CN107579226B - Preparation method of strontium-improved nickel-cobalt-manganese ternary material - Google Patents
Preparation method of strontium-improved nickel-cobalt-manganese ternary material Download PDFInfo
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- CN107579226B CN107579226B CN201710773250.2A CN201710773250A CN107579226B CN 107579226 B CN107579226 B CN 107579226B CN 201710773250 A CN201710773250 A CN 201710773250A CN 107579226 B CN107579226 B CN 107579226B
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- strontium
- cobalt
- nickel
- compound
- manganese
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- 239000000463 material Substances 0.000 title claims abstract description 77
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 229910001427 strontium ion Inorganic materials 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 10
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 9
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 9
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 9
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 7
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 7
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims abstract description 7
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims abstract description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 238000007600 charging Methods 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910001437 manganese ion Inorganic materials 0.000 claims description 9
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- 150000002642 lithium compounds Chemical class 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 150000003438 strontium compounds Chemical class 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 6
- 235000006748 manganese carbonate Nutrition 0.000 claims description 6
- 239000011656 manganese carbonate Substances 0.000 claims description 6
- 229940093474 manganese carbonate Drugs 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010277 constant-current charging Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229940071264 lithium citrate Drugs 0.000 claims description 3
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 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
- 150000001875 compounds Chemical class 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
- 230000000630 rising effect Effects 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 claims 2
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 claims 2
- 238000001035 drying Methods 0.000 abstract description 5
- -1 strontium ion compound Chemical class 0.000 abstract description 3
- 238000001238 wet grinding Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 50
- 229910052759 nickel Inorganic materials 0.000 description 20
- 238000000975 co-precipitation Methods 0.000 description 18
- 239000011572 manganese Substances 0.000 description 18
- 239000006104 solid solution Substances 0.000 description 17
- 229910017052 cobalt Inorganic materials 0.000 description 15
- 239000010941 cobalt Substances 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910021311 NaFeO2 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910013191 LiMO2 Inorganic materials 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 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 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229910014920 LiMn6 Inorganic materials 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910016483 Mn1/3Co1/3O2 Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of a nickel-cobalt-manganese ternary material improved by strontium, which is characterized in that a strontium ion compound is strontium oxide, strontium chloride, strontium nitrate, strontium hydroxide or strontium carbonate, a nickel compound, a cobalt compound, a manganese compound and the strontium ion compound are mixed according to a molar ratio, a dry precursor is prepared through the steps of wet grinding, ammonia water addition, lithium addition, aging, drying and the like, the dry precursor is placed in an oxygen atmosphere, and the strontium-improved nickel-cobalt-manganese ternary material is prepared by adopting a programmed heating method or a temperature-zone-by-temperature heating method2The characteristic diffraction peaks of the structure are matched, no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peak characteristics generated by diffraction.
Description
Technical Field
The invention belongs to the technical field of battery electrode material preparation, and relates to a preparation method of a nickel-cobalt-manganese ternary material which can be used for lithium batteries, lithium ion batteries, polymer batteries and super capacitors and is improved by strontium.
Technical Field
With the increasing exhaustion of fossil energy, energy problems become a focus of attention. The search for new energy storage materials becomes one of the hot spots of research. The lithium ion battery of the new energy storage system has the advantages of high voltage, large capacity, no memory effect, long service life and the like, and can be widely applied to digital products such as mobile phones, digital cameras, notebook computers and the like and power tools such as electric vehicles, hybrid electric vehicles and the like.
The lithium ion battery comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte, a current collector and the like. Among them, the positive electrode material largely determines the performance of the battery. The positive electrode materials that have been successfully commercialized include lithium cobaltate, lithium manganate, lithium iron phosphate, and the like. However, the above materials have many disadvantages, and it is a hot research to find a positive electrode material with higher cost performance. In 1997, Ohzuku et al [ Ohzuku t.et al, chem.lett., 1997, 68: 642.]LiNi was first studied1/3Mn1/3Co1/3O2The properties of type III ternary materials. Research shows that the material fuses LiCoO2、LiNiO2And LiMn2O4Has the advantages of high reversible capacity, low cost, low toxicity and the like. The nickel cobalt manganese ternary material can be represented as: LiNixCoyMnzO2For example, the ternary material with the molar ratio of nickel, cobalt and manganese (x: y: z) of 3: 3 is called 333 type for short, the ternary material with the molar ratio of nickel, cobalt and manganese of 5: 2: 3 is called 523 type, the ternary material with the molar ratio of nickel, cobalt and manganese of 8: 1 is called 811 type, and other similar types are used, the 333 type, 523 type, 622 type and 811 type ternary materials all have α -NaFeO2Shaped layerAnd (5) structure. In the ternary material, the valence of nickel, cobalt and manganese elements is +2 valence, +3 valence and +4 valence respectively. Ni is the main active element. Theoretically, the higher the relative content of nickel, the higher the discharge capacity of the ternary material.
