WO2022041025A1 - 正极材料及包含其的电化学装置和电子装置 - Google Patents
正极材料及包含其的电化学装置和电子装置 Download PDFInfo
- Publication number
- WO2022041025A1 WO2022041025A1 PCT/CN2020/111604 CN2020111604W WO2022041025A1 WO 2022041025 A1 WO2022041025 A1 WO 2022041025A1 CN 2020111604 W CN2020111604 W CN 2020111604W WO 2022041025 A1 WO2022041025 A1 WO 2022041025A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- present application
- metal
- lithium
- fluoride
- Prior art date
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 238000000137 annealing Methods 0.000 claims description 14
- 239000010406 cathode material Substances 0.000 claims description 13
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229910016509 CuF 2 Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910015475 FeF 2 Inorganic materials 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 36
- 238000000498 ball milling Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 20
- -1 FeF 3 Inorganic materials 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000003273 ketjen black Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910021392 nanocarbon Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229920005993 acrylate styrene-butadiene rubber polymer Polymers 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000005466 carboxylated polyvinylchloride Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920005994 diacetyl cellulose Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 229920000973 polyvinylchloride carboxylated Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Definitions
- the present application relates to the field of energy storage, in particular to a positive electrode material and an electrochemical device and an electronic device including the same, in particular to an all-solid-state secondary lithium battery.
- the battery is not only required to be light, but also required to have a high capacity and a long operating life.
- Lithium-ion batteries have taken a mainstream position in the market due to their outstanding advantages such as high energy density, high safety, no memory effect and long working life.
- the embodiments of the present application provide a positive electrode material, in an attempt to solve at least one problem existing in the related field at least to some extent.
- Embodiments of the present application also provide a positive electrode, an electrochemical device, and an electronic device using the positive electrode material.
- the present application provides a positive electrode material, which includes a composite material, and the composite material includes a metal fluoride, wherein the molar ratio of the fluorine element F to the metal element M in the metal fluoride is y , the molar ratio of the fluorine element F and the metal element M in the composite material is z, wherein y ⁇ z ⁇ y+2; and wherein the M includes at least one of Al, Cu, Co, Ni, Mn, Fe or Ag A sort of.
- the present application provides a method of making a composite material, the method comprising:
- the molar ratio of fluorine element F to metal element M in the metal fluoride is y; the molar ratio of fluorine element F to metal element M in the positive electrode material is z, y ⁇ z ⁇ y+2;
- the M includes at least one of Al, Cu, Co, Ni, Mn, Fe or Ag.
- the present application provides a positive electrode comprising the positive electrode material according to the embodiments of the present application.
- the present application provides an electrochemical device including the positive electrode according to the embodiments of the present application.
- the electrochemical device is an all-solid-state secondary lithium battery.
- an all-solid-state secondary lithium battery includes a positive electrode, a negative electrode, and a solid-state electrolyte.
- the positive electrode includes the positive electrode material of the above embodiments.
- the present application provides an electronic device including an electrochemical device according to an embodiment of the present application.
- the positive electrode material of the present application has the advantages of wide source of raw materials, simple preparation process, easy operation, and low production cost.
- the lithium battery prepared from the positive electrode material of the present application has improved specific capacity, rate performance and cycle performance of the positive electrode material, as well as better charge-discharge performance.
- FIG. 1 shows a schematic diagram of the electrochemical reaction of the composite cathode active material in Example 9 of the present application after the first charge and discharge.
- FIG. 2 shows the curves of the capacity retention rate of the all-solid-state secondary lithium batteries of Comparative Example 2, Comparative Example 4 and Example 4 of the present application as a function of the number of cycles.
- a list of items joined by the terms "one of,” “one of,” “one of,” or other similar terms can mean that any of the listed items one.
- the phrase “one of A and B” means A only or B only.
- the phrase “one of A, B, and C” means A only; B only; or C only.
- Item A may contain a single element or multiple elements.
- Item B may contain a single element or multiple elements.
- Item C may contain a single element or multiple elements.
- a list of items joined by the terms "at least one of,” “at least one of,” “at least one of,” or other similar terms may mean the listed items any combination of .
- the phrase “at least one of A and B” means A only; B only; or A and B.
