TWI837083B - 鋰離子陰極的製造方法及鋰離子陰極及包含該鋰離子陰極的電池 - Google Patents
鋰離子陰極的製造方法及鋰離子陰極及包含該鋰離子陰極的電池 Download PDFInfo
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- TWI837083B TWI837083B TW107101632A TW107101632A TWI837083B TW I837083 B TWI837083 B TW I837083B TW 107101632 A TW107101632 A TW 107101632A TW 107101632 A TW107101632 A TW 107101632A TW I837083 B TWI837083 B TW I837083B
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- Prior art keywords
- lithium ion
- manufacturing
- ion cathode
- cathode
- carbonate
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 95
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims description 60
- 239000002243 precursor Substances 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 102
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 127
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 239000011572 manganese Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 54
- 239000000126 substance Substances 0.000 claims description 40
- 235000006408 oxalic acid Nutrition 0.000 claims description 37
- 239000011029 spinel Substances 0.000 claims description 36
- 229910052596 spinel Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- 239000002002 slurry Substances 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 239000002019 doping agent Substances 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 229910013716 LiNi Inorganic materials 0.000 claims description 21
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000007921 spray Substances 0.000 claims description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 16
- 239000011656 manganese carbonate Substances 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
- 239000002904 solvent Substances 0.000 claims description 15
- 229940093474 manganese carbonate Drugs 0.000 claims description 14
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 14
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 6
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- VMZXTHCNVOQXRZ-UHFFFAOYSA-N 3,4-dioxohexanedioic acid Chemical compound OC(=O)CC(=O)C(=O)CC(O)=O VMZXTHCNVOQXRZ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 description 55
- 239000000243 solution Substances 0.000 description 43
- 239000007789 gas Substances 0.000 description 42
- 229910052723 transition metal Inorganic materials 0.000 description 42
- 229910001868 water Inorganic materials 0.000 description 40
- 238000002441 X-ray diffraction Methods 0.000 description 37
- 150000003624 transition metals Chemical class 0.000 description 37
- 239000000843 powder Substances 0.000 description 33
- 235000002639 sodium chloride Nutrition 0.000 description 31
- 239000000463 material Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 27
- 238000010586 diagram Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 230000008569 process Effects 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 238000010899 nucleation Methods 0.000 description 17
- 230000006911 nucleation Effects 0.000 description 17
- 238000001354 calcination Methods 0.000 description 16
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 14
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- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000012546 transfer Methods 0.000 description 11
- -1 lithium-ion metal oxide Chemical class 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
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- 239000011780 sodium chloride Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
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- 239000007858 starting material Substances 0.000 description 8
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- 150000003891 oxalate salts Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
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- 229910021450 lithium metal oxide Inorganic materials 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 3
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 3
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- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 description 3
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- 229910018626 Al(OH) Inorganic materials 0.000 description 2