Koymaya et al [ Koymaya y., et al, j.power Sources, 2003, 119 (2): 644-648.]It is considered that Li1-xNi1/3Co1/3Mn1/3O2Charging process with LiNi1/3Co1/3Mn1/3O2The examples are: with the elimination of Li ions, different electron pairs react. When 0 < x < 1/3, Ni occurs2+/Ni3+A transition of (a); when 1/3 < x < 2/3, Ni occurs3+/Ni4+A transition of (a); when 2/3 < x < 1, Co occurs3+/Co4+Is performed.
When 0 < x < 1/3
When 1/3 < x < 2/3
When 2/3 < x < 1:
for ternary materials, Ni at charging voltages below 4.3V (vs Li/Li +)2+As the main active material, Co3 +Can improve the cyclability and rate capability of the material, while Mn4+Does not participate in the oxidation-reduction reaction in the circulation process.
Due to xLi2MnO3·(1-x)LiMO2The structure and chemical composition of solid solution (M ═ Ni, Co, Mn) materials are very close to those of ternary materials, and many documents incorrectly express the structures of the two materials. For xLi2MnO3·(1-x)LiMO2Solid solution (M ═ Ni, Co, Mn)Charging voltage<4.4V, Li in solid solution2MnO3No electrochemical activity [ Yang f., Zhang q.et al, electrochim. acta, 2015, 165: 182-190.]. At this voltage, the LiMO in solid solution is mainly involved in the electrochemical reaction during charging2。Li+From LiMO2Is removed while M is oxidized to MO2. During discharge in this case, with Li+Embedding, MO2Can not be completely converted into LiMO2Resulting in a partially irreversible reaction. When charging voltage>Li in solid solution at 4.4V2MnO32 Li being extractable+And O2-Incorporation (actually taking off Li)2O), producing electrochemically active MnO2Phase (1); during discharge, part of Li originally extracted+Can be embedded back into MnO2In (1). [ Chen c.j., et al, j.am. chem.soc., 2016, 138: 8824-8833.]It can be seen from the above discussion that while both ternary and solid solution materials have the layered α -NaFeO2The structure and chemical composition are very similar. However, the charge-discharge curves and XRD diffraction patterns of the ternary material and the solid solution material are obviously different. From the relation curve of the discharge voltage and the discharge capacity of charge and discharge, when the charge voltage is higher than 4.4V, the charge specific capacity and the discharge specific capacity of the solid solution are obviously increased, and the discharge curve of the solid solution has the characteristic of oblique lines and has no obvious discharge voltage platform; in this case, the charging specific capacity and the discharging specific capacity of the ternary material are only slightly increased and are not obviously increased, and the discharging curve of the ternary material presents an S-shaped characteristic and has an obvious discharging voltage platform.
In recent years, spray drying and other preparation methods are also concerned, however, the coprecipitation method is still the main method for preparing the nickel, cobalt and manganese ternary material. Other methods are not industrially valuable. Briefly discussed below.
The coprecipitation method is to add a precipitator and a complexing agent into a mixed solution of various cations to control the nucleation and growth processes of precipitation, so as to obtain coprecipitation with controllable morphology and particle size. And filtering and drying the prepared coprecipitation to obtain a precursor. Mixing the precursor with lithium salt, and sintering at high temperatureThe method is used for preparing the anode material. The synthesis method has good reproducibility, and the prepared product has uniform composition. The coprecipitation with controllable appearance and particle size can be prepared by controlling the stirring speed, pH value, aging temperature, precipitator, the dripping speed of the precipitator, the proportion of ammonia water and metal ions and the like in the precipitation process, and the problems of uneven material mixing, too wide particle size distribution and the like in the solid-phase synthesis method are solved. The coprecipitation method is classified into a hydroxide and carbonate coprecipitation method. Specifically, hydroxide and carbonate precipitating agents are respectively used for forming precursor precipitates of transition metal ions, then the precursor precipitates are mixed with lithium salt, and finally the ternary material is prepared by sintering. The hydroxide coprecipitation method is a common method for synthesizing ternary material precursors. The method generally uses NaOH as a precipitator and ammonia water as a complexing agent, controls the pH value in the reaction process through the precipitator, realizes the purpose of controlling the particle size and the morphology of a precursor through controlling the reaction temperature and the stirring speed, and finally controls the morphology and the electrochemical performance of the ternary material. During the preparation, due to the intermediate product Mn (OH) formed2The precursor is unstable and is easily oxidized by air, and the performance of the material is affected, so nitrogen needs to be introduced for protection in the process of preparing the precursor. The hydroxide coprecipitation method has the advantages that a precursor with uniform particle size distribution is obtained by controlling reaction conditions; the disadvantage is the complex preparation process. In the preparation process, the concentration of raw materials, the dropping speed, the stirring speed, the pH value and the reaction temperature all influence the tap density and the particle size uniformity of the material. The biggest problems with this approach are: the precipitation conditions of hydroxide coprecipitation generated by nickel, cobalt and manganese are greatly different, and if the dosage of alkali in the precipitation process is insufficient, nickel and cobalt ions may be incompletely precipitated; if the amount of the alkali used in the precipitation process is excessive, the precipitated manganese ions may be dissolved, so that the room-temperature chemical composition and the performance of the prepared sample are difficult to be consistent.