- the phrase "at least one of A, B, and C” means A only; or B only; C only; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
- Item A may contain a single element or multiple elements.
- Item B may contain a single element or multiple elements.
- Item C may contain a single element or multiple elements.
- the present application provides a positive electrode material, which includes a composite material, and the composite material includes a metal fluoride, wherein the molar ratio of the fluorine element F to the metal element M in the metal fluoride is y, the molar ratio of the fluorine element F and the metal element M in the composite material is z, wherein y ⁇ z ⁇ y+2; and wherein the M includes Al, Cu, Co, Ni, Mn, Fe or Ag. at least one.
- the M includes Cu, Fe, or a combination thereof.
- y ⁇ z ⁇ y+1.5 In some embodiments, y ⁇ z ⁇ y+0.05, y ⁇ z ⁇ y+0.1, y ⁇ z ⁇ y+0.15, y ⁇ z ⁇ y+0.2, y ⁇ z ⁇ y+0.5, y ⁇ z ⁇ y+0.7, y ⁇ z ⁇ y+0.9, y ⁇ z ⁇ y+1, or y ⁇ z ⁇ y+1.2.
- the composite material further includes fluorinated graphite, the structural formula of the fluorinated graphite is CF x , and the molar ratio of the fluorine element F to the carbon element C in the CF x is x, wherein 0 ⁇ x ⁇ 1.
- the mass ratio of the graphite fluoride to the metal fluoride is w, 0 ⁇ w ⁇ 0.2. In some embodiments, 0 ⁇ w ⁇ 0.15. In some embodiments, 0 ⁇ w ⁇ 0.1. In some embodiments, 0 ⁇ w ⁇ 0.05. In some embodiments, w may also be 0.02, 0.03, 0.06, 0.07, and the like.
- the metal fluoride includes at least one of CoF 3 , NiF 3 , MnF 2 , MnF 3 , FeF 3 , FeF 2 , AlF 3 , or CuF 2 . In some embodiments, the metal fluoride includes FeF 3 , CuF 2 , or a combination thereof.
- the cathode material contains lithium. In some embodiments, the positive electrode material does not contain lithium.
- the composite material included in the cathode material can be represented as MF y .w(CF x ), wherein the definitions of M, w, x, and y are as described above, respectively.
- the embodiments of the present application provide a method for preparing a composite material, the method comprising:
- the molar ratio of fluorine element F to metal element M in the metal fluoride is y; the molar ratio of fluorine element F to metal element M in the composite material is z, y ⁇ z ⁇ y+2;
- the M includes at least one of Al, Cu, Co, Ni, Mn, Fe or Ag.
- metal fluoride and graphite fluoride are as defined above.
- the mixing is performed by a ball mill, V-blender, three-dimensional blender, airflow blender, or horizontal mixer. In some embodiments, the mixing is high energy ball mill mixing.
- the ball milling is a wet ball milling or a dry ball milling. In some embodiments, the ball milling is a wet ball milling.
- a ball milling dispersant is used in the ball milling process.
- the ball milled dispersant includes absolute ethanol.
- the volume ratio of ball mill material to mill balls is 1:3 to 1:20. In some embodiments, the ratio of ball milling material to milling ball volume is 1:10.
- the rotational speed in the ball milling step is 300 r/min to 1200 r/min. In some embodiments, the rotational speed in the ball milling step is 800 r/min.
- the ball milling time is 4 hr to 24 hr. In some embodiments, the ball milling time is 4hr, 6hr, 10hr, 15hr, 20hr, 24hr, or a range of any two of these values.
- the drying temperature is 60°C to 120°C. In some embodiments, the drying temperature is 60°C, 70°C, 80°C, 100°C, 120°C, or a range of any two of these values.
- the annealing temperature is 200°C to 600°C. In some embodiments, the annealing temperature is 200°C, 250°C, 300°C, 350°C, 400°C, 500°C, 600°C, or a range of any two of these values.
- the annealing time is 10 hr to 72 hr. In some embodiments, the annealing time is 10hr, 15hr, 20hr, 25hr, 30hr, 35hr, 40hr, 50hr, 60hr, 65hr, 72hr, or a range of any two of these values.
- the annealing process is performed in an atmosphere sintering furnace.
