
4. lithium ion battery anode active material according to claim 3, it is characterised in that the average grain diameter of the Li-Si alloy particle is 0.5 ~ 2 μm.
5. lithium ion battery anode active material according to claim 1, it is characterised in that the porosity of the carbon-coating is less than 5%.
6. lithium ion battery anode active material according to claim 1, it is characterised in that the thickness of the carbon-coating is 3-10 μm.
7. lithium ion battery anode active material according to claim 1, it is characterised in that the mass ratio of the Li-Si alloy particle and carbon-coating is 1：1~1：5.
8. lithium ion battery anode active material according to claim 1, it is characterised in that the carbon-coating is pyrolytic carbon layer.
9. lithium ion battery anode active material according to claim 8, it is characterised in that the carbon-coating also contains additive, the additive is the one or more in carbon black, CNT, carbon fiber, graphene, graphite microparticles.
10. lithium ion battery anode active material according to claim 8, it is characterised in that on the basis of the gross mass of the carbon-coating, the content of the additive is 1-20%.
11. a kind of preparation method of lithium ion battery anode active material, it is characterised in that including：
(1) carbon source presoma, Li-Si alloy particle powder are mixed and disperseed with organic solvent, obtain slurries；
(2) removal organic solvent is dried in the slurries in step (1), obtains the presoma that carbon source presoma coats Li-Si alloy alloying pellet；
(3) presoma in step (2) is placed under inert atmosphere and be sintered, obtain the lithium ion battery anode active material that core is Li-Si alloy particle, shell is carbon-coating.
12. the preparation method of lithium ion battery anode active material according to claim 11, it is characterised in that the mass ratio of carbon source presoma and Li-Si alloy particle powder is 5 in the step (1):1~20:1.
13. the preparation method of lithium ion battery anode active material according to claim 11, characterized in that, one or more of the carbon source presoma in glucose, polyethylene, polypropylene, polybutene, polyacrylonitrile, polyvinyl chloride, pitch, phenolic resin, sulphurated siliastic, paraffin, inclined tetrafluoroethene；The organic solvent is selected from the one or more in hexane, thiacyclohexane, heptane, octane, decane, ethylene carbonate, dimethyl ether, diethyl ether, phenylate, toluene, dimethylbenzene, tetrahydrofuran, oxinane, dimethyl sulfoxide, dimethylformamide, 1-METHYLPYRROLIDONE.
14. the preparation method of lithium ion battery anode active material according to claim 11, it is characterized in that, also include adding additive, one or more of the additive in carbon black, CNT, carbon fiber, graphene, graphite microparticles in the step (1).
15. the preparation method of lithium ion battery anode active material according to claim 14, it is characterised in that sintering temperature is 400 ~ 1000 DEG C in the step (3), sintering time is 6 ~ 12h.
16. a kind of negative electrode of lithium ion battery, it is characterised in that the negative pole includes the lithium ion battery anode active material described in claim 1-9 any one.
17. a kind of lithium ion battery, it is characterised in that the battery includes the negative pole described in claim 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610204053.4A CN107293701A (en) | 2016-03-31 | 2016-03-31 | A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610204053.4A CN107293701A (en) | 2016-03-31 | 2016-03-31 | A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107293701A true CN107293701A (en) | 2017-10-24 |
Family
ID=60087429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610204053.4A Pending CN107293701A (en) | 2016-03-31 | 2016-03-31 | A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107293701A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108574091A (en) * | 2018-04-12 | 2018-09-25 | 合肥国轩高科动力能源有限公司 | Novel vanadium-based hydride negative electrode material of lithium ion battery and preparation method thereof |
