CN110797529A - Doped high-nickel high-voltage NCM positive electrode material and preparation method thereof - Google Patents
Doped high-nickel high-voltage NCM positive electrode material and preparation method thereof Download PDFInfo
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- CN110797529A CN110797529A CN201911075309.6A CN201911075309A CN110797529A CN 110797529 A CN110797529 A CN 110797529A CN 201911075309 A CN201911075309 A CN 201911075309A CN 110797529 A CN110797529 A CN 110797529A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 57
- 239000011572 manganese Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000002019 doping agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 20
- 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 18
- 230000008569 process Effects 0.000 claims description 14
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 10
- 229940044175 cobalt sulfate Drugs 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 125000005341 metaphosphate group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000748 compression moulding Methods 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- 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 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 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
- 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 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 71
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 46
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 7
- 230000001351 cycling effect Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 4
- 229910003005 LiNiO2 Inorganic materials 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 229910013292 LiNiO Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000036284 oxygen consumption Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910002993 LiMnO2 Inorganic materials 0.000 description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 2
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 2
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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 discloses a doped high-nickel high-voltage NCM (negative polarity metal) positive electrode material and a preparation method thereof, belonging to the field of lithium ion batteries, wherein an NCM precursor is obtained by doping manganese and cobalt at the same time, and then a dopant M is added into the precursor and the precursor is sintered in a high-pressure oxygen atmosphere to obtain the lithium ion battery positive electrode material; the four solutions are adopted to prepare the anode material by combining parallel-flow coprecipitation with a high-pressure solid-phase synthesis method, and the prepared product has high purity, high crystallization quality, large and uniform particle density of the product, excellent electrochemical performance and low manufacturing cost, is an ideal anode material with high energy density, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a doped high-nickel high-voltage NCM positive electrode material and a preparation method thereof.
Background
With the increasingly worsening of global environment and the exhaustion of fossil energy resources, the research and development of energy conservation and emission reduction and green energy resources are urgently and urgently needed, and the development and application of new energy and renewable clean energy resources are very important at home and abroad. The lithium ion battery is a novel green and environment-friendly energy source with a good prospect. Because it has the advantages of high energy density, quick charging, small self-discharge, long-time storage, excellent cycle performance, no memory effect, wide working temperature, light weight and the like, the lithium ion battery has been widely applied to various portable electronic devices and is gradually becoming an ideal power source for electric vehicles and hybrid electric vehicles.
The main anode material currently applied to lithium ion batteries in batches is lithium cobaltate (LiCoO)2) Lithium nickelate (LiNiO)2) Lithium manganate (LiMn)2O4) Lithium iron phosphate (LiFePO)4) Lithium nickel cobalt manganese oxide (LiNi)1-x-yCoxMnyO2). Lithium cobaltate is the anode material which is the earliest to realize commercial application, has mature large-scale production technology, is widely applied to low-power movable electronic products, but has the defects of deficient cobalt resource, high price, high toxicity and environmental protection; although lithium manganate has the advantages of rich resources, low price, no pollution to the environment, high de-intercalation potential and high power density, the application of lithium manganate is limited by the low capacity and unstable cycle performance of lithium manganate; although the lithium iron phosphate anode material is environment-friendly and nontoxic, rich in mineral resources, low in raw material cost, excellent in temperature tolerance and excellent in cycle stability, the lithium iron phosphate anode material has poor ionic and electronic conductivity, small density, large volume, low energy density and poor low-temperature performance, so that the application and development of the lithium iron phosphate anode material are limited, and the lithium iron phosphate anode material is particularly limited in the aspects of endurance mileage and low-temperature performance and is difficult to apply on a large scale.