- the atmosphere sintering furnace can be an atmosphere tube furnace, an atmosphere box furnace, or other sintering furnaces with similar atmosphere protection functions.
- the atmosphere used in the atmosphere sintering furnace is an inert gas.
- the inert gas is high purity argon or high purity nitrogen.
- the working principle of solid-state lithium batteries is basically the same as that of traditional lithium-ion batteries.
- the structural change is to replace traditional liquid organic electrolytes and separators with solid-state electrolytes, making the battery safer.
- the structure of solid-state lithium battery is also simpler, mainly composed of positive electrode, solid electrolyte and negative electrode.
- the cathodes used in solid-state lithium batteries are mostly traditional lithium-containing cathode materials, such as LiCoO 2 , LiFePO 4 , and the like.
- the specific capacity of these lithium-containing cathode materials is far lower than that of the anode, which cannot meet the needs of high-energy density all-solid-state lithium batteries.
- Solid-state lithium batteries using lithium metal as the negative electrode must be matched with positive electrode materials with higher energy density.
- Metal fluoride (such as FeF 3 , FeF 2 and CuF 2 , etc.) cathode materials can provide energy densities as high as 1000Wh/Kg to 1600Wh/Kg, much higher than the 600Wh/Kg to 800Wh/Kg of the LiCoO 2 system, so it is very useful potential.
- lithium-free cathode materials such as metal fluorides often use cheap iron elements, so they also have the advantages of abundant resources, low cost, and environmental friendliness.
- metal fluoride and other lithium-free cathode materials have the following shortcomings that cannot be ignored: First, the conductivity of metal fluoride is generally low. It is reported that the conductivity of FeF 3 is only 10 -17 S/cm, which is close to that of an insulator. ; In the process of charging and discharging, the discharge voltage is lower than the charging voltage, that is, the so-called voltage hysteresis phenomenon occurs, and the rate and cycle stability of the material are poor. Second, the transition metal ions are easily dissolved from the positive electrode material during the charge and discharge process, enter the electrolyte and have side reactions with it, which accelerates the capacity decay during the cycle.
- the present invention provides a positive electrode material for a lithium battery.
- the initial state of the positive electrode material is a composite material of metal fluoride and fluorinated graphite.
- the composite material of the metal fluoride and fluorinated graphite of the present application has the following advantages as a positive electrode material: (1) the addition of graphite fluoride can significantly improve the specific capacity of the positive electrode material; (2) such as As shown in Figure 1, during the first discharge process, the fluorinated graphite on the surface of the positive electrode material reacts with the lithium ions released from the negative electrode to generate nanocarbons in situ, thereby increasing the conductivity of the positive electrode, which is conducive to stabilizing the discharge voltage and improving the discharge.
- the graphite fluoride will generate LiF in addition to the in-situ generation of nano-carbon, and these products can also be used as a lithium source to compensate for the excess of the cathode material. Lithium loss during secondary cycling, thereby improving long-term cycling stability.
- the metal fluoride and fluorinated graphite composite cathode material of the present invention has higher specific capacity and improved rate performance and cycle performance.
- the lithium battery positive electrode material provided by the present invention has wide raw material sources, simple preparation process, easy operation and low production cost.
- the all-solid-state secondary lithium battery prepared with the positive electrode material of the present invention has good charge-discharge performance, and has a great application prospect in the field of 3C electronic products and batteries for electric vehicles.
- Embodiments of the present application provide an electrochemical device including any device that undergoes an electrochemical reaction.
- the electrochemical device of the present application includes a negative electrode having a negative electrode active material capable of occluding and releasing metal ions; a positive electrode according to embodiments of the present application; an electrolyte; and a separator disposed between the positive electrode and the negative electrode membrane.
- the electrochemical devices of the present application include, but are not limited to, secondary batteries.
- the electrochemical device is a lithium secondary battery.
- the lithium secondary battery includes, but is not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery, an all-solid-state secondary lithium battery.
- the material, composition, and manufacturing method of the negative electrode used in the electrochemical device of the present application may include any of the techniques disclosed in the prior art.
- the negative electrode is the negative electrode described in US Patent Application US9812739B, which is incorporated herein by reference in its entirety.