Liang et al [ Liang L, et al, Electrochim Acta, 2014, 130: 82-89.]With NiSO4·6H2O、CoSO4·7H2O and MnSO4·H2Taking O as a raw material and 0.6mol/L ammonia water as a complexing agent, and preparing a uniformly mixed spherical precursor at a stirring speed of 800r/min and a pH value of 11.2. Will be the forebodyThe bulk is washed, filtered, dried and calcined to obtain the product with tap density of 2.59g/cm3622 type material. Under the current of 1C multiplying power and the voltage range of 2.8-4.3V, the discharge specific capacity of the prepared sample at the 1 st cycle is 172.1 mAh.g-1The capacity retention rates at 100 cycles were 94.3%, respectively. Wen Lei et al [ Wen Lei, et al, Beijing university school newspaper, 2006, 42 (1): 12-17.]With LiOH. H2O、NaHCO3、CoSO4·7H2O、NiSO4·6H2O and MnSO4·5H2O is used as a raw material, carbonate precursor precipitate is prepared, and LiNi is prepared by washing, filtering, drying and secondary sintering1/3Mn1/3Co1/3O2And (3) sampling. Research shows that in a voltage range of 2.5-4.4V, the first discharge capacity of the prepared sample is 162 mAh.g-1And has good cycle performance.
Mao yu qin, etc. (Mao yu qin, Chinese patent: CN 103972499A, 2014-08-06]Firstly, preparing soluble nickel salt, cobalt salt, aluminum salt and lithium salt into spherical LiNi by a coprecipitation method1-a-bCoaAlbO2Mixing the material with nano TiO2Spraying the powder into a coating device to obtain LiNi1-a-bCoaAlbO2/TiO2Capacity retention of greater than 99% at 50 cycles.
Previous researches show that the concentration of raw materials, the dropping speed of a precipitator, the stirring speed, the pH value and the reaction temperature are the key points for preparing the ternary material with high tap density and uniform particle size distribution. Zhou new east et al [ zhou new east et al, chinese patent: CN102244239A, 2011-11]The spherical nickel-cobalt-aluminum ternary material is prepared by using a nickel, cobalt and aluminum salt solution and a lithium source through a secondary precipitation method, and the prepared sample has high tap density (3.02 g/cm)3) And the like. Further studies have shown that, in addition to the composition, particle size and particle size distribution of particles prepared by co-precipitation having an effect on the properties of the prepared samples, the radial distribution of the sample particle composition also has a significant effect on the properties of the samples. Hua et al [ Hua C, et al, j. alloys and Compounds, 2014, 614: 264-270.]With NiSO4·6H2O、CoSO4·7H2O、MnSO4·5H2Dissolving O as raw material in a circulating stirring kettle, adding ammonia water as complexing agent, and adding sodium hydroxide solution to adjust pH to 11.5. Stirring the mixture for 24 hours at the rotating speed of 750rpm and at the temperature of 55 ℃ to prepare a hydroxide precursor. And filtering, washing and drying the prepared precursor, and mixing and calcining the precursor and lithium hydroxide to prepare the 811 type ternary material with linear gradient. Studies show that the nickel content gradually decreases and the manganese content gradually increases from the core to the surface of the sample particles. Under the condition of large multiplying current, the discharge capacity and the cycle performance of the 811 type ternary material with the composition gradient distribution are obviously superior to those of the corresponding material with the uniform composition distribution. The discharge capacity of the 811 type ternary material forming the linear gradient distribution in the 1 st cycle is 185.2 mAh.g in a voltage interval of 2.8-4.3 and under a current of 1C multiplying power-1The capacity retention at 100 cycles was 93.2%.
Hou et al, j.power Sources, 2014, 265: 174-181 ] sample preparation by fractional precipitation: pumping reactant solution with the molar ratio of nickel, cobalt and manganese of 8: 1 into a reaction kettle to form 811 nuclei, and pumping reactant solution with the molar ratio of nickel, cobalt and manganese of 3: 3 to form a first shell layer; then pumping reactant solution with the molar ratio of nickel, cobalt and manganese being 4: 2 to form a second shell layer; finally, the ternary material with a core of 811 type and a shell of 333 type and 422 type is prepared. The capacity retention for the 300 cycles of the prepared sample at 4C rate current was 90.9%.