Lithium nickelate LiNiO2Positive electrode material and LiCoO2The anode materials are all materials with a laminated structure, the discharge specific capacity of the anode materials is up to 210mAh/g, and the anode materials are specific to LiCoO2The discharge specific capacity is much higher than 140mAh/g, the power density and the energy density are high, the conductivity is good, and the material is relatively cheapThe price and the lower toxicity of the lithium nickelate anode material lead the lithium nickelate anode material to be hopeful to replace the lithium cobaltate anode material, and particularly have better application prospect in the aspects of electric automobiles and hybrid electric automobiles. However, the lithium nickelate has very harsh preparation conditions, is not easy to prepare products with ideal stoichiometric ratio, has poor electrochemical cycle performance and thermal stability, and has the safety problem of oxygen precipitation in the charging process, thereby limiting the practical process. And LiNi1-x-yCoxMnyO2The positive electrode material can be seen to be LiCoO2、LiNiO2、LiMnO2A solid solution of the three, which has LiCoO2High stability and long cycle life and high conductivity, LiNiO2High specific capacity and low cost, LiMnO2High thermal stability and high safety. The organic combination of the three components makes the anode material especially suitable for manufacturing high energy density lithium ion power batteries, especially high nickel LiNi1-x-yCoxMnyO2The positive electrode material can effectively and greatly improve the endurance mileage, the safety and the cycle life when used on the electric automobile. However, in the production process of the material, strong alkali lithium hydroxide is used as a lithium source, and the lithium source is greatly excessive, so that the surface residual alkali of a final finished product is excessive, the water absorption is strong, the processing performance and the storage performance are poor, and the use environment is harsh. Therefore, it is necessary to find a method for reducing the content of surface residual alkali and improving the processability. In addition, because the product is sintered at high temperature in a pure oxygen atmosphere, the pressure of oxygen in a sintering furnace is low due to the requirement of exhausting equipment, the utilization rate of the oxygen is lower than 20 percent, the cost of the product is increased, and the performance of the product is also adversely affected.
Disclosure of Invention
The invention aims to: aiming at the anode material lithium nickelate (LiNiO) of the lithium ion battery2) The lithium ion battery anode material prepared by the invention has very high discharge specific capacity and excellent cycling stability, can be fully recycled under 4.50V high voltage, and can simultaneously meet the requirement of large timesThe preparation method overcomes the defects of long preparation time, difficult control of stoichiometric ratio, uneven particle size distribution of products, poor electrochemical performance and the like of a solid-phase synthesis method, and the prepared products have high purity, high crystallization quality, large and uniform particle density of the products, excellent electrochemical performance and low manufacturing cost.
The technical scheme adopted by the invention is as follows:
a doped high-nickel high-voltage NCM cathode material comprises the following molecular structure expression: li [ Ni ]1-x- yCoxMny]1-δMδO2Wherein, 0<x≤0.2，0<y≤0.2，0<x+y≤0.4，0<δ is less than or equal to 0.1, M ═ Sc, Y, La, Ti, Zr, B, Mg, Ce, Pr, Sm, Ga, In, Al metaphosphates, phosphites, and hypophosphites.
Further, the molecular structure expression is included as follows: li [ Ni ]0.85Co0.05Mn0.10]1-δMδO2Or Li [ Ni ]0.80Co0.10Mn0.10]1-δMδO2And derivatives thereof, 0<δ≤0.1。
The preparation method of the doped high-nickel high-voltage NCM cathode material comprises the following steps:
s1, dissolving a nickel source raw material and a manganese source raw material into water according to a molar ratio of Ni to Mn (1-x-y) to (y/2) to obtain a solution A;
s2, dissolving a cobalt source raw material and a manganese source raw material in water according to a molar ratio of Co to Mn to x (y/2) to obtain a solution B;
s3, taking a NaOH solution with the concentration of 4mol/L as a solution C;
s4, dissolving strong ammonia water into water according to the volume ratio of 1:1 to obtain a solution D; wherein the molar ratio (NH)3):(Ni+Co+Mn)＝2.47:1；
S5, enabling solution A, B, C, D with the volume ratio of 5:2.5:5:3 to flow in parallel, and enabling the solution to be at 50-80 ℃ and N2Stirring and coprecipitating under the protection of atmosphere, controlling the flow rate of the solution to completely add the four solutions at the same time, and then adjusting the pH value to 10-12 to obtain coprecipitation solution;
s6, standing and aging the coprecipitation liquid obtained in the step S5 for 11-13h, filtering, washing and drying to obtain a precursor;
s7, uniformly mixing the precursor obtained in the step S6 with the dopant M and the lithium source raw material, and performing compression molding to obtain a material; wherein the molar ratio of the lithium source raw material, the nickel source raw material, the cobalt source raw material, the manganese source raw material and the dopant M raw material is [ (1.05-1.15) to (1-x-y) to x: y ] to delta to (1-delta) to delta;
s8, pre-sintering the material obtained in the step S7 at 450-550 ℃ for 4-8 h, and sintering in an oxygen airflow at 690-900 ℃ and with oxygen partial pressure not lower than 500Pa for 16-24h to obtain the material.
