CN103094576A - Nickel-based positive electrode material, and preparation method thereof and battery - Google Patents
Nickel-based positive electrode material, and preparation method thereof and battery Download PDFInfo
- Publication number
- CN103094576A CN103094576A CN2011103384141A CN201110338414A CN103094576A CN 103094576 A CN103094576 A CN 103094576A CN 2011103384141 A CN2011103384141 A CN 2011103384141A CN 201110338414 A CN201110338414 A CN 201110338414A CN 103094576 A CN103094576 A CN 103094576A
- Authority
- CN
- China
- Prior art keywords
- source
- nickel
- anode material
- carbonate
- base anode
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 title abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 238000001238 wet grinding Methods 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims description 40
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 38
- 239000011572 manganese Substances 0.000 claims description 37
- 229910013716 LiNi Inorganic materials 0.000 claims description 27
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 26
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 26
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011656 manganese carbonate Substances 0.000 claims description 16
- 229940093474 manganese carbonate Drugs 0.000 claims description 16
- 235000006748 manganese carbonate Nutrition 0.000 claims description 16
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 16
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 6
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical group [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical group O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000012707 chemical precursor Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- ZYKTVIDNXTWTNS-UHFFFAOYSA-L [Co].[Mn].[Ni](O)O Chemical compound [Co].[Mn].[Ni](O)O ZYKTVIDNXTWTNS-UHFFFAOYSA-L 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003835 carbonate co-precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- -1 lithium transition metal compound Chemical class 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
- 150000002696 manganese Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940006444 nickel cation Drugs 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a nickel-based positive electrode material, and a preparation method thereof and a battery. The composition of the nickel-based positive electrode material is LiaNibCocMndMeM'fO2-g/2Fg (M is at least one selected from Ti, Zr, Al, Fe, Cr, Si, and Cu; M' is at least one selected from Mg, Ca, Sr, Ba, and W; a is no smaller than 0.95 and no greater than 1.2; b is no smaller than 0.2 and no greater than 0.9; c is no smaller than 0 and no greater than 0.4; d is no smaller than 0 and no greater than 0.4; e+f is greater than 0.05and no greater than 0.2; and g is greater than 0.02 and no greater than 0. 1). Anions and cations are used in co-doping. With a synergistic effect, nickel-based positive electrode material capacity, structural stability and circulation performance are greatly improved. The preparation method at least comprises the 4 steps that: (1) corresponding raw materials are weighed according to the molar ratio consistent with LiaNibCocMndMeM'fO2-g/2Fg; (2) the raw materials are subjected to wet grinding; (3) slurry obtained by grinding is dried; and (4) the dried material is subjected to solid-phase synthesis under a temperature of 500-1100 DEG C. With the process, the raw materials can be more uniformly dispersed, and the obtained product has the advantages of high capacity and good circulation performance. The process is simple, and has the advantages of low cost and suitability for large-scale industrialized productions. With the process, problems such as complicated process and acid and alkali pollution of a wet chemical precursor preparation method are avoided. The invention also relates to a battery with the material as an active substance.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof and battery, belong to the energy and material technical field.
Background technology
1999, LiNi
1-x-yCo
xMn
yO
2(0＜x＜0.5,0＜y＜0.5) (nickel-base anode material) by reported first, and this material has significantly improved the capacity of material by introducing nickel ion, reduce lithium-nickel cation mixing, the fail safe that improves material by introducing manganese ion by introducing cobalt ions.This material combines LiCoO
2, LiNiO
2, LiMnO
2The advantage of three class materials is considered to best and can replaces LiCoO
2One of positive electrode.But in this material, the radius of lithium ion and bivalent nickel ion approaches, and mixing easily occurs, and makes the structural stability variation, thus also variation of the cycle performance of material.In order to suppress this mixing phenomenon, usually adopt cation or (with) anion doped structural stability, thermal stability and the high rate performance etc. that improve this material.
Synthesizing of nickel-base anode material adopted liquid-phase coprecipitation and high temperature solid-state method mostly at present.Liquid-phase coprecipitation is first the aqueous solution of nickel salt, cobalt salt, manganese salt and lithium hydroxide, NaOH or sodium carbonate co-precipitation to be generated hydroxide or carbonate precursor, then this presoma is synthesized with at high temperature roasting after lithium salts mixes.Lv Xiangyang etc. (CN101269849A) first adopt special depositing technology to prepare a kind of high density spherical nickel-cobalt manganese presoma, then with this presoma and the lithium source mixed after roasting under given conditions, obtained at last the high density nickle cobalt lithium manganate.The method can evenly be mixed on atomic level by three kinds of transition metals, but complex process, poor repeatability.The high temperature solid-state rule is with direct synthetic product at high temperature after the compound of nickel, cobalt, manganese and lithium ground and mixed together.The people such as Liao Qinlin (CN1610153A) are take oxide, hydroxide or the carbonate of nickel, lithium, cobalt as raw material, add wherein a kind of element of Ti, Mg, Cr, Mn, mix in ball mill, under the 600-800 degree pre-burning 5-15 hour, then synthesized 5-20 hour under the 700-900 degree, obtain end product after pulverizing, ball milling, classification.The people such as K.W.Eberman (US7211237B2) have improved solid phase method, to contain cobalt, contain manganese, oxide or oxide precursor nickeliferous and that contain lithium carry out wet-milling, the fine particle slurry material that contains cobalt, manganese, nickel and the lithium of abundant dispersion with formation, then slurry is heated to form have single-phase lithium transition metal compound.Above-mentioned two kinds of methods are simple, but are difficult to obtain the pattern of homogeneous.The Zhi mound is virtuous controls (CN101093887A) provides a kind of method for preparing the layered lithium-nickel-based compound oxide powder of high density lithium secondary battery positive electrode material, first will contain nickel compound, can partly replace the metallic element compound pulp spray drying of nickel, then with the compound of lithium, then prepare the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell by baking.This kind method is simple, and pattern is easily controlled, and easily again causes the element uneven distribution but be dry mixed.