Guokai et al [ guokai et al, chinese patent: CN 104979553A, 2015-10-14]Soluble nickel salt, cobalt salt, aluminum salt, lithium carbonate or lithium hydroxide are prepared into LiNi by a coprecipitation methodcCo1-c-dAldO2(c is more than 0.5, 0.5 is more than d is more than 0, 1 is more than c + d) coated LiNiaCo1-a-bAlbO2(a is more than 0.7, b is more than or equal to 0.05 and more than or equal to 0, and a + b is more than 1). Research shows that the coated micron LiNiaCo1-a-bAlbO2The cycle stability and the thermal stability of (a is more than 0.7, b is more than or equal to 0 and more than 1 and more than a + b) are obviously improved, and the flatulence rate is obviously reduced. Micron LiNi0.8Co0.15Al0.05O2Has a tap density of2.51g/cm3. Under the voltage range of 3.0-4.3V and the current with 0.1C multiplying power, the first discharge capacity of the sample is 194.5mAh/g, and the first charge-discharge efficiency is 91.9%.
However, despite the above improvements, the ternary materials prepared at present have problems such as low electronic conductivity, poor high rate stability, poor high voltage cycling stability, cation shuffling, poor high and low temperature performance, and the like. In response to the above problems, the performance is currently improved mainly by doping, surface coating and post-treatment. However, the actual improvement effect is not significant at present.
Disclosure of Invention
The coprecipitation method is to add a precipitant into a solution of mixed metal salts to precipitate two or more cations in the solution together to produce a precipitate mixture or a pure solid solution precursor. The sample prepared by the coprecipitation method has the advantages of narrow particle size distribution, high tap density, excellent electrochemical performance and the like. However, the coprecipitation method requires energy-consuming and water-consuming preparation steps such as filtration and washing. A large amount of industrial wastewater is generated. In the preparation process of the coprecipitation method, the added precipitant is difficult to form uniform concentration in each part of the solution, so that precipitated particles are agglomerated or form nonuniform composition. In addition, the precipitation concentration products of nickel, cobalt and manganese salts have large difference, and the precipitation conditions of different ions have large difference. Manganese ions are easy to over-dissolve in a strong alkaline solution, the stoichiometric ratio of precursors is difficult to control, and the electrochemical properties of samples in different batches are affected. In order to improve the preparation process conditions and reduce the defects of the preparation method, the invention adopts a direct precipitation method to prepare the nickel-cobalt-manganese ternary material. In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
according to the molar ratio x of nickel ions, cobalt ions, manganese ions, lithium ions and strontium ions: y: z: k: and m, respectively weighing a nickel compound, a cobalt compound, a manganese compound, a lithium compound and a strontium compound. A nickel compound, a cobalt compound, a manganese compound and a strontium compound were mixed to obtain a mixture 1. And adding deionized water with the volume 1-80 times of the total volume of the mixture 1, and uniformly mixing. Dropwise adding ammonia water under the condition of continuous stirring until the pH value of the solution falls within the range of 10.5-13.5, adding the weighed lithium compound, uniformly mixing through mixing equipment, and aging at any temperature within the temperature range of 60-90 ℃ for 5-48 hours under the inert atmosphere without oxygen to obtain a mixture serving as a precursor 2. Heating the precursor 2 at any temperature within the range of 120-230 ℃ under the vacuum condition of less than 1 atmospheric pressure to prepare a dried precursor 3, or preparing the dried precursor 3 at any temperature within the range of 120-230 ℃ by adopting a spray drying method. And (3) placing the dried precursor 3 in an oxygen atmosphere, and preparing the strontium-improved nickel-cobalt-manganese ternary material by adopting a programmed heating method or a temperature-region-by-temperature-region heating method.
Two or more of the nickel compound, the cobalt compound, the manganese compound, the lithium compound and the strontium compound are soluble in water.
The molar ratio x of nickel ions, cobalt ions, manganese ions, lithium ions and strontium ions is as follows: y: z: k: m satisfies the following relationship:
x: y: z: m is (0.42-0.49): (0.17-0.19): (0.25-0.30): (0.01-0.08), k is more than or equal to 0.95 and less than or equal to 1.10, and x + y + z + m is equal to k;
or x: y: z: m is (0.52-0.59): (0.17-0.19): (0.17-0.19): (0.01-0.08), k is more than or equal to 0.95 and less than or equal to 1.10, and x + y + z + m is equal to k;
or x: y: z: m ═ 0.72 to 0.79: (0.07-0.10): (0.07-0.10): (0.01-0.07), k is more than or equal to 0.95 and less than or equal to 1.10, and x + y + z + m is equal to k.
The ternary material simultaneously satisfies the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; under the conditions of 0.2C multiplying current and 1 st charge-discharge cycle, the proportion of increasing the charging specific capacity to 4.6V to 4.4V is less than 18 percent relative to the constant current charging of a lithium electrode of the button type half cell prepared from the material; li which does not correspond to JCPDS card 27-1252 in the range of 20-25 degrees of 2 theta angle of sample XRD diffraction pattern2MnO3The diffraction peak of (1).