The invention replaces LiNiO by doping cobalt (Co) element and manganese (Mn) element at the same time2The nickel element (Ni) In the anode material obtains a coprecipitation NCM precursor containing Ni, Co and Mn, and then metaphosphate, phosphite and hypophosphite of dopants M (namely Sc, Y, La, Ti, Zr, B, Mg, Ce, Pr, Sm, Ga, In and Al) are added into the NCM precursor, and the lithium ion battery anode material Li [ Ni ] is obtained by sintering at high temperature In a pure oxygen atmosphere with certain pressure1-x-yCoxMny]1-δMδO2(0<x≤0.2，0<y≤0.2，0<x+y≤0.4，0<Delta. ltoreq.0.1), in particular typical Li [ Ni ]0.85Co0.05Mn0.10]1-δMδO2And Li [ Ni ]0.8Co0.10Mn0.10]1-δMδO2And derivatives thereof.
The manganese ions replace nickel elements in the anode material, so that the voltage, the structural stability and the thermal stability of the anode material can be improved; cobalt is a transition metal element similar to nickel, and the introduction of cobalt ions can improve the structural stability of the nickel-based layered anode material, reduce the preparation difficulty, improve the conductivity of the nickel-based anode material, improve the structural stability and prolong the cycle life of the anode material.
The cobalt element and the manganese element are doped, so that the comprehensive performance of the anode material can be improved by fully utilizing the advantages of each doped element; the material has high discharge specific capacity and excellent cycling stability, and is suitable for the requirements of high energy density and high-power discharge of electric automobiles; the addition of metaphosphates, phosphites or hypophosphites as dopants M inhibits the material from cyclingThe phase change in the ring process, especially the phase change of circulation under high voltage, simultaneously reduces the residual alkali content and water absorption on the surface, inhibits the side reaction on the surface of the electrode, improves the processing performance of the material, and further improves the cycle life and the safety of the material. In particular to a lithium ion battery anode material Li [ Ni ]0.85Co0.05Mn0.10]1-δMδO2Under the room temperature environment, when the constant current charge-discharge multiplying power is 0.2C and the voltage range is 2.75-4.30V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 211.3mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can still reach 182.4mAh/g, and the capacity retention rate is 86.3%. When the constant current charge-discharge rate is 0.2C and the voltage range is 2.75-4.50V, the first specific discharge capacity of the lithium ion battery anode material with the laminated structure can reach 224.9mAh/g, after the lithium ion battery anode material is cycled for 101 times, the specific discharge capacity can still reach 190.5mAh/g, and the capacity retention rate is 84.7%.
The invention adopts four solutions to co-flow and co-precipitate, combines precursor doping and high-pressure oxygen atmosphere solid phase reaction synthesis method to prepare Li [ Ni ] of lithium ion battery anode material1-x-yCoxMny]1-δMδO2(0<x≤0.2，0≤y≤0.2，0<x+y≤0.4，0<Delta is less than or equal to 0.1), Ni in the reaction process2+、Co2+、Mn2+Co-precipitating with alkali solution at constant speed, and precipitating with Ni2+、Co2+、Mn2+The concentration of the active carbon is always kept constant and consistent; ni only after the four solutions are added at the same time2+、Co2+、Mn2+The concentration of the precipitate gradually decreases at a constant speed until the precipitate is complete; in the coprecipitation process, the speed of precipitation is controlled by an ammonia water complexing agent, and Ni in the reaction raw material2 +、Co2+、Mn2+Ions are fully precipitated, the defects of the traditional solid phase synthesis method and the conventional coprecipitation synthesis method are overcome, and the prepared product has the advantages of excellent crystallization quality, chemical composition close to a theoretical value, high product phase purity and excellent lamellar structure; compared with the simple traditional solid phase synthesis method, the preparation process of the four solutions combining co-current and co-precipitation with precursor doping and the high-pressure solid phase synthesis method is simple and independentParticularly, the sintering time is obviously shortened, the sintering temperature is obviously reduced, so the energy consumption is obviously reduced, the oxygen consumption is reduced, the product has better spherical shape, is convenient to use, process and coat, is convenient for industrial production and application, and obviously reduces the harsh requirement on the use environment.