Summary of the invention
The main technical problem to be solved in the present invention is: for the problems referred to above of nickel-base anode material, provide a kind of anode material for lithium-ion batteries and preparation method thereof and battery.Improve capacity and the stability of material by anion and cation co-doped.The oxygen that replaces part by the anion fluorine can be so that material has stable cycle performance under high cut-ff voltage, better high rate performance and thermal stability.The replacement of fluorine ion can also promote the growth of primary particle, thereby obtains higher tap density.And by at least a replacement part Mn in Mg, Ca, Sr, Ba, W, because these elements self are not participated in reaction, so in the situation that do not affect the stability that the capacity of material can also improve material structure.Discharge capacity not only can be improved by at least a doping the in Ti, Zr, Al, Fe, Cr, Si, Cu, the decomposition of active material can also be suppressed.
The chemical formula of nickel-base anode material of the present invention is Li
aNi
bCo
cMn
dM
eM’
fO
2-g/2F
g, wherein M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05＜e+f≤0.2,0.02＜g≤0.1.
Preferred 0.05＜e+f≤0.1,0.02＜g≤0.05.
Preferred M is: at least a in Ti, Zr, Al, Fe, Si, M ' is: at least a in Mg, Ca, W.
Nickel-base anode material of the present invention is a kind of in following composition:
LiNi
0.5Co
0.28Mn
0.16Si
0.03Zr
0.03O
1.98F
0.04、
LiNi
0.58Co
0.18Mn
0.18Si
0.03Zr
0.03O
1.98F
0.04、
LiNi
0.68Co
0.13Mn
0.13Si
0.03Zr
0.03O
1.98F
0.04、
LiNi
0.78Co
0.08Mn
0.08Si
0.03Zr
0.03O
1.98F
0.04、
LiNi
0.68Co
0.13Mn
0.11Al
0.05Zr
0.03O
1.98F
0.04、
LiNi
0.5Co
0.28Mn
0.15Al
0.04Zr
0.03O
1.98F
0.04、LiNi
0.86Co
0.08Al
0.03Mg
0.03O
1.975F
0.05、
LiNi
0.58Co
0.18Mn
0.18Al
0.03Mg
0.03O
19.8F
0.04、
Li
0.98Ni
0.78Co
0.16Si
0.02Al
0.02Mg
0.03O
1.975F
0.05、
Li
1.04Ni
0.76Co
0.16Al
0.03Mg
0.03O
1.985F
0.03、
LiNi
1/3Co
1/3Mn
1/3-0.06Al
0.04Mg
0.02O
1.985F
0.03。
The present invention proposes simultaneously this nickel-base anode material preparation method of preparation, the method comprises following processing step at least:
1) respectively with lithium source, manganese source, cobalt source, nickel source, and be selected from Ti source, Zr source, Al source, Fe source, Cr source, Si source, Cu source at least a, and be selected from least a in Mg source, Ca source, Sr source, Ba source, W source and the F source as raw material, press chemical formula Li
aNi
bCo
cMn
dM
eM’
fO
2-g/2F
gA mole proportioning take corresponding raw material, wherein M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05＜e+f≤0.2,0.02＜g≤0.1;
2) add appropriate liquid to carry out wet-milling in raw material;
3) with the slurry drying after wet-milling;
4) at high temperature carry out roasting after drying and synthesize, the roasting synthesis temperature is 500-1100 ℃.
A kind of nickel-base anode material preparation method of the present invention, described lithium source be anhydrous lithium hydroxide, it is at least a to contain in crystallization water lithium hydroxide, lithium carbonate, preferred lithium carbonate.
A kind of nickel-base anode material preparation method of the present invention, described manganese source are at least a in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate, and be at least a in preferable alloy manganese, manganese carbonate.
A kind of nickel-base anode material preparation method of the present invention, described cobalt source are at least a in cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, cobalt hydroxide, cobalt carbonate, are preferably in cobalt sesquioxide, cobaltosic oxide at least a.