The programmed heating method is carried out as follows: and (3) placing the dried precursor 3 in an oxygen atmosphere, heating the precursor to any temperature in a temperature range of 790-880 ℃ from the room temperature program at a speed of 0.1-10 ℃/min, and cooling the precursor to the room temperature to obtain the strontium-improved nickel-cobalt-manganese ternary material.
The temperature rising method by temperature zones is carried out as follows: and (3) placing the dried precursor 3 in an oxygen atmosphere, heating from a room temperature region to any temperature in a temperature range of 790-880 ℃ at a heating speed of 0.1-10 ℃/temperature region, and cooling to room temperature to obtain the strontium-improved nickel-cobalt-manganese ternary material.
The nickel compound is nickel hydroxide, nickel oxide, nickel nitrate, nickel chloride, nickel acetate or nickel carbonate.
The cobalt compound is cobalt hydroxide, cobalt oxide, cobalt nitrate, cobalt chloride, cobalt acetate or cobalt carbonate.
The manganese compound is manganese hydroxide, manganese oxide, manganese nitrate, manganese carbonate, manganese chloride or manganese acetate.
The lithium compound is lithium hydroxide, lithium oxide, lithium fluoride, lithium citrate, lithium nitrate, lithium chloride, lithium carbonate or lithium acetate.
The strontium compound is strontium oxide, strontium chloride, strontium nitrate, strontium acetate, strontium hydroxide or strontium carbonate.
The temperature-region-by-temperature-region heating method is used for sintering in a roller kiln, a tunnel kiln or a mesh belt furnace.
The tunnel kiln is a push plate type tunnel kiln.
The temperature in different zones of roller kiln, tunnel kiln or mesh belt furnace is different, which is equivalent to different temperature zones, i.e. the temperature in each temperature zone is different, and generally the temperature is gradually increased from room temperature zone to the temperature needing sintering, and then the temperature is decreased from the temperature needing sintering to room temperature.
The spray drying method is drying at any temperature in a temperature range of 120-230 ℃. The inert atmosphere is nitrogen, argon or helium.
The mixing equipment is ball milling or sanding equipment.
The invention has the advantages of low cost of raw materials, wide raw material sources, simple preparation process, simple and convenient operation and less time consumption. Compared with a coprecipitation method, the sewage discharged in the preparation process is obviously reduced, and the prepared sampleIn the absence of LiMn6The proportion of the super-lattice structure to the increase of the charging specific capacity of 4.6V to 4.4V relative to the constant current charging of the lithium electrode is less than 18%, the prepared electrode material has good consistency, uniform composition and excellent discharge performance, particularly the discharge cycle performance under the condition of large current is good, and a good foundation is laid for industrialization.
Compared with the invention patents (ZL201210391584.0, 201210391629.4, 201210391413.8, 201210391672.0, 201210391441.x) related to solid solution preparation, which were applied in the earlier stage of this project group, the invention patents are patents with completely different compositions. From a structural point of view, the samples prepared herein do not have LiMn6Superlattice structure, and the structure of the solid solution sample has LiMn6A superlattice structure; from the chemical composition of the sample, the compositions of the 523, 622, 811 type ternary materials are close to Li [ Ni ]0.5Co0.2Mn0.3]O2、Li[Ni0.6Co0.2Mn0.2]O2、Li[Ni0.8Co0.1Mn0.1]O2(ii) a And solid solution xLi2MnO3(1-x)Li[NiyMnzCok]O2Has the chemical formula of Li(1+x)[Ni(1-x)yCo(1-x)kMn(x+z-xz)]O(2+x). If the formula xLi in patent ZL201210391584.0 is considered2MnO3(1-x)Li[NiyMnzCok]O2The value range of (a) can be calculated to obtain the theoretical composition of a solid solution sample: li: ni: co: mn: the O molar ratio is (1-1.39): (0.0173-0.333): (0.0174-0.443): (0.204-0.952): (1.87-2.26). The theoretical composition of the solid solution patent applied in the previous period of this project group is similar to that of patent ZL201210391584.0, therefore, the chemical formulas of the solid solution patent applied in the previous period and the solid solution applied in the previous period have certain similarities, but the two are completely different inventions.
Drawings
Figure 1 is an XRD diffractogram of a sample prepared in example 1 of the present invention.
Fig. 2 is a graph of the discharge at cycle 1 at 1C rate current for the sample prepared in example 1 of the present invention at a voltage interval of 2.5 to 4.3V.
FIG. 3 is a graph of discharge capacity versus cycle performance for samples prepared in example 1 of the present invention at a voltage interval of 2.5 to 4.3V and a current rate of 1C.
Detailed Description
The present invention will be further described with reference to the following examples. The examples are merely further additions and illustrations of the present invention, and are not intended to limit the invention.