- the negative electrode includes a current collector and a layer of negative active material on the current collector.
- the anode active material layer includes an anode active material.
- the negative active material includes, but is not limited to: lithium metal, structured lithium metal, natural graphite, artificial graphite, mesophase microcarbon beads (MCMB), hard carbon, soft carbon, silicon, silicon-carbon Composite, silicon-oxygen material, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO 2 , lithiated TiO 2 -Li 4 Ti 5 O 12 of spinel structure, Li-Al alloy or any of them combination.
- MCMB mesophase microcarbon beads
- the negative active material layer includes a binder.
- binders include, but are not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyfluoro Ethylene, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene Rubber, epoxy or nylon.
- the anode active material layer includes a conductive material.
- the conductive material includes, but is not limited to: natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel, aluminum, silver, or polyphenylene derivative.
- the current collector includes, but is not limited to, copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, or a conductive metal clad polymer substrate.
- the negative electrode may be obtained by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a current collector.
- the solvent may include, but is not limited to: deionized water, N-methylpyrrolidone.
- the negative electrode in the all-solid-state secondary lithium battery is a metallic lithium foil.
- a positive electrode in an all-solid-state secondary lithium battery includes a positive electrode material and a conductive agent according to any of the embodiments of the present application.
- the positive electrode includes a current collector and a layer of positive active material on the current collector.
- the positive electrode active material layer includes the positive electrode material according to the embodiment of the present application.
- the positive active material layer further includes a binder and/or a conductive agent.
- the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
- the binder includes at least one of the following compounds: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, containing Ethylene oxide polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, ring Oxygen resin or nylon, etc.
- the conductive agent includes at least one of the following compounds: conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, carbon nanotube.
- the current collector may include, but is not limited to, aluminum.
- the positive electrode can be prepared by a preparation method known in the art.
- the positive electrode can be obtained by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and coating the active material composition on a current collector.
- the solvent may include, but is not limited to: N-methylpyrrolidone.
- the electrolyte that can be used in the embodiments of the present application may be an electrolyte known in the prior art.
- the electrolyte includes an organic solvent, a lithium salt, and an additive.
- the organic solvent of the electrolytic solution according to the present application may be any organic solvent known in the prior art that can be used as a solvent of the electrolytic solution.
- the electrolyte used in the electrolyte solution according to the present application is not limited, and it may be any electrolyte known in the prior art.
- the additive for the electrolyte according to the present application may be any additive known in the art as an additive for the electrolyte.
- the organic solvent includes, but is not limited to: ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate or ethyl propionate.
- the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt.
- the lithium salts include, but are not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium difluorophosphate (LiPO 2 F 2 ), bistrifluoromethanesulfonimide Lithium LiN(CF 3 SO 2 ) 2 (LiTFSI), Lithium Bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 )(LiFSI), Lithium Bisoxalate Borate LiB(C 2 O 4 ) 2 (LiBOB) ) or lithium difluorooxalate borate LiBF 2 (C 2 O 4 ) (LiDFOB).
- LiPF 6 lithium hexafluorophosphate
- LiBF 4 lithium tetrafluoroborate
- LiPO 2 F 2 lithium difluorophosphate
- LiPFSI bistrifluoromethanesulfonimide Lithium LiN(CF 3 SO
- the concentration of the lithium salt in the electrolyte is: 0.5 mol/L to 3 mol/L, 0.5 mol/mol/L to 2 mol/L, or 0.8 mol/L to 1.5 mol/L.
- the solid-state electrolyte used in the all-solid-state secondary lithium battery includes at least one of the following compounds: Li 3 YCl 6 , Li 3 YBr 6 , Li 3 OCl, LiPON, Li 0.5 La 0.5 TiO 3 , Li 1+x Al x Ti 2-x (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , Li 10 GeP 2 S 12 (LGPS), Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , Li 3.25 Ge 0.25 P 0.75 S 4 , Li 11 AlP 2 S 12 and Li 7 P 3 S 11 .
- a separator is provided between the positive electrode and the negative electrode to prevent short circuits.
- the material and shape of the separator that can be used in the present application are not particularly limited, and it may be any of the techniques disclosed in the prior art.
- the separator includes a polymer or inorganic or the like formed from a material that is stable to the electrolyte of the present application.