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- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- INARWLVFBQDLIN-UHFFFAOYSA-L manganese(2+);oxalate;hydrate Chemical compound O.[Mn+2].[O-]C(=O)C([O-])=O INARWLVFBQDLIN-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
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- C01G53/54—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (Mn2O4)-, e.g. Li(NixMn2-x)O4 or Li(MyNixMn2-x-y)O4
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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| US20200373560A1 (en) * | 2019-05-21 | 2020-11-26 | Nano One Materials Corp. | Stabilized High Nickel NMC Cathode Materials for Improved Battery Performance |
| US12355063B2 (en) | 2018-04-18 | 2025-07-08 | Nano One Materials Corp. | Battery with spinel cathode |
| WO2019200464A1 (en) * | 2018-04-18 | 2019-10-24 | Nano One Materials Corp. | One-pot synthesis for linbo3 coated spinel |
| US11316157B1 (en) * | 2018-05-26 | 2022-04-26 | Ge Solartech, LLC | Methods for the production of cathode materials for lithium ion batteries |
| WO2020264461A1 (en) * | 2019-06-28 | 2020-12-30 | Feng Lin | Methods and compositions for high-energy battery cathodes |
| KR20210079130A (ko) * | 2019-12-19 | 2021-06-29 | 주식회사 포스코 | 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
| CN111430683A (zh) * | 2020-01-17 | 2020-07-17 | 蜂巢能源科技有限公司 | 锂离子电池的无钴正极材料及其制备方法和锂离子电池 |
| CN111498908A (zh) * | 2020-04-27 | 2020-08-07 | 中信大锰矿业有限责任公司 | 一种类球形富锰三元前驱体的制备方法 |
| US20210359300A1 (en) * | 2020-05-14 | 2021-11-18 | Nano One Materials Corp. | Alternative Method for Making Lithium Battery Cathode Materials |
| CN116235329A (zh) * | 2020-09-03 | 2023-06-06 | 加拿大商纳诺万麦帝瑞尔公司 | 使用金属原料制备cam前体的替代一锅法 |
| EP4229702A4 (en) * | 2020-10-13 | 2025-07-23 | Nano One Mat Corp | IMPROVED SPINEL CATHODE BATTERY |
| US12077452B2 (en) | 2021-05-17 | 2024-09-03 | Nano One Materials Corp. | Intermediate material between precursor and cathode active material |
| CN114361444B (zh) * | 2021-12-31 | 2024-08-06 | 中国有研科技集团有限公司 | 一种具有单晶均质核-辐射状梯度壳的高镍材料及其应用 |
| US20240097225A1 (en) * | 2022-09-19 | 2024-03-21 | Nano One Materials Corp | Process for Efficient Recycling of Cathode Active Materials |
| CN115763783A (zh) * | 2022-12-01 | 2023-03-07 | 荆门市格林美新材料有限公司 | 一种三元正极材料及其制备方法和应用 |
| CN116751120B (zh) * | 2023-06-16 | 2025-07-29 | 惠州亿纬锂能股份有限公司 | 一种草酸锂及其制备方法与用途 |
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2018
- 2018-01-17 CN CN201880007543.2A patent/CN110495025B/zh active Active
- 2018-01-17 KR KR1020197022064A patent/KR102443307B1/ko active Active
- 2018-01-17 EP EP18742255.5A patent/EP3571735A4/en active Pending
- 2018-01-17 TW TW107101632A patent/TWI837083B/zh active
- 2018-01-17 WO PCT/CA2018/050044 patent/WO2018132903A1/en not_active Ceased
- 2018-01-17 CN CN202310991073.0A patent/CN116845217A/zh active Pending
- 2018-01-17 JP JP2019538406A patent/JP7100648B2/ja active Active
- 2018-01-17 CA CA3048267A patent/CA3048267A1/en active Pending
- 2018-01-17 US US16/472,956 patent/US11121370B2/en active Active
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2021
- 2021-08-12 US US17/400,223 patent/US20210376320A1/en not_active Abandoned
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| CN103066263A (zh) * | 2013-01-14 | 2013-04-24 | 思伊纳化学科技（北京）有限公司 | 一种锂离子电池正极材料及其制备方法 |
| CN103825014A (zh) * | 2014-01-09 | 2014-05-28 | 北京理工大学 | 一种锂离子电池高电压正极材料锂镍锰复合氧化物的制备方法 |
| CN104157831A (zh) * | 2014-08-19 | 2014-11-19 | 哈尔滨工业大学 | 一种核壳结构的尖晶石镍锰酸锂、层状富锂锰基复合正极材料及其制备方法 |
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| Publication number | Publication date |
|---|---|
| CN110495025B (zh) | 2023-09-05 |
| CA3048267A1 (en) | 2018-07-26 |
| JP7100648B2 (ja) | 2022-07-13 |
| KR102443307B1 (ko) | 2022-09-15 |
| EP3571735A1 (en) | 2019-11-27 |
| KR20190127671A (ko) | 2019-11-13 |
| JP2020505724A (ja) | 2020-02-20 |
| CN116845217A (zh) | 2023-10-03 |
| US20210376320A1 (en) | 2021-12-02 |
| WO2018132903A1 (en) | 2018-07-26 |
| TW201841836A (zh) | 2018-12-01 |
| US11121370B2 (en) | 2021-09-14 |
| CN110495025A (zh) | 2019-11-22 |
| EP3571735A4 (en) | 2020-10-21 |
| US20190372120A1 (en) | 2019-12-05 |
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