Example 1
Respectively weighing nickel acetate, cobalt acetate, manganese carbonate, lithium hydroxide and strontium oxide according to the molar ratio of nickel ions, cobalt ions, manganese ions, lithium ions and strontium ions of 0.49: 0.19: 0.3: 1.06: 0.08, mixing the nickel acetate, the cobalt acetate, the manganese carbonate and the strontium ions to obtain a mixture 1, adding deionized water with the volume being 3 times of the total volume of the mixture 1, uniformly mixing, dropwise adding ammonia water under the condition of continuous stirring until the acidity of the solution is pH 12.5, adding the weighed lithium hydroxide, uniformly mixing through a ball milling device, aging for 24 hours at the temperature of 85 ℃ in a nitrogen atmosphere to obtain a precursor 2, heating the precursor 2 at the temperature of 230 ℃ under the vacuum condition of 0.1 atmospheric pressure to obtain a dried precursor 3, placing the precursor 3 in an oxygen atmosphere, heating from room temperature to 850 ℃ at the speed of 5 ℃/min, cooling to the room temperature to obtain layered α -NaFeO2Structural nickel-cobalt-manganese ternary material improved by strontium.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; under the conditions of 0.2C multiplying current and 1 st cycle charge and discharge, the proportion of increasing the charging specific capacity to 4.6V to 4.4V by the constant current charge of the lithium electrode is 15 percent; no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peaks resulting from diffraction.
Example 2
According to the mole ratio of nickel, cobalt, manganese, lithium and doped strontium ions of 0.47: 0.17: 0.30: 1.01: 0.07 separately weighing the nickel oxideMixing nickel oxide, cobalt nitrate, manganese acetate and strontium oxide to obtain a mixture 1, adding deionized water with the volume being 1 time of the total volume of the mixture 1, uniformly mixing, dropwise adding ammonia water under the condition of continuous stirring until the acidity pH value of the solution is 13.5, adding weighed lithium citrate, uniformly mixing through a sanding device, aging at 60 ℃ for 48 hours under the argon atmosphere to obtain a precursor 2, preparing a dried precursor 3 by using a spray drying method at 120 ℃ for the precursor 2, placing the precursor 3 in an oxygen atmosphere, performing programmed heating from room temperature to 880 ℃ at the speed of 10 ℃/min, and cooling to room temperature to obtain layered α -NaFeO2Structural nickel-cobalt-manganese ternary material improved by strontium.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; the button half-cell prepared from the prepared ternary material is charged to 4.6V to 4.4V at a constant current relative to a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charge and discharge, and the ratio of the increase of the specific charge capacity is 16 percent; no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peaks resulting from diffraction.
Example 3
Respectively weighing nickel nitrate, cobalt carbonate, manganese hydroxide, lithium nitrate and strontium nitrate according to the molar ratio of nickel, cobalt, manganese, lithium and doped strontium ions of 0.52: 0.19: 0.98: 0.08, mixing the nickel nitrate, the cobalt carbonate, the manganese hydroxide and the strontium nitrate to obtain a mixture 1, adding deionized water with the volume being 80 times of the total volume of the mixture 1, uniformly mixing, dropwise adding ammonia water under the condition of continuous stirring until the acidity of the solution is pH 10.5, adding the weighed lithium nitrate, uniformly mixing by using a ball mill, aging for 48 hours at 90 ℃ in a helium atmosphere to obtain a precursor 2, heating the precursor 2 at 120 ℃ under the vacuum condition of 0.9 atmospheric pressure to obtain a dried precursor 3, placing the precursor 3 in an oxygen atmosphere, heating from room temperature to 880 ℃ at the speed of 0.1 ℃/min, cooling to room temperature to obtain α -NaFeO with the structure2Structural strontium modified nickelA cobalt manganese ternary material.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; the button half-cell prepared from the prepared ternary material is charged to 4.6V to 4.4V at a constant current relative to a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charge and discharge, and the ratio of the increase of the charging specific capacity is 15 percent; no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peaks resulting from diffraction.
Example 4
Respectively weighing nickel chloride, cobalt oxide, manganese nitrate, lithium oxide and strontium chloride according to the molar ratio of nickel, cobalt, manganese, lithium and doped strontium ions of 0.59: 0.19: 0.98: 0.01, mixing the nickel chloride, the cobalt oxide, the manganese nitrate and the strontium chloride to obtain a mixture 1, adding deionized water with the volume being 1 time of the total volume of the mixture 1, uniformly mixing, dropwise adding ammonia water under the condition of continuous stirring until the acidity of the solution is pH 13.5, adding the weighed lithium oxide, uniformly mixing through a sand grinding device, aging for 5 hours at the temperature of 60 ℃ and under the nitrogen atmosphere to obtain a precursor 2, heating the precursor 2 at the temperature of 200 ℃ under the vacuum condition of 0.01 atmospheric pressure to obtain a dried precursor 3, placing the precursor 3 in an oxygen atmosphere, heating from room temperature to 790 ℃ at the speed of 1 ℃/min, cooling to room temperature to obtain the layered α -NaFeO2Structural nickel-cobalt-manganese ternary material improved by strontium.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; the button half-cell prepared from the prepared ternary material is charged to 4.6V to 4.4V at a constant current relative to a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charge and discharge, and the ratio of the increase of the specific charge capacity is 16 percent; no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peaks resulting from diffraction.