- the release film may include a substrate layer and a surface treatment layer.
- the base material layer is a non-woven fabric, film or composite film with a porous structure, and the material of the base material layer is selected from at least one of polyethylene, polypropylene, polyethylene terephthalate and polyimide.
- a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene non-woven fabric, a polyethylene non-woven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected.
- At least one surface of the base material layer is provided with a surface treatment layer, and the surface treatment layer may be a polymer layer or an inorganic material layer, or a layer formed by mixing a polymer and an inorganic material.
- the inorganic layer includes inorganic particles and a binder, and the inorganic particles are selected from aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconium oxide, One or a combination of yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and barium sulfate.
- the binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, One or a combination of polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene.
- the polymer layer contains a polymer, and the material of the polymer is selected from polyamide, polyacrylonitrile, acrylate polymer, polyacrylic acid, polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyvinylidene fluoride or polyvinylidene fluoride. At least one of (vinylidene fluoride-hexafluoropropylene).
- the electronic device of the present application may be any device using the electrochemical device according to the embodiments of the present application.
- the electronic devices include, but are not limited to: notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets , VCR, LCD TV, Portable Cleaner, Portable CD Player, Mini Disc, Transceiver, Electronic Notepad, Calculator, Memory Card, Portable Recorder, Radio, Backup Power, Motor, Automobile, motorcycle, Power-assisted Bicycle, Bicycle , lighting equipment, toys, game consoles, clocks, power tools, flashes, cameras, large household batteries or lithium-ion capacitors, etc.
- lithium batteries The preparation of lithium batteries is described below by taking lithium batteries as an example and in conjunction with specific embodiments. Those skilled in the art will understand that the preparation methods described in this application are only examples, and any other suitable preparation methods are within the scope of this application. .
- the positive electrode active material powders prepared in Comparative Examples and Examples were subjected to XRD tests.
- the reference standard for the test is JIS K 0131-1996 General Principles of X-ray Diffraction Analysis.
- Test working conditions CuK alpha radiation
- the working current is 250mA
- the continuous scanning is adopted
- the working voltage is 40kV
- the scanning range is 2 ⁇ 10-70°
- the step size is 0.1°
- the scanning speed is 0.2 seconds/step.
- the XRD test principle is that when a beam of monochromatic X-rays is incident on a crystal, since the crystal is composed of a unit cell with atoms regularly arranged, the distance between these regularly arranged atoms is of the same order of magnitude as the wavelength of the incident X-ray, so different atoms scatter.
- the X-rays interfere with each other and produce strong X-ray diffraction in some special directions.
- the phase existing in the material is determined.
- the positive electrode active material powders prepared in Comparative Examples and Examples were subjected to SEM tests.
- the SEM test standard refers to JY/T010-1996 General Principles of Analytical Scanning Electron Microscopy. Testing principle of scanning electron microscope: Scanning electron microscope is based on the interaction of electrons and matter. It uses a very finely focused high-energy electron beam to scan on the sample to excite various physical information. Through the reception, magnification and display imaging of this information, an observation of the surface topography of the test specimen is obtained.
- the equipment used in the gram capacity test of the all-solid-state secondary lithium batteries prepared in the comparative examples and examples is a blue electric tester (model CT2001A), and the test environment temperature is normal temperature (25° C.).
- the test method is to discharge with a constant current at a set rate to the discharge cut-off voltage, and then charge it with a constant current at a certain rate to the charge cut-off voltage.
- the charging and discharging test rates in the present invention are all 0.1C, with reference to the theoretical specific capacity of FeF 3 of 712 mAh/g and the theoretical specific capacity of CuF 2 of 893 mAh/g.
- the positive electrode active materials prepared in the Examples and Comparative Examples and the conductive agent Ketjen Black were mixed uniformly.
- the obtained powder and solid electrolyte Li 7 P 3 S 11 were placed in a stainless steel cold-pressing mold, and cold-pressed under a pressure of 300 MPa to obtain a double-layer sheet of positive electrode and solid electrolyte, wherein the positive electrode active material, solid electrolyte Li 7
- the mass ratio of P 3 S 11 and the conductive agent Ketjen Black is 60:30:10.