| CN109461911A (en) * | 2018-10-22 | 2019-03-12 | 江西省科学院科技战略研究所(江西省科学院科技信息中心) | A kind of cladded type Li-Si alloy and its preparation method and application |
| CN109585838A (en) * | 2018-12-27 | 2019-04-05 | 蜂巢能源科技有限公司 | Silicon-carbon cathode material and preparation method thereof, power battery and electric vehicle |
| CN109786670A (en) * | 2019-01-24 | 2019-05-21 | 南开大学 | A kind of preparation method of high first-efficiency lithium ion secondary battery negative electrode active material |
| CN110444751A (en) * | 2019-08-05 | 2019-11-12 | 张振刚 | Li-Si-N nano compound film and preparation method thereof, negative pole structure and lithium battery |
| CN111146420A (en) * | 2019-12-26 | 2020-05-12 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
| CN111354925A (en) * | 2018-12-21 | 2020-06-30 | 浙江伏打科技有限公司 | Synthesis of carbon-bound lithium ion conductor-carbon composite negative electrode material with carbon fiber structure |
| CN111416110A (en) * | 2020-04-02 | 2020-07-14 | 上海电气集团股份有限公司 | Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof |
| CN111916704A (en) * | 2020-08-04 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Negative electrode material, preparation method, negative plate and battery |
| CN114388790A (en) * | 2020-10-21 | 2022-04-22 | 比亚迪股份有限公司 | Battery prelithiation slurry, battery negative plate and lithium ion battery |
| US11316147B2 (en) * | 2016-02-15 | 2022-04-26 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and method for producing negative electrode active material |
| WO2022194089A1 (en) * | 2021-03-19 | 2022-09-22 | 比亚迪股份有限公司 | Negative electrode material and preparation method therefor, and all-solid-state lithium battery |
| CN115117343A (en) * | 2021-03-19 | 2022-09-27 | 比亚迪股份有限公司 | Negative electrode material, preparation method thereof and all-solid-state lithium battery |
| CN115117331A (en) * | 2021-03-19 | 2022-09-27 | 比亚迪股份有限公司 | Composite silicon-based negative electrode material, negative plate and all-solid-state lithium battery |
| CN115117309A (en) * | 2021-03-19 | 2022-09-27 | 深圳市比亚迪锂电池有限公司 | Negative electrode material, preparation method thereof and all-solid-state lithium battery |
| CN115241448A (en) * | 2022-09-22 | 2022-10-25 | 北京阿特精思智能科技有限公司 | Honeycomb-structured carbon-silicon-lithium-carbon-based nano composite material and preparation method thereof |
| CN115377397A (en) * | 2022-10-09 | 2022-11-22 | 江苏正力新能电池技术有限公司 | Preparation method of carbon-layer-containing silicon negative electrode material, negative electrode plate and manufacturing method thereof, and lithium ion battery |
| CN117293297A (en) * | 2023-10-27 | 2023-12-26 | 上海屹锂新能源科技有限公司 | Preparation method and application of lithium silicon alloy material |
| WO2024139392A1 (en) * | 2022-12-26 | 2024-07-04 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method therefor and lithium-ion battery |
| CN115117309B (en) * | 2021-03-19 | 2025-04-15 | 深圳市比亚迪锂电池有限公司 | Negative electrode material and preparation method thereof and all-solid-state lithium battery |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07326342A (en) * | 1994-05-30 | 1995-12-12 | Mitsubishi Cable Ind Ltd | Negative electrode for lithium secondary battery, and lithium secondary battery using the same |
| US6383686B1 (en) * | 1999-01-26 | 2002-05-07 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, lithium secondary battery using said anode material, and method for charging of said secondary battery |
| CN1717822A (en) * | 2002-11-26 | 2006-01-04 | 昭和电工株式会社 | Electrode material comprising silicon and/or tin particles and production method and use thereof |
| CN1738075A (en) * | 2004-08-17 | 2006-02-22 | 比亚迪股份有限公司 | Lithium alloy composite material and its preparing method, minus pole material, negative pole structure and lithium secondary cells |
| CN1795573A (en) * | 2003-06-25 | 2006-06-28 | 株式会社Lg化学 | Anode material for lithium secondary cell with high capacity |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| JP2007335086A (en) * | 2006-06-12 | 2007-12-27 | Matsushita Electric Ind Co Ltd | Manufacturing method of electrode for lithium battery |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| US8241793B2 (en) * | 2009-01-02 | 2012-08-14 | Nanotek Instruments, Inc. | Secondary lithium ion battery containing a prelithiated anode |