Example 5
Weighing nickel oxide, cobalt nitrate, manganese chloride, lithium carbonate and strontium chloride according to the molar ratio of nickel ions, cobalt ions, manganese ions, lithium ions and strontium ions of 0.79: 0.10: 0.10: 1.06: 0.07 respectively, mixing the nickel oxide, the cobalt nitrate, the manganese chloride and the strontium chloride to obtain a mixture 1, adding deionized water with the volume being 20 times of the total volume of the mixture 1, uniformly mixing, dropwise adding ammonia water under the condition of continuous stirring until the acidity of the solution is pH 10.5, adding the weighed lithium carbonate, uniformly mixing through a sand mill, aging for 26 hours at the temperature of 80 ℃ in a nitrogen atmosphere to obtain a precursor 2, heating the precursor 2 at 230 ℃ under the vacuum condition of 0.1 atmospheric pressure to obtain a dried precursor 3, placing the precursor 3 in an oxygen atmosphere, carrying out programmed heating from room temperature to 790 ℃ at the speed of 0.2 ℃/min, cooling to room temperature to obtain layered α -NaFeO2Structural nickel-cobalt-manganese ternary material improved by strontium.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; the button half-cell prepared from the prepared ternary material is charged to 4.6V to 4.4V at a constant current relative to a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charge and discharge, and the ratio of the increase of the charging specific capacity is 17 percent; no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peaks resulting from diffraction.
Example 6
According to the mole ratio of nickel, cobalt, manganese, lithium and doped strontium ions of 0.72: 0.07: 0.09: 0.95: 0.07 part of nickel carbonate, cobalt carbonate, manganese nitrate, lithium acetate and strontium hydroxide were weighed. Nickel carbonate, cobalt carbonate, manganese nitrate and strontium hydroxide were mixed to obtain mixture 1. Deionized water was added in an amount of 1 time the total volume of the mixture 1 and mixed well. Dropwise adding ammonia water under the condition of continuous stirring until the acidity of the solution is pH 11.0, adding weighed lithium acetate, uniformly mixing by using ball-milling mixing equipment, and aging for 48 hours at 90 ℃ in an argon atmosphere to obtain a precursor 2. Precursor 2 was spray dried at 230 ℃ to prepare dried precursor 3. The precursor 3 is placed in an oxygen atmosphere toHeating from room temperature to 880 deg.C gradually at a heating rate of 0.1 deg.C/temperature region, cooling to room temperature to obtain α -NaFeO with layered structure2Structural nickel-cobalt-manganese ternary material improved by strontium.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; the button half-cell prepared from the prepared ternary material is charged to 4.6V to 4.4V at a constant current relative to a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charge and discharge, and the ratio of the increase of the specific charge capacity is 12%; no weak diffraction peak appears in the range of 20-25 degrees of 2 theta angle of XRD diffraction pattern of the sample, and no Li corresponding to JCPDS card 27-12522MnO3Diffraction peaks resulting from diffraction.
Example 7
Respectively weighing nickel acetate, cobalt chloride, manganese carbonate, lithium nitrate and strontium hydroxide according to the molar ratio of nickel ions, cobalt ions, manganese ions, lithium ions and doped strontium ions of 0.78: 0.09: 0.07: 0.95: 0.01, mixing the nickel acetate, the cobalt chloride, the manganese carbonate and the strontium hydroxide to obtain a mixture 1, adding deionized water with the volume being 80 times of the total volume of the mixture 1, uniformly mixing, dropwise adding ammonia water under the condition of continuous stirring until the acidity pH value of the solution is 13.0, adding the weighed lithium nitrate, uniformly mixing by using a common ball mill, aging for 5 hours at 70 ℃ in an argon atmosphere to obtain a precursor 2, preparing a dried precursor 3 by using a spray drying method at 220 ℃, placing the precursor 3 in an oxygen atmosphere, heating the precursor from a room temperature region to a 790 ℃ temperature region at a heating speed of 10 ℃/DEG C, cooling to the room temperature to obtain α -NaFeO with a layered structure2Structural nickel-cobalt-manganese ternary material improved by strontium.
The ternary material simultaneously meets the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; the button half-cell prepared from the prepared ternary material is charged to 4.6V to 4.4V at a constant current relative to a lithium electrode under the conditions of 0.2C rate current and 1 st cycle charge and discharge, and the ratio of the increase of the charging specific capacity is 11 percent; the 2 theta angle of the XRD diffraction pattern of the sample is 20-25 degrees, no weak diffraction peak is generated, and no weak diffraction peak is generatedWith Li corresponding to JCPDS cards 27-12522MnO3Diffraction peaks resulting from diffraction.