- the lithium metal foil is placed on the other side of the solid electrolyte in the above-mentioned double-layer sheet, placed together in a cold pressing mold, and a pressure of 200 MPa is further applied to ensure sufficient contact between the lithium metal and the solid electrolyte film, that is, to obtain an all-solid secondary lithium battery.
- the resulting mixture was transferred to a tube furnace, and heated to 300-500°C at a heating rate of 3°C/min under the protection of a high-purity argon gas flow of 0.3 L/min, followed by annealing for 24 hours. After the annealing is completed, the material is cooled to room temperature with the furnace, and then the material is crushed and sieved to obtain a composite material MF y .w (CF x ) of metal fluoride and fluorinated graphite, which is used as the positive electrode active material of the present application; wherein y is the molar ratio of fluorine element F to metal element M in the metal fluoride; z is the molar ratio of fluorine element F and metal element M in the composite material; x is the fluorine element F and carbon element in the CF x The molar ratio of C; and w is the mass ratio of the graphite fluoride to the metal fluoride. Wherein Example 7 did not perform annealing treatment after drying.
- Table 2 shows the relevant performance test results of some examples and comparative examples.
- Table 3 shows the test results of some examples and comparative examples under different charge and discharge rates.
- ⁇ indicates that the battery has no charge and discharge capacity after 20 cycles of charge and discharge.
- the annealing temperature has a significant effect on the gram capacity of the graphite fluoride and iron trifluoride composite cathode active material.
- the initial discharge and charge capacities of the material are 377.5mAh/g and 232.9mAh/g, respectively.
- the annealing temperature increased from 150 °C to 350 °C, the initial discharge and charge capacities of the materials were greatly improved, which were 554.8mAh/g and 458.7mAh/g, respectively. This is due to the easier diffusion reaction of CFx with FeF3 lattice with increasing temperature.
- the electrochemical performance of the copper fluoride material can also be improved by composite treatment of copper fluoride and graphite fluoride.
- the charge-discharge capacity of the composite cathode material is also related to the fluorocarbon molar ratio x in the fluorinated graphite material. The higher the fluorocarbon molar ratio, the more favorable it is to improve the discharge gram capacity of the material.
- the solid-state lithium batteries prepared from the positive electrode material of the present invention were charged and discharged at different rates, and the capacity retention rates were all above 85%, while the capacity of the comparative example showed a large attenuation, especially in the comparative example.
- At high rates of 0.2C and 0.5C there is almost no charge-discharge capacity after 20 cycles. This is because in the embodiment, after the metal fluoride material and the fluorinated graphite material are composited, during the first discharge process, the fluorinated graphite on the surface of the positive electrode material can undergo a conversion reaction with lithium to generate nano-carbon in situ, thereby increasing the conductivity of the positive electrode. It is beneficial to improve the kinetics of the conversion reaction.
- lithium fluoride will also be generated, which can also be used as a lithium source to compensate for the lithium loss of the cathode material during multiple cycles, thereby improving the material's performance. Long-term cycling stability.