| CN102709565A (en) * | 2012-05-30 | 2012-10-03 | 力芯（青岛）新能源材料有限公司 | Preparation method of lithium ion battery porous silicon carbon composite negative material |
| CN102754250A (en) * | 2010-02-19 | 2012-10-24 | 松下电器产业株式会社 | Coin-shaped lithium secondary battery |
| CN102832378A (en) * | 2012-08-28 | 2012-12-19 | 浙江瓦力新能源科技有限公司 | Carbon anode material for lithium ion battery and preparation method for carbon anode material |
| CN102867983A (en) * | 2011-07-04 | 2013-01-09 | 中国人民解放军63971部队 | Nonaqueous secondary lithium battery |
| CN103219504A (en) * | 2013-03-28 | 2013-07-24 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof |
| CN103280571A (en) * | 2013-05-27 | 2013-09-04 | 华南师范大学 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN104091920A (en) * | 2014-07-17 | 2014-10-08 | 黄冈师范学院 | A carbon-coated nano-scale lithium aluminum alloy negative electrode material and preparation method thereof |
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
| CN104766965A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Nano-scale lithium-silicon alloy material and its preparation method and application |
| CN105098250A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Lithium ion battery with lithium-free positive plate |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN105118971A (en) * | 2015-07-06 | 2015-12-02 | 新乡远东电子科技有限公司 | Lithium ion battery negative electrode material and preparation method |
| CN105359304A (en) * | 2013-03-13 | 2016-02-24 | 新强能电池公司 | Silicon particles for battery electrodes |
-
2016
- 2016-03-31 CN CN201610204053.4A patent/CN107293701A/en active Pending
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07326342A (en) * | 1994-05-30 | 1995-12-12 | Mitsubishi Cable Ind Ltd | Negative electrode for lithium secondary battery, and lithium secondary battery using the same |
| US6383686B1 (en) * | 1999-01-26 | 2002-05-07 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, lithium secondary battery using said anode material, and method for charging of said secondary battery |
| CN1717822A (en) * | 2002-11-26 | 2006-01-04 | 昭和电工株式会社 | Electrode material comprising silicon and/or tin particles and production method and use thereof |
| CN1795573A (en) * | 2003-06-25 | 2006-06-28 | 株式会社Lg化学 | Anode material for lithium secondary cell with high capacity |
| CN1738075A (en) * | 2004-08-17 | 2006-02-22 | 比亚迪股份有限公司 | Lithium alloy composite material and its preparing method, minus pole material, negative pole structure and lithium secondary cells |
| JP2007335086A (en) * | 2006-06-12 | 2007-12-27 | Matsushita Electric Ind Co Ltd | Manufacturing method of electrode for lithium battery |
| CN1909268A (en) * | 2006-07-10 | 2007-02-07 | 深圳市贝特瑞电子材料有限公司 | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method |
| US8241793B2 (en) * | 2009-01-02 | 2012-08-14 | Nanotek Instruments, Inc. | Secondary lithium ion battery containing a prelithiated anode |
| CN102754250A (en) * | 2010-02-19 | 2012-10-24 | 松下电器产业株式会社 | Coin-shaped lithium secondary battery |
| CN102867983A (en) * | 2011-07-04 | 2013-01-09 | 中国人民解放军63971部队 | Nonaqueous secondary lithium battery |
| CN102332571A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Silicon-carbon compound cathode material and manufacturing method thereof as well as lithium ion battery and cathode piece |
| CN102709565A (en) * | 2012-05-30 | 2012-10-03 | 力芯（青岛）新能源材料有限公司 | Preparation method of lithium ion battery porous silicon carbon composite negative material |
| CN102832378A (en) * | 2012-08-28 | 2012-12-19 | 浙江瓦力新能源科技有限公司 | Carbon anode material for lithium ion battery and preparation method for carbon anode material |
| CN105359304A (en) * | 2013-03-13 | 2016-02-24 | 新强能电池公司 | Silicon particles for battery electrodes |
| CN103219504A (en) * | 2013-03-28 | 2013-07-24 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof |
| CN103280571A (en) * | 2013-05-27 | 2013-09-04 | 华南师范大学 | Positive pole material of lithium ion battery and preparation method of positive pole material |
| CN104766965A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Nano-scale lithium-silicon alloy material and its preparation method and application |