A kind of nickel-base anode material preparation method of the present invention, described nickel source are at least a in nickel sesquioxide, nickel protoxide, nickel hydroxide, nickelous carbonate, are preferably in nickel sesquioxide or nickel protoxide at least a.
a kind of nickel-base anode material preparation method of the present invention, described titanium source is titanium dioxide, described zirconium source is zirconia, described aluminium source is metallic aluminium, alundum (Al2O3), at least a in aluminium hydroxide, described source of iron is iron oxide, ferrous oxide, iron hydroxide, at least a in ferrous hydroxide, described chromium source is crome metal, chrome green, at least a in chromium hydroxide, described silicon source is silicon dioxide, described copper source is cupric oxide, cuprous oxide, at least a in copper carbonate, described magnesium source is magnesium carbonate, at least a in magnesium oxide, described calcium source is calcium carbonate, calcium oxide, at least a in calcium hydroxide, described strontium source is strontium carbonate, at least a in strontium oxide strontia, described barium source is brium carbonate, described tungsten source is tungstic acid, described fluorine source is lithium fluoride.
A kind of nickel-base anode material preparation method of the present invention, described step 2) wet-milling in comprises in pre-grinding, corase grind, fine grinding two kinds at least.Pre-grinding is to make slurry particle diameter (D
50) less than 3 microns; Corase grind is to make slurry particle diameter (D
50) less than 1 micron; Fine grinding is to make slurry particle diameter (D
50) less than 0.1 micron.
In described step 2) in, pre-time consuming was for 2-30 hour.
In described step 2) in, the corase grind time is 2-5 hour.
In described step 2) in, the fine grinding time is 2-5 hour.
A kind of nickel-base anode material preparation method of the present invention, described step 3) grain diameter (D of gained powder after dry in
50) less than 1 micron.
In described step 3) in, dry temperature is 80-250 ℃.
A kind of nickel-base anode material preparation method of the present invention, the synthetic temperature of described roasting is preferred 800-1000 ℃, most preferably is 800-900 ℃.
In described step 4) in, roasting time is 5-40 hour.
A kind of positive pole of the present invention will mix with conductive agent and bonding agent by the nickel-base anode material that above-mentioned composition and preparation method obtain, and the mixture that obtains is coated in the positive pole that supports formation lithium ion battery on conducting base.
A kind of battery of the present invention, negative pole, barrier film, electrolyte that above-mentioned positive pole is compatible with electricity are placed in container and form lithium ion battery.
Advantage of the present invention is:
(1) realize anion and cation co-doped in the nickel-base anode material, by synergy, capacity, structural stability and the cycle performance of nickel-base anode material all are improved.
(2) adopt respectively the different model ball mill to carry out the pre-grinding in pre-grinding, corase grind, fine grinding, two kinds of combinations of corase grind according to the particle diameter distribution of raw material and the features such as hardness of material, or two kinds of combinations of pre-grinding, fine grinding, or the combination of two kinds of corase grind, fine grinding, or the combination of three kinds of pre-grinding, corase grind, fine grinding; Fully the advantage with ball millings at different levels is used, and not only increases work efficiency, and raw material is disperseed more even, and particle diameter is more tiny.The tiny motive force that can increase sintering of particle has shortened the diffusion length of atom, accelerates sintering process, and can reduce sintering temperature.The method all adds raw material is disposable, need not to add any raw material in the subsequent technique process, has avoided secondary ball milling mixing (secondary ball milling mixes and refers to again add after raw material mixing and ball milling again) again to cause the element skewness.The method adopts solid phase method synthetic, and technical process is simple, and cost is low, is easy to large industrial production, has avoided wet chemistry method to prepare the flow process of presoma complexity and the pollution problem of soda acid.
Description of drawings
The FE-SEM picture of the nickel-base anode material that Fig. 1 the present invention synthesizes (embodiment 7).
The X ray diffracting spectrum of the nickel-base anode material that Fig. 2 the present invention synthesizes (embodiment 7).
The first charge-discharge curve of the nickel-base anode material that Fig. 3 the present invention synthesizes (embodiment 7).
The cycle performance of the nickel-base anode material that Fig. 4 the present invention synthesizes (embodiment 7).
Embodiment
Below with embodiment, technical scheme of the present invention is further described; to help product of the present invention and manufacture method are done further to understand; protection scope of the present invention is not subjected to the restriction of these embodiment, and protection scope of the present invention is decided by claims.