- FIG. 2 shows the curves of the capacity retention rate of the all-solid-state secondary lithium batteries of Comparative Example 2, Comparative Example 4 and Example 4 of the present application as a function of the number of cycles. It can be seen from Figure 2 that the incorporation of CFx into FeF3 can significantly improve the capacity retention rate of all-solid-state secondary lithium batteries.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims (9)
- 一种正极材料,其包括一种复合材料,所述复合材料包括金属氟化物,其中所述金属氟化物中氟元素F与金属元素M的摩尔比为y,所述复合材料中氟元素F和金属元素M的摩尔比为z,其中y<z≤y+2;并且其中所述M包括Al、Cu、Co、Ni、Mn、Fe或Ag中的至少一种。
- 根据权利要求1所述的正极材料,其中所述复合材料进一步包括氟化石墨,所述氟化石墨的结构式为CF x,所述CF x中氟元素F和碳元素C的摩尔比为x,其中0<x≤1。
- 根据权利要求2所述的正极材料,其中所述氟化石墨与所述金属氟化物的质量比为w,0<w≤0.2。
- 根据权利要求1所述的正极材料,其中所述金属氟化物包括CoF 3、NiF 3、MnF 2、MnF 3、FeF 3、FeF 2、AlF 3或CuF 2中的至少一种。
- 一种制备复合材料的方法,所述方法包括:(1)将金属氟化物和氟化石墨混合、烘干;和(2)在200℃至600℃下退火10hr至72hr、破碎、筛分得到复合材料;其中所述金属氟化物中氟元素F与金属元素M的摩尔比为y;所述复合材料中氟元素F和金属元素M的摩尔比为z,y<z≤y+2;并且其中所述M包括Al、Cu、Co、Ni、Mn、Fe或Ag中的至少一种。
- 一种正极,其包含如权利要求1-4中任一项所述的正极材料或根据权利要求5所述方法制备得到的复合材料。
- 一种电化学装置,其包含如权利要求6所述的正极。
- 根据权利要求7所述的电化学装置,其为全固态二次锂电池。
- 一种电子装置,其包含如权利要求7或8所述的电化学装置。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20950697.1A EP4207368A4 (en) | 2020-08-27 | 2020-08-27 | POSITIVE ELECTRODE MATERIAL AND ELECTROCHEMICAL DEVICE AND ELECTRONIC DEVICE THEREOF |
PCT/CN2020/111604 WO2022041025A1 (zh) | 2020-08-27 | 2020-08-27 | 正极材料及包含其的电化学装置和电子装置 |
JP2023512754A JP7565433B2 (ja) | 2020-08-27 | 2020-08-27 | 正極材料、並びにそれを含む電気化学装置及び電子装置 |
KR1020237007040A KR20230037673A (ko) | 2020-08-27 | 2020-08-27 | 양극재 및 이를 포함하는 전기화학 디바이스와 전자 디바이스 |
CN202080103114.2A CN116134642A (zh) | 2020-08-27 | 2020-08-27 | 正极材料及包含其的电化学装置和电子装置 |
US18/113,641 US20230216026A1 (en) | 2020-08-27 | 2023-02-24 | Positive electrode material, and electrochemical apparatus and electronic apparatus containing same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2020/111604 WO2022041025A1 (zh) | 2020-08-27 | 2020-08-27 | 正极材料及包含其的电化学装置和电子装置 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/113,641 Continuation US20230216026A1 (en) | 2020-08-27 | 2023-02-24 | Positive electrode material, and electrochemical apparatus and electronic apparatus containing same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022041025A1 true WO2022041025A1 (zh) | 2022-03-03 |
Family
ID=80352260
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2020/111604 WO2022041025A1 (zh) | 2020-08-27 | 2020-08-27 | 正极材料及包含其的电化学装置和电子装置 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230216026A1 (zh) |
EP (1) | EP4207368A4 (zh) |
JP (1) | JP7565433B2 (zh) |
KR (1) | KR20230037673A (zh) |
CN (1) | CN116134642A (zh) |
WO (1) | WO2022041025A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117154080B (zh) * | 2023-10-31 | 2024-02-23 | 有研(广东)新材料技术研究院 | 一种全固态电池包覆型卤化物正极复合材料及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9812739B2 (en) | 2015-03-31 | 2017-11-07 | Ningde Amperex Technology Limited | Electrolyte additive and use thereof in lithium-ion battery |
CN107634224A (zh) * | 2017-09-14 | 2018-01-26 | 辽宁兰晶科技有限公司 | 一种含氟化铁插层物的外壁氟化多壁碳纳米管的制备方法 |
CN108172765A (zh) * | 2016-12-08 | 2018-06-15 | 宁德时代新能源科技股份有限公司 | 动力电池及其正极极片 |
CN110112394A (zh) * | 2019-05-14 | 2019-08-09 | 中国民航大学 | 一种氟化碳/氟化金属复合正极材料的制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5091517B2 (ja) | 2007-03-28 | 2012-12-05 | 国立大学法人九州大学 | フッ化物正極作製法 |