| CN105098250A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Lithium ion battery with lithium-free positive plate |
| CN105098138A (en) * | 2014-05-08 | 2015-11-25 | 微宏动力系统（湖州）有限公司 | Negative plate used for lithium ion battery and preparation method thereof |
| CN104091920A (en) * | 2014-07-17 | 2014-10-08 | 黄冈师范学院 | A carbon-coated nano-scale lithium aluminum alloy negative electrode material and preparation method thereof |
| CN104124431A (en) * | 2014-08-12 | 2014-10-29 | 湖南元素密码石墨烯研究院（有限合伙） | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
| CN105118971A (en) * | 2015-07-06 | 2015-12-02 | 新乡远东电子科技有限公司 | Lithium ion battery negative electrode material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| SHINICHIROH IWAMURA等: "Li-Rich Li-Si Alloy As A Lithium-Containing Negative Electrode Material Towards High Energy Lithium-Ion Batteries", 《SCIENTIFIC REPORTS》 * |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11316147B2 (en) * | 2016-02-15 | 2022-04-26 | Shin-Etsu Chemical Co., Ltd. | Negative electrode active material, mixed negative electrode active material, negative electrode for nonaqueous electrolyte secondary battery, lithium ion secondary battery, and method for producing negative electrode active material |
| CN108574091A (en) * | 2018-04-12 | 2018-09-25 | 合肥国轩高科动力能源有限公司 | Novel vanadium-based hydride negative electrode material of lithium ion battery and preparation method thereof |
| CN109461911A (en) * | 2018-10-22 | 2019-03-12 | 江西省科学院科技战略研究所(江西省科学院科技信息中心) | A kind of cladded type Li-Si alloy and its preparation method and application |
| CN111354925A (en) * | 2018-12-21 | 2020-06-30 | 浙江伏打科技有限公司 | Synthesis of carbon-bound lithium ion conductor-carbon composite negative electrode material with carbon fiber structure |
| CN111354925B (en) * | 2018-12-21 | 2021-04-20 | 浙江伏打科技有限公司 | Synthesis of carbon-bound lithium ion conductor-carbon composite negative electrode material with carbon fiber structure |
| CN109585838A (en) * | 2018-12-27 | 2019-04-05 | 蜂巢能源科技有限公司 | Silicon-carbon cathode material and preparation method thereof, power battery and electric vehicle |
| CN109786670A (en) * | 2019-01-24 | 2019-05-21 | 南开大学 | A kind of preparation method of high first-efficiency lithium ion secondary battery negative electrode active material |
| CN109786670B (en) * | 2019-01-24 | 2021-08-06 | 南开大学 | A kind of preparation method of high first-efficiency lithium ion secondary battery negative electrode active material |
| CN110444751A (en) * | 2019-08-05 | 2019-11-12 | 张振刚 | Li-Si-N nano compound film and preparation method thereof, negative pole structure and lithium battery |
| CN111146420A (en) * | 2019-12-26 | 2020-05-12 | 宁德新能源科技有限公司 | Negative electrode material, and electrochemical device and electronic device comprising same |
| CN111416110A (en) * | 2020-04-02 | 2020-07-14 | 上海电气集团股份有限公司 | Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof |
| CN111916704B (en) * | 2020-08-04 | 2023-02-21 | 珠海冠宇电池股份有限公司 | Negative electrode material, preparation method, negative plate and battery |
| CN111916704A (en) * | 2020-08-04 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Negative electrode material, preparation method, negative plate and battery |
| CN114388790B (en) * | 2020-10-21 | 2023-11-14 | 比亚迪股份有限公司 | Pre-lithiation slurry for battery, negative plate for battery and lithium ion battery |
| CN114388790A (en) * | 2020-10-21 | 2022-04-22 | 比亚迪股份有限公司 | Battery prelithiation slurry, battery negative plate and lithium ion battery |
| WO2022194089A1 (en) * | 2021-03-19 | 2022-09-22 | 比亚迪股份有限公司 | Negative electrode material and preparation method therefor, and all-solid-state lithium battery |
| CN115117343A (en) * | 2021-03-19 | 2022-09-27 | 比亚迪股份有限公司 | Negative electrode material, preparation method thereof and all-solid-state lithium battery |
| CN115117331A (en) * | 2021-03-19 | 2022-09-27 | 比亚迪股份有限公司 | Composite silicon-based negative electrode material, negative plate and all-solid-state lithium battery |
| CN115117309A (en) * | 2021-03-19 | 2022-09-27 | 深圳市比亚迪锂电池有限公司 | Negative electrode material, preparation method thereof and all-solid-state lithium battery |