Specific embodiment 1:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi
0.5Co
0.28Mn
0.16Si
0.03Zr
0.03O
1.98F
0.04363.2g lithium carbonate, 10.6g lithium fluoride, 382.1g nickel protoxide, 230.0g cobaltosic oxide, 32.9g zirconia, 18.4g silicon dioxide, 188.2g manganese carbonate, after mixing with the 6000ml absolute ethyl alcohol, be placed on the corase grind machine and roughly grind 200min, slurry is moved in atomizer mill fine grinding 200min, take out material from the fine grinding machine, dry under 80 ℃.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 2:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi
0.5Co
0.28Mn
0.16Si
0.03Zr
0.03O
1.98F
0.04363.2g lithium carbonate, the 10.6g lithium fluoride, the 382.1g nickel protoxide, the 230.0g cobaltosic oxide, the 32.9g zirconia, 18.4g silicon dioxide, the 188.2g manganese carbonate joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 24h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, roughly grind 200min on the corase grind machine, after raw material is mixed, take out material from the corase grind machine, dry under 80 ℃.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 3:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi
0.5Co
0.28Mn
0.16Si
0.03Zr
0.03O
1.98F
0.04363.2g lithium carbonate, the 10.6g lithium fluoride, the 382.1g nickel protoxide, the 230.0g cobaltosic oxide, the 32.9g zirconia, 18.4g silicon dioxide, the 188.2g manganese carbonate joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 24h on the bar type ball mill.Material after pre-grinding is taken out, add the 6000ml absolute ethyl alcohol, roughly grind 200min on the corase grind machine, will expect to move in atomizer mill, fine grinding 200min is dry under 80 ℃ with the compound after fine grinding.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 4:
Adopting lithium carbonate, manganese powder, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi
0.78Co
0.08Mn
0.08Si
0.03Zr
0.03O
1.98F
0.04Weighing 355.9g lithium carbonate, the 10.6g lithium fluoride, 407.8 nickel protoxides, the 78.3g cobaltosic oxide, 32.9 zirconias, 18.4g silicon dioxide, the 73.0g manganese powder joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, roughly grind 150min on the corase grind machine, the material after corase grind is moved in atomizer mill, fine grinding 200min is dry under 100 ℃ with compound.The powder that obtains after dry is through 900 ℃ of roasting 20h, and is cooling with stove.
Specific embodiment 5:
Adopting lithium carbonate, manganese powder, metal cobalt powder, metal nickel powder is that primary raw material prepares Li
1Ni
0.68Co
0.13Mn
0.11Al
0.05Zr
0.03O
1.98F
0.04Weighing 380.0g lithium carbonate, the 10.6g lithium fluoride, 466.2 metal nickel powders, the 48.0g metal cobalt powder, the 32.8g zirconia, 18.4g silicon dioxide, the 44.8g manganese powder joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, after corase grind 150min on the corase grind machine, will expect to move in atomizer mill, fine grinding 200min is dry under 100 ℃ with the compound after fine grinding.The powder that obtains after dry is through 900 ℃ of roasting 25h, and is cooling with stove.
Specific embodiment 6:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, metal nickel powder is that primary raw material prepares LiNi
0.58Co
0.18Mn
0.18Si
0.03Zr
0.03O
1.98F
0.04Weighing 363.2g lithium carbonate, the 10.6g lithium fluoride, 347.9 nickel, the 147.7g cobaltosic oxide, 32.9 zirconias, 18.4g silicon dioxide, the 211.5g manganese carbonate joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 12h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Carry out under 100 ℃ the compound after fine grinding dry.The powder that obtains after dry is through 950 ℃ of roasting 10h, and is cooling with stove.
Specific embodiment 7:
Adopting lithium carbonate, manganese powder, metal cobalt powder, metal nickel powder is that primary raw material prepares LiNi
1/3Co
1/3Mn
1/3-0.06Al
0.04Mg
0.02O
1.985F
0.03Weighing 355.9g lithium carbonate, the 10.6g lithium fluoride, 407.8 nickel, the 78.3g cobalt, the 32.9g zirconia, 18.4g silicon dioxide, the 73.0g manganese carbonate joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 5000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 950 ℃ of roasting 5h, and is cooling with stove.
Specific embodiment 8:
Adopting lithium carbonate, manganese powder, metal cobalt powder, metal nickel powder is that primary raw material prepares LiNi
0.5Co
0.28Mn
0.15Al
0.04Zr
0.03O
1.98F
0.04Weighing 364.7g lithium carbonate, the 10.6g lithium fluoride, 301.1 metal nickel powders, the 169.3g metal cobalt powder, the 33.0g zirconia, the 20.9g alundum (Al2O3), the 84.5g manganese powder joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 950 ℃ of roasting 10h, and is cooling with stove.
Specific embodiment 9:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi
0.58Co
0.18Mn
0.18Al
0.03Mg
0.03O
1.98F
0.04375.2g lithium carbonate, the 10.9g lithium fluoride, the 453.5g nickel protoxide, the 151.2g cobaltosic oxide, 26.5g magnesium carbonate, the 16.0g alundum (Al2O3), the 216.6g manganese carbonate joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 900 ℃ of roasting 8h, and is cooling with stove.
Specific embodiment 10:
Adopting lithium carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares Li
1.04Ni
0.76Co
0.16Al
0.03Mg
0.03O
1.985F
0.03387.5g lithium carbonate, the 8.08g lithium fluoride, the 605.0g nickel protoxide, the 133.4g cobaltosic oxide, 26.3g magnesium carbonate, the 15.9g alundum (Al2O3) joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 24h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 200min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 11:
Adopt the material of specific embodiment 1-10 preparation as active material, with the proportioning weighing according to 88: 7: 5 of conductive agent (SP), binding agent (PVDF), first active material and conductive agent are dry mixed 4h, PVDF is dissolved in the N-N dimethyl formamide, then the conductive agent with the active material that mixes adds wherein, stirs, and is coated on aluminium foil, dry in drying box, as the positive pole of battery.