The invention adopts sintering under the high-pressure oxygen atmosphere, which can reduce the consumption of oxygen, improve the utilization rate of oxygen and reduce the production cost (the utilization rate of oxygen is lower than 10 percent when sintering is carried out under the general flowing oxygen atmosphere, and the utilization rate of oxygen is more than 90 percent when a back-end high-pressure oxygen atmosphere smoldering method is adopted), and can also improve the quality of the product.
Further, the lithium source raw material is at least one of lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium citrate and lithium oxalate.
Further, the nickel source raw material is at least one of nickel nitrate, nickel sulfate, nickel oxide, nickel chloride, nickel hydroxide and nickel acetate.
Further, the cobalt source raw material is at least one of cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt chloride, cobalt oxide and cobalt hydroxide.
Further, the manganese source raw material is at least one of manganese nitrate, manganese sulfate, manganese acetate, manganese chloride, manganese oxide, manganese hydroxide and manganese oxyhydroxide.
Further, after aging in step S5, it was filtered and washed with 50 ℃ water several times, and then vacuum-dried at 105 ℃ for 24-30 hours.
Further, in step S8, the flow rate of the oxygen gas flow in the sintering process is 400mL/min, and the oxygen partial pressure is 500-10000 Pa.
The doped high-nickel high-voltage NCM cathode material is applied to a lithium ion battery.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the inventionBy simultaneously doping cobalt element and manganese element to replace LiNiO2Obtaining a coprecipitation NCM precursor containing Ni, Co and Mn from nickel element in the anode material, adding a dopant M into the NCM precursor, and sintering at a high temperature in a pure oxygen atmosphere at a certain pressure to obtain the Li [ Ni ] of the anode material of the lithium ion battery1-x-yCoxMny]1-δMδO2(0<x≤0.2，0<y≤0.2，0<x+y≤0.4，0<Delta. ltoreq.0.1), in particular typical Li [ Ni ]0.85Co0.05Mn0.10]1-δMδO2And Li [ Ni ]0.8Co0.10Mn0.10]1-δMδO2And derivatives thereof;
2. according to the invention, the manganese ions replace nickel in the anode material, so that the voltage, structural stability and thermal stability of the anode material can be improved; cobalt is a transition metal element similar to nickel, and the introduction of cobalt ions can improve the structural stability of the nickel-based layered anode material, reduce the preparation difficulty, improve the conductivity of the nickel-based anode material, improve the structural stability and prolong the cycle life of the anode material;
3. the invention can improve the comprehensive performance of the anode material by fully using the advantages of each doping element by doping the cobalt element and the manganese element, and has very high discharge specific capacity and excellent cycling stability;
4. the metaphosphate, phosphite or hypophosphite added with the dopant M can inhibit the phase change of the material in the circulating process, particularly the circulating phase change under high voltage, simultaneously reduce the residual alkali content and water absorption of the surface, inhibit the side reaction of the electrode surface, improve the processing performance of the material and further improve the circulating life and the safety of the material; in particular to a lithium ion battery anode material Li [ Ni ]0.85Co0.05Mn0.10]1-δMδO2Under the room temperature environment, when the constant current charge-discharge multiplying power is 0.2C and the voltage range is 2.75-4.30V, the first discharge specific capacity of the anode material of the lithium ion battery with the laminated structure can reach 211.3mAh/g, after the lithium ion battery is cycled for 101 times, the discharge specific capacity can still reach 182.4mAh/g, and the capacity is ensuredThe retention rate was 86.3%. When the constant current charge-discharge rate is 0.2C and the voltage range is 2.75-4.50V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 224.9mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can still reach 190.5mAh/g, and the capacity retention rate is 84.7%;