Claims (9)
1. The preparation method of the nickel-cobalt-manganese ternary material improved by strontium is characterized in that the molar ratio x of nickel ions to cobalt ions to manganese ions to lithium ions to strontium ions is as follows: y: z: k: m, respectively weighing a nickel compound, a cobalt compound, a manganese compound, a lithium compound and a strontium compound; mixing a nickel compound, a cobalt compound, a manganese compound and a strontium compound to obtain a mixture 1; adding deionized water with the volume 1-80 times of the total volume of the mixture 1, and uniformly mixing; dropwise adding ammonia water under the condition of continuous stirring until the pH value of the solution falls within the range of 10.5-13.5, adding the weighed lithium compound, uniformly mixing through mixing equipment, and aging at any temperature within the temperature range of 60-90 ℃ for 5-48 hours under the inert atmosphere of nitrogen, argon or helium without oxygen to obtain a mixture as a precursor 2; heating the precursor 2 at any temperature within the range of 120-230 ℃ under the vacuum condition of less than 1 atmospheric pressure to prepare a dried precursor 3 or preparing the dried precursor 3 at any temperature within the range of 120-230 ℃ by adopting a spray drying method; placing the dried precursor 3 in an oxygen atmosphere, and preparing the strontium-improved nickel-cobalt-manganese ternary material by adopting a programmed heating method or a temperature-region-by-temperature-region heating method;
two or more compounds of the nickel compound, the cobalt compound, the manganese compound, the lithium compound and the strontium compound are soluble in water;
the molar ratio x of nickel ions, cobalt ions, manganese ions, lithium ions and strontium ions is as follows: y: z: k: m satisfies the following relationship:
x: y: z: m = (0.42 to 0.49): (0.17-0.19): (0.25-0.30): (0.01-0.08), k is more than or equal to 0.95 and less than or equal to 1.10, and x + y + z + m = k;
or x: y: z: m = (0.52 to 0.59): (0.17-0.19): (0.17-0.19): (0.01-0.08), k is more than or equal to 0.95 and less than or equal to 1.10, and x + y + z + m = k;
or x: y: z: m = (0.72 to 0.79): (0.07-0.10): (0.07-0.10): (0.01-0.07), k is more than or equal to 0.95 and less than or equal to 1.10, and x + y + z + m = k;
the ternary material simultaneously satisfies the following characteristics that diffraction peaks on an XRD diffraction pattern are all equal to those of layered α -NaFeO of JCPDS card 09-00632The characteristic diffraction peaks of the structure are matched; under the conditions of 0.2C multiplying current and 1 st charge-discharge cycle, the proportion of increasing the charging specific capacity to 4.6V to 4.4V is less than 18 percent relative to the constant current charging of a lithium electrode of the button type half cell prepared from the material; li which does not correspond to JCPDS card 27-1252 in the range of 20-25 degrees of 2 theta angle of sample XRD diffraction pattern2MnO3A diffraction peak of (a);
the temperature rising method by temperature zones is carried out as follows: placing the dried precursor 3 in an oxygen atmosphere, heating from a room temperature region to any temperature in a temperature range of 790-880 ℃ at a heating speed of 0.1-10 ℃/temperature region, and cooling to room temperature to obtain the strontium-improved nickel-cobalt-manganese ternary material; the programmed heating method is carried out as follows: and (3) placing the dried precursor 3 in an oxygen atmosphere, heating the precursor to any temperature in a temperature range of 790-880 ℃ from the room temperature program at a speed of 0.1-10 ℃/min, and cooling the precursor to the room temperature to obtain the strontium-improved nickel-cobalt-manganese ternary material.
2. The method of claim 1, wherein the nickel compound is selected from the group consisting of nickel hydroxide, nickel oxide, nickel nitrate, nickel chloride, nickel acetate, and nickel carbonate.
3. The method of claim 1, wherein the cobalt compound is cobalt hydroxide, cobalt oxide, cobalt nitrate, cobalt chloride, cobalt acetate, or cobalt carbonate.
4. The method of claim 1, wherein the manganese compound is manganese hydroxide, manganese oxide, manganese nitrate, manganese carbonate, manganese chloride or manganese acetate.
5. The method of claim 1, wherein the lithium compound is selected from the group consisting of lithium hydroxide, lithium oxide, lithium fluoride, lithium citrate, lithium nitrate, lithium chloride, lithium carbonate, and lithium acetate.
6. The method for preparing a strontium-modified Ni-Co-Mn ternary material as claimed in claim 1, wherein the strontium compound is strontium oxide, strontium chloride, strontium nitrate, strontium acetate, strontium hydroxide or strontium carbonate.
7. The method of claim 1, wherein the mixing device is a ball mill or a sand mill.
8. The method for preparing the strontium-modified Ni-Co-Mn ternary material according to claim 1, wherein the temperature-region-by-temperature-region heating method is performed in a roller kiln, a tunnel kiln or a mesh belt furnace.
9. The method of claim 8, wherein the tunnel kiln is a push plate tunnel kiln.
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