Specific embodiment 12: the positive pole that embodiment 11 is prepared after drying, adopts the graphite conduct to electrode in vacuum drying oven, and the composition of electrolyte is mainly the LiPF of 1M
6And DMC/EC.Charging and discharging currents density 0.2C, discharging and recharging upper and lower limit voltage is 2.5-4.3V, specific capacity computational methods C=mA * h/g, wherein C: specific capacity, temperature is 25 ± 2 ℃, the constant current tester that computerizeds control carries out electrochemistry capacitance and loop test.
Comparative Examples 1: adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi
1/3Co
1/3Mn
1/3O
2Weighing 19.2g lithium carbonate, 12.9g nickel protoxide, 13.9g cobaltosic oxide, 19.8g manganese carbonate is put into ball mill, adds the mixture of 100 milliliters of absolute ethyl alcohols and water, adds the 60g agate ball, wet-milling 2 hours is taken out, and puts into corundum crucible after 120 ℃ of oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 4 ℃/minutes intensification speed, be incubated 10 hours, cooling is taken out, and grinds, cross 300 mesh sieves, obtain end product.
Comparative Examples 2: press chemical formula Li (Ni
1/3Co
1/3Mn
1/3)
0.99Mg
0.01O
1.99F
0.01Synthesized 16 hours under 900 ℃ in air after taking appropriate lithium carbonate, nickel hydroxide cobalt manganese, lithium fluoride, magnesium hydroxide mixing, cooling is taken out, and 300 mesh sieves are crossed in grinding, obtain end product.
Table 1 is the nickel-base anode material that synthesizes by composition of the present invention and method and the discharge capacity contrast that contrasts sample.The result of table 1 demonstrates with composition of the present invention and the synthetic nickel-base anode material of method has performance preferably.
Table 1
| Discharge capacity mAhg first -1 | |
| Embodiment 1 | 165 |
| |
170 |
| Embodiment 3 | 178 |
| Embodiment 4 | 198 |
| Embodiment 5 | 183 |
| Comparative Examples 1 | 148 |
| Comparative Examples 2 | 160 |
Claims (13)
1. nickel-base anode material, it consists of: Li
aNi
bCo
cMn
dM
eM’
fO
2-g/2F
g, wherein M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05＜e+f≤0.2,0.02＜g≤0.1.
2. a kind of nickel-base anode material according to claim 1, is characterized in that: 0.05＜e+f≤0.1,0.02＜g≤0.05.
3. a kind of nickel-base anode material according to claim 1, it is characterized in that described M is: at least a in Ti, Zr, Al, Fe, Si, described M ' is: at least a in Mg, Ca, W.
4. a kind of nickel-base anode material according to claim 1, is characterized in that, described nickel-base anode material is a kind of in following composition: LiNi
0.5Co
0.28Mn
0.16Si
0.03Zr
0.03O
1.98F
0.04, LiNi
0.58Co
0.18Mn
0.18Si
0.03Zr
0.03O
1.98F
0.04, LiNi
0.68Co
0.13Mn
0.13Si
0.03Zr
0.03O
1.98F
0.04, LiNi
0.78Co
0.08Mn
0.08Si
0.03Zr
0.03O
1.98F
0.04, LiNi
0.68Co
0.13Mn
0.11Al
0.05Zr
0.03O
1.98F
0.04, LiNi
0.5Co
0.28Mn
0.15Al
0.04Zr
0.03O
1.98F
0.04, LiNi
0.86Co
0.08Al
0.03Mg
0.03O
1.975F
0.05, LiNi
0.58Co
0.18Mn
0.18Al
0.03Mg
0.03O
1.98F
0.04, Li
0.98Ni
0.78Co
0.16Si
0.02Al
0.02Mg
0.03O
1.975F
0.05, Li
1.04Ni
0.76Co
0.16Al
0.03Mg
0.03O
1.985F
0.03, LiNi
1/3Co
1/3Mn
1/3-0.06Al
0.04Mg
0.02O
1.985F
0.03
5. method for preparing the described nickel-base anode material of claim 1, it is characterized in that containing at least following 4 steps: 1) respectively with lithium source, manganese source, cobalt source, nickel source, with be selected from Ti source, Zr source, Al source, Fe source, Cr source, Si source, Cu source at least a, and be selected from least a in Mg source, Ca source, Sr source, Ba source, W source and the F source as raw material, according to the chemical expression Li of the described nickel-base anode material of claim 1
aNi
bCo
cMn
dM
eM’
fO
2-g/2F
g, mole proportioning of requirement takes corresponding raw material; Wherein, M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05＜e+f≤0.2,0.02＜g≤0.1; 2) add solution to carry out wet-milling in raw material; 3) slurry with milled carries out drying; 4) dried material is synthesized under high temperature, the roasting synthesis temperature is 500-1100 ℃.
6. nickel-base anode material preparation method according to claim 5, is characterized in that described step 3) in the temperature of drying be 80-250 ℃.