JP2013073792A (ja) | 2011-09-28 | 2013-04-22 | Panasonic Corp | 非水電解質二次電池 |
-
2020
- 2020-08-27 EP EP20950697.1A patent/EP4207368A4/en active Pending
- 2020-08-27 JP JP2023512754A patent/JP7565433B2/ja active Active
- 2020-08-27 CN CN202080103114.2A patent/CN116134642A/zh active Pending
- 2020-08-27 WO PCT/CN2020/111604 patent/WO2022041025A1/zh active Application Filing
- 2020-08-27 KR KR1020237007040A patent/KR20230037673A/ko unknown
-
2023
- 2023-02-24 US US18/113,641 patent/US20230216026A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9812739B2 (en) | 2015-03-31 | 2017-11-07 | Ningde Amperex Technology Limited | Electrolyte additive and use thereof in lithium-ion battery |
CN108172765A (zh) * | 2016-12-08 | 2018-06-15 | 宁德时代新能源科技股份有限公司 | 动力电池及其正极极片 |
CN107634224A (zh) * | 2017-09-14 | 2018-01-26 | 辽宁兰晶科技有限公司 | 一种含氟化铁插层物的外壁氟化多壁碳纳米管的制备方法 |
CN110112394A (zh) * | 2019-05-14 | 2019-08-09 | 中国民航大学 | 一种氟化碳/氟化金属复合正极材料的制备方法 |
Non-Patent Citations (2)
Title |
---|
See also references of EP4207368A4 |
WEN LIU ET AL.: "Enhanced electrochemical activity of rechargeable carbon fluorides-sodium battery with catalysts", CARBON, vol. 93, 3 June 2015 (2015-06-03), pages 523 - 532, XP029255420, ISSN: 0008-6223, DOI: 10.1016/j.carbon.2015.05.092 * |
Also Published As
Publication number | Publication date |
---|---|
EP4207368A1 (en) | 2023-07-05 |
KR20230037673A (ko) | 2023-03-16 |
JP2023538140A (ja) | 2023-09-06 |
EP4207368A4 (en) | 2023-10-18 |
JP7565433B2 (ja) | 2024-10-10 |
CN116134642A (zh) | 2023-05-16 |
US20230216026A1 (en) | 2023-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20220158176A1 (en) | Anode material, electrochemical device and electronic device including the same | |
KR101436762B1 (ko) | 부극 재료, 금속 2차 전지 및 부극 재료의 제조 방법 | |
CN111029543B (zh) | 负极材料及包含其的电化学装置和电子装置 | |
CN111403693B (zh) | 负极活性材料和使用其的负极极片、电化学装置和电子装置 | |
CN111370695B (zh) | 负极活性材料及使用其的电化学装置和电子装置 | |
WO2021217617A1 (zh) | 负极活性材料、其制备方法、二次电池及包含二次电池的装置 | |
WO2022140973A1 (zh) | 负极极片、电化学装置和电子装置 | |
US20220052324A1 (en) | Negative electrode material and electrochemical apparatus and electronic apparatus containing the negative electrode material | |
CN112110448A (zh) | 一种氮掺杂碳与纳米硅复合负极材料及其制备方法 | |
CN114144919A (zh) | 一种正极极片、包含该正极极片的电化学装置和电子装置 | |
CN117317137A (zh) | 电化学装置和电子装置 | |
US20230216026A1 (en) | Positive electrode material, and electrochemical apparatus and electronic apparatus containing same | |
WO2024168471A1 (zh) | 二次电池及用电装置 | |
CN113517442B (zh) | 负极材料、电化学装置和电子装置 | |
WO2023184125A1 (zh) | 电化学装置和电子设备 | |
CN113921914B (zh) | 电解液以及使用其的电化学装置和电子装置 | |
CN112599742B (zh) | 电化学装置和电子装置 | |
WO2023039877A1 (zh) | 一种正极材料、电化学装置和电子装置 | |
WO2022140975A1 (zh) | 一种负极极片、包含该负极极片的电化学装置及电子装置 | |
WO2024197436A1 (zh) | 正极材料、包含该正极材料的电化学装置和电子装置 | |
JP2024129066A (ja) | 負極、ならびにこれを用いた電気化学装置および電子装置 | |
CN114824217A (zh) | 一种改性铁酸盐电化学材料及其制备方法和应用 | |
CN113054167A (zh) | 负极材料及包含其的电化学装置和电子装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20950697 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2023512754 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20237007040 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202327020333 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2020950697 Country of ref document: EP Effective date: 20230327 |