| CN115133011A (en) * | 2021-03-19 | 2022-09-30 | 比亚迪股份有限公司 | Negative electrode material, preparation method thereof and all-solid-state lithium battery |
| CN115117309B (en) * | 2021-03-19 | 2025-04-15 | 深圳市比亚迪锂电池有限公司 | Negative electrode material and preparation method thereof and all-solid-state lithium battery |
| CN115117343B (en) * | 2021-03-19 | 2024-12-10 | 比亚迪股份有限公司 | Negative electrode material and preparation method thereof and all-solid-state lithium battery |
| CN115241448B (en) * | 2022-09-22 | 2022-12-09 | 北京阿特精思智能科技有限公司 | Honeycomb-structured carbon-silicon-lithium-carbon-based nano composite material and preparation method thereof |
| CN115241448A (en) * | 2022-09-22 | 2022-10-25 | 北京阿特精思智能科技有限公司 | Honeycomb-structured carbon-silicon-lithium-carbon-based nano composite material and preparation method thereof |
| CN115377397B (en) * | 2022-10-09 | 2024-05-17 | 江苏正力新能电池技术有限公司 | Preparation method of carbon-layer-silicon-containing anode material, anode piece, preparation method of anode piece and lithium ion battery |
| CN115377397A (en) * | 2022-10-09 | 2022-11-22 | 江苏正力新能电池技术有限公司 | Preparation method of carbon-layer-containing silicon negative electrode material, negative electrode plate and manufacturing method thereof, and lithium ion battery |
| WO2024139392A1 (en) * | 2022-12-26 | 2024-07-04 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method therefor and lithium-ion battery |
| CN117293297A (en) * | 2023-10-27 | 2023-12-26 | 上海屹锂新能源科技有限公司 | Preparation method and application of lithium silicon alloy material |
| CN117293297B (en) * | 2023-10-27 | 2024-08-13 | 上海屹锂新能源科技有限公司 | Preparation method and application of lithium silicon alloy material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107293701A (en) | A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole | |
| US10770728B2 (en) | Anode material having porous core-shell structure and method of preparing the same and battery | |
| CN107808978B (en) | A kind of liquid active lithium supplement, its preparation method and use | |
| JP5329898B2 (en) | Negative electrode active material for lithium secondary battery and lithium secondary battery including the same | |
| CN101515640B (en) | Cathode and lithium ion secondary battery containing same | |
| CN110635116B (en) | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery | |
| CN100583501C (en) | Lithium ion battery cathode and preparation method thereof | |
| JP6448017B2 (en) | Lithium secondary battery | |
| KR101666871B1 (en) | Positive electrode active material and method of manufacturing the same, and rechargeable lithium battery including the positive electrode active material | |
| CN112310352B (en) | Negative electrode active material and secondary battery | |
| KR102769585B1 (en) | Lithium metal anode and method for manufacturing the same, and lithium battery using the anode | |
| EP3678229A1 (en) | Anode active material and anode using same, electrochemical device and electronic device | |
| JPWO2011001666A1 (en) | Non-aqueous electrolyte secondary battery positive electrode, method for producing the same, and non-aqueous electrolyte secondary battery | |
| CN114144919A (en) | Positive pole piece, electrochemical device comprising positive pole piece and electronic device | |
| CN102487151A (en) | Lithium ion secondary battery | |
| CN111213260A (en) | Anode, anode preparation method and lithium ion battery | |
| JP2005251684A (en) | Nonaqueous electrolyte secondary battery | |
| CN103794814B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN115101711A (en) | Negative plate, preparation method thereof and secondary battery | |
| CN110190258B (en) | Silicon-carbon composite material water-based composite slurry, preparation method thereof and lithium ion battery | |
| CN108539188A (en) | A kind of preparation method of liquid metal nano-particle and the preparation method of lithium ion battery | |
| EP3312909A1 (en) | Electroactive composites comprising silicon particles, metal nanoparticles and carbon nanostructures | |
| JP6691906B2 (en) | Secondary battery | |
| CN117317383A (en) | Battery and energy storage device | |
| CN115249786B (en) | Battery positive plate, preparation method thereof and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171024 |