7. nickel-base anode material preparation method according to claim 5, is characterized in that, described lithium source is anhydrous lithium hydroxide, contain crystallization water lithium hydroxide, at least a in lithium carbonate, described manganese source is manganese metal, manganese monoxide, manganese dioxide, at least a in manganese carbonate, described cobalt source is metallic cobalt, cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, cobalt hydroxide, at least a in cobalt carbonate, described nickel source is metallic nickel, nickel sesquioxide, nickel protoxide, nickel hydroxide, at least a in nickelous carbonate, described titanium source is titanium dioxide, and described zirconium source is zirconia, and described aluminium source is metallic aluminium, alundum (Al2O3), at least a in aluminium hydroxide, described source of iron is iron oxide, ferrous oxide, iron hydroxide, at least a in ferrous hydroxide, described chromium source is crome metal, chrome green, at least a in chromium hydroxide, described silicon source is silicon dioxide, and described copper source is cupric oxide, cuprous oxide, at least a in copper carbonate, described magnesium source is magnesium carbonate, at least a in magnesium oxide, described calcium source is calcium carbonate, calcium oxide, at least a in calcium hydroxide, described strontium source is strontium carbonate, at least a in strontium oxide strontia, described barium source is brium carbonate, and described tungsten source is tungstic acid, and described fluorine source is lithium fluoride.
8. nickel-base anode material preparation method according to claim 5, is characterized in that described step 2) in wet-milling comprise at least in pre-grinding, corase grind, fine grinding two kinds; Wherein, pre-grinding is the average grain diameter D that makes particle in slurry
50Less than 3 μ m; Corase grind is the average grain diameter D that makes particle in slurry
50Less than 1 μ m; Fine grinding is the average grain diameter D that makes particle in slurry
50Less than 0.1 μ m.
9. nickel-base anode material preparation method according to claim 5, is characterized in that, described drying is at least a in forced air drying, vacuumize, spray drying.
10. nickel-base anode material preparation method according to claim 5, is characterized in that, the synthetic temperature of roasting is 800-1000 ℃.
11. nickel-base anode material preparation method according to claim 5 is characterized in that, the synthetic temperature of roasting is 800-900 ℃.
12. a positive pole is characterized in that, the described nickel-base anode material of claim 1 is mixed with conductive agent and bonding agent, and the mixture that obtains is coated in the positive pole that supports formation lithium ion battery on conducting base.
13. a battery is characterized in that, anode, barrier film, electrolyte that the described positive pole of claim 12 is compatible with electricity are placed in container and form lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110338414.1A CN103094576B (en) | 2011-10-31 | 2011-10-31 | A kind of nickel-base anode material and preparation method thereof and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110338414.1A CN103094576B (en) | 2011-10-31 | 2011-10-31 | A kind of nickel-base anode material and preparation method thereof and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103094576A true CN103094576A (en) | 2013-05-08 |
| CN103094576B CN103094576B (en) | 2015-09-30 |
Family
ID=48206900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110338414.1A Active CN103094576B (en) | 2011-10-31 | 2011-10-31 | A kind of nickel-base anode material and preparation method thereof and battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103094576B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972487A (en) * | 2014-05-16 | 2014-08-06 | 厦门钨业股份有限公司 | Multi-component composite oxide material and industrial preparation method thereof |
| CN103972495A (en) * | 2014-05-16 | 2014-08-06 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of lithium ion battery positive pole material lithium nickelate manganate |
| CN104425814A (en) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | Lithium manganate material and preparation method thereof and lithium ion battery cathode material |
| CN105322157A (en) * | 2015-10-31 | 2016-02-10 | 芜湖迈特电子科技有限公司 | Preparation method of manganese-doped lithium cobalt oxide of lithium polymer battery for charge pal |
| CN106784748A (en) * | 2017-03-21 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of silicon substrate nickel cobalt manganese lithium ternary electrode material of lithium battery and preparation method thereof |
| CN107074588A (en) * | 2014-10-31 | 2017-08-18 | 株式会社Lg 化学 | Precursor, the compound of lithium and transition metal oxide, the positive pole and secondary cell comprising the compound of transition metal oxide |
| CN107221667A (en) * | 2017-07-10 | 2017-09-29 | 苏州柏晟纳米材料科技有限公司 | A kind of preparation method of composite metal oxide electrode material |
| CN107565126A (en) * | 2017-08-31 | 2018-01-09 | 福建师范大学 | The method that Direct precipitation prepares the nickel-cobalt-manganese ternary material of doping bivalent cation |
| CN107742712A (en) * | 2017-10-24 | 2018-02-27 | 长沙理工大学 | A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method |
| US20180183045A1 (en) * | 2016-12-28 | 2018-06-28 | Sichuan FuHua New Energy High-Tech Co., LTD. | High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof |
| CN110289415A (en) * | 2019-07-05 | 2019-09-27 | 福州大学 | A kind of class monocrystalline tertiary cathode material and preparation method thereof that cation-anion co-doping is miscellaneous |
| WO2021111249A1 (en) * | 2019-12-04 | 2021-06-10 | 株式会社半導体エネルギー研究所 | Positive electrode active material, secondary battery, and vehicle |
| CN112960704A (en) * | 2021-02-01 | 2021-06-15 | 福建金山锂科新材料有限公司 | Preparation method of high-voltage lithium nickel manganese oxide positive electrode material |
| CN113800574A (en) * | 2021-08-05 | 2021-12-17 | 广州大学 | Nickel-manganese-iron-aluminum-lithium cathode material and preparation method thereof |
| WO2022237328A1 (en) * | 2021-05-12 | 2022-11-17 | 蜂巢能源科技股份有限公司 | Coated ternary anode material, preparation method therefor, and lithium ion battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701451A (en) * | 2003-03-14 | 2005-11-23 | 清美化学股份有限公司 | Positive electrode active material powder for lithium secondary battery |
| CN101582497A (en) * | 2009-06-18 | 2009-11-18 | 中南大学 | Method for preparing composite anode material of high-capacity lithium ion battery |
| CN101622741A (en) * | 2007-03-05 | 2010-01-06 | 户田工业株式会社 | Li-ni composite oxide particles for non-aqueous electrolyte secondary b attery, process for producing the same, and non-aqueous electrolyte secondary battery |
| CN101728529A (en) * | 2008-10-10 | 2010-06-09 | 深圳市天骄科技开发有限公司 | Lithium ion battery anode material and manufacturing method thereof |
| WO2010089931A1 (en) * | 2009-02-04 | 2010-08-12 | 独立行政法人産業技術総合研究所 | Method for producing lithium silicate compound |
| US20100279172A1 (en) * | 2009-04-29 | 2010-11-04 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
-
2011
- 2011-10-31 CN CN201110338414.1A patent/CN103094576B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701451A (en) * | 2003-03-14 | 2005-11-23 | 清美化学股份有限公司 | Positive electrode active material powder for lithium secondary battery |
| CN101622741A (en) * | 2007-03-05 | 2010-01-06 | 户田工业株式会社 | Li-ni composite oxide particles for non-aqueous electrolyte secondary b attery, process for producing the same, and non-aqueous electrolyte secondary battery |
| CN101728529A (en) * | 2008-10-10 | 2010-06-09 | 深圳市天骄科技开发有限公司 | Lithium ion battery anode material and manufacturing method thereof |
| WO2010089931A1 (en) * | 2009-02-04 | 2010-08-12 | 独立行政法人産業技術総合研究所 | Method for producing lithium silicate compound |
| US20100279172A1 (en) * | 2009-04-29 | 2010-11-04 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
| CN101582497A (en) * | 2009-06-18 | 2009-11-18 | 中南大学 | Method for preparing composite anode material of high-capacity lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| YANHUAI DING: "Synthesis and electrochemical properties of LiNi0.375Co0.25Mn0.375−xCrxO2−xFx cathode materials prepared by sol–gel method", 《MATERIALS RESEARCH BULLETIN》 * |
| YANHUAI DING: "Synthesis and electrochemical properties of LiNi0.375Co0.25Mn0.375−xCrxO2−xFx cathode materials prepared by sol–gel method", 《MATERIALS RESEARCH BULLETIN》, 22 October 2007 (2007-10-22), XP022717537, DOI: doi:10.1016/j.materresbull.2007.10.009 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425814A (en) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | Lithium manganate material and preparation method thereof and lithium ion battery cathode material |
| CN104425814B (en) * | 2013-09-09 | 2017-03-29 | 北京国能电池科技有限公司 | The preparation method of LiMn2O4, lithium manganate material, anode material for lithium-ion batteries |
| CN103972495A (en) * | 2014-05-16 | 2014-08-06 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of lithium ion battery positive pole material lithium nickelate manganate |
| CN103972495B (en) * | 2014-05-16 | 2016-03-23 | 盐城市新能源化学储能与动力电源研究中心 | A kind of preparation method of lithium ion battery anode material nickel LiMn2O4 |
| CN103972487B (en) * | 2014-05-16 | 2016-08-24 | 厦门钨业股份有限公司 | A kind of multicomponent composite oxide material and industrial production process thereof |
| CN103972487A (en) * | 2014-05-16 | 2014-08-06 | 厦门钨业股份有限公司 | Multi-component composite oxide material and industrial preparation method thereof |
| CN107074588A (en) * | 2014-10-31 | 2017-08-18 | 株式会社Lg 化学 | Precursor, the compound of lithium and transition metal oxide, the positive pole and secondary cell comprising the compound of transition metal oxide |
| CN107074588B (en) * | 2014-10-31 | 2019-05-14 | 株式会社Lg 化学 | The precursor of transition metal oxide, the compound of lithium and transition metal oxide, anode and secondary cell comprising the compound |
| CN105322157A (en) * | 2015-10-31 | 2016-02-10 | 芜湖迈特电子科技有限公司 | Preparation method of manganese-doped lithium cobalt oxide of lithium polymer battery for charge pal |
| US10446830B2 (en) * | 2016-12-28 | 2019-10-15 | Sichuan FuHua New Energy High-Tech Co., LTD. | High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof |
| US20180183045A1 (en) * | 2016-12-28 | 2018-06-28 | Sichuan FuHua New Energy High-Tech Co., LTD. | High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof |
| CN106784748A (en) * | 2017-03-21 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of silicon substrate nickel cobalt manganese lithium ternary electrode material of lithium battery and preparation method thereof |
| CN106784748B (en) * | 2017-03-21 | 2018-01-26 | 宝汽宏泰新能源有限公司 | A kind of silicon substrate nickel cobalt manganese lithium ternary electrode material of lithium battery and preparation method thereof |
| CN107221667A (en) * | 2017-07-10 | 2017-09-29 | 苏州柏晟纳米材料科技有限公司 | A kind of preparation method of composite metal oxide electrode material |
| CN107565126A (en) * | 2017-08-31 | 2018-01-09 | 福建师范大学 | The method that Direct precipitation prepares the nickel-cobalt-manganese ternary material of doping bivalent cation |
| CN107565126B (en) * | 2017-08-31 | 2020-10-23 | 福建师范大学 | Method for preparing bivalent cation-doped nickel-cobalt-manganese ternary material by direct precipitation |
| CN107742712A (en) * | 2017-10-24 | 2018-02-27 | 长沙理工大学 | A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method |
| CN107742712B (en) * | 2017-10-24 | 2019-11-12 | 长沙理工大学 | A kind of conducting polymer coating-doping type anode material for lithium-ion batteries and its synthetic method |
| CN110289415A (en) * | 2019-07-05 | 2019-09-27 | 福州大学 | A kind of class monocrystalline tertiary cathode material and preparation method thereof that cation-anion co-doping is miscellaneous |
| WO2021111249A1 (en) * | 2019-12-04 | 2021-06-10 | 株式会社半導体エネルギー研究所 | Positive electrode active material, secondary battery, and vehicle |
| CN112960704A (en) * | 2021-02-01 | 2021-06-15 | 福建金山锂科新材料有限公司 | Preparation method of high-voltage lithium nickel manganese oxide positive electrode material |
| WO2022237328A1 (en) * | 2021-05-12 | 2022-11-17 | 蜂巢能源科技股份有限公司 | Coated ternary anode material, preparation method therefor, and lithium ion battery |
| CN113800574A (en) * | 2021-08-05 | 2021-12-17 | 广州大学 | Nickel-manganese-iron-aluminum-lithium cathode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103094576B (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103094576B (en) | A kind of nickel-base anode material and preparation method thereof and battery | |
| CN107275573B (en) | Positive electrode active material for nonaqueous electrolyte secondary battery | |
| CN110697787B (en) | High-volume energy density ternary cathode material for lithium ion battery and preparation method thereof | |
| CN105449169B (en) | Anode material for lithium-ion batteries, preparation method and lithium ion battery | |
| CN104300145B (en) | Preparation method for high-tapping-density modified nickel-cobalt lithium manganate positive material | |
| CN106299352A (en) | The preparation method of positive pole material of secondary lithium battery | |
| CN113690414B (en) | Mixed lithium-rich cathode material and preparation method and application thereof | |
| CN104600285B (en) | Method for preparing spherical lithium nickel manganese oxide positive pole material | |
| JP6708326B2 (en) | Positive electrode material for sodium secondary batteries | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN103332754A (en) | High voltage lithium ion battery cathode material and preparation method thereof | |
| CN106910887B (en) | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material | |
| CN107978751A (en) | A kind of high electrochemical activity tertiary cathode material and preparation method thereof | |
| CN102627332A (en) | Oxide solid solution, preparation method of oxide solid solution, lithium ion battery anode material and preparation method of lithium ion battery anode material | |
| WO2015039490A1 (en) | Lithium-rich anode material and preparation method thereof | |
| CN110233250A (en) | A kind of preparation method of single crystal grain tertiary cathode material | |
| CN103606675B (en) | A kind of preparation method of lithium-nickel-cobalt-oxygen positive electrode of metal ion mixing | |
| CN106935845A (en) | Doping type small particle nickel-cobalt lithium manganate cathode material and its presoma and both preparation methods | |
| CN107634196A (en) | Adulterate the preparation method of the nickel-cobalt-manganese ternary material of zinc | |
| CN102263238A (en) | Lithium nickel cobalt manganese oxide and preparation method thereof | |
| CN113845153A (en) | Multi-element high-entropy solid solution cathode material and preparation method and application thereof | |
| Xian et al. | P3-type layered Na0. 26Co1− xMnxO2 cathode induced by Mn doping for high-performance sodium-ion batteries | |
| CN107579224A (en) | The preparation method of the nickel-cobalt-manganese ternary material of doping with rare-earth ions | |
| CN107634197A (en) | The method that two-step sintering prepares nickel-cobalt-manganese ternary material | |
| CN107579226A (en) | The preparation method of the nickel-cobalt-manganese ternary material improved by strontium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160318 Address after: 101407 Beijing Yanqi Yanqi Economic Development Zone Huairou District Road No. 3 Patentee after: CHINA AUTOMOTIVE BATTERY RESEARCH INSTITUTE Co.,Ltd. Address before: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Patentee before: General Research Institute for Nonferrous Metals |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20130508 Assignee: Youyan New Energy Materials (Jiangxi) Co.,Ltd. Assignor: CHINA AUTOMOTIVE BATTERY RESEARCH INSTITUTE Co.,Ltd. Contract record no.: X2024980000338 Denomination of invention: A nickel based positive electrode material and its preparation method and battery Granted publication date: 20150930 License type: Common License Record date: 20240110 |
|
| EE01 | Entry into force of recordation of patent licensing contract |