5. the invention adopts four solutions to co-flow and co-precipitate, combines precursor doping and high-pressure oxygen atmosphere solid phase reaction synthesis method to prepare Li [ Ni ] of lithium ion battery anode material1-x-yCoxMny]1-δMδO2(0<x≤0.2，0≤y≤0.2，0<x+y≤0.4，0<Delta is less than or equal to 0.1), overcomes the defects of the traditional solid phase synthesis method and the conventional coprecipitation synthesis method, and the prepared product has excellent crystallization quality, high product phase purity and excellent lamellar structure, and the chemical composition is close to the theoretical value; compared with the simple traditional solid-phase synthesis method, the preparation process of the four solutions combining co-current and co-precipitation with precursor doping and the high-pressure solid-phase synthesis method is simple and unique, the sintering time is obviously shortened, and the sintering temperature is obviously reduced, so that the energy consumption is obviously reduced, the oxygen consumption is reduced, and the product has a better spherical shape, is convenient to use, process and coat, is convenient for industrial production and application, and obviously reduces the harsh requirements on the use environment;
6. the invention adopts sintering in high-pressure oxygen atmosphere, which can reduce oxygen consumption, improve oxygen utilization ratio, reduce production cost and improve product quality.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows the preparation of Li [ Ni ] as the positive electrode material of lithium ion battery0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2XRD pattern of (a);
FIG. 2 shows the preparation of Li [ Ni ] as the anode material of lithium ion battery0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2SEM picture of (1);
FIG. 3 shows the preparation of Li [ Ni ] as the anode material of lithium ion battery0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2A first charge-discharge curve chart under 0.5C multiplying power and 2.75-4.35V;
FIG. 4 shows the preparation of Li [ Ni ] as the anode material of lithium ion battery0.85Co0.10Mn0.05]0.995[Y(PO3)3]0.005O2A first charge-discharge curve chart under 0.2C multiplying power and 2.75-4.50V;
FIG. 5 shows the preparation of Li [ Ni ] as the anode material of lithium ion battery0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2A cycle performance curve chart under 0.5C multiplying power and 2.75-4.35V;
FIG. 6 is a graph showing the cycle performance of 500ppm yttrium metaphosphate coated NCM.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Example 1
The preparation method of the doped high-nickel high-voltage NCM cathode material provided by the preferred embodiment of the invention comprises the following steps: dissolving 0.85mol of nickel sulfate and 0.025mol of manganese nitrate in 500mL of deionized water to completely dissolve the nickel sulfate and the manganese nitrate to obtain a solution A; dissolving 0.10mol of cobalt sulfate and 0.025mol of manganese nitrate in 250mL of deionized water to completely dissolve the cobalt sulfate and the manganese nitrate to obtain a solution B; dissolving 2.0mol of NaOH in 500mL of fresh deionized water, and completely dissolving the NaOH to obtain a solution C; dissolving 150mL of concentrated ammonia water into 150mL of fresh deionized water, and completely dissolving to obtain a solution D;
solution A, B, C, D was co-currently fed at a rate of stirring 600rpm with N2Coprecipitation is carried out in a protected reaction kettle, the flow rate of the solution is controlled to ensure that the four solutions are added simultaneously, and the temperature in the reaction kettle is controlled to be 50-80 ℃; after the addition, the pH value of the materials in the reaction tank is adjusted to be about 11.0; aging at room temperatureDissolving for 12 hr, filtering, washing with 50 deg.C deionized water for several times until no Na is detected+And SO4 2-Until the end; then the filter cake is dried for 12 hours in a forced air drying oven at 105 ℃;
the dried precursor was mixed with 0.1646g of yttrium metaphosphate [ Y (PO) ]3)3]And 5-15% excess lithium hydroxide (used as a lithium source) are mixed by a mortar, absolute ethyl alcohol is added for even grinding, drying, pressing and forming by a powder tablet machine, and finally the mixture is placed in a tube furnace for presintering at 550 ℃ of 450-0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2。
The same method can be adopted to prepare the Li [ Ni ] which is a target anode material of the lithium ion battery and has excellent laminated structure0.80Co0.15Mn0.05]0.9995[Y(PO3)3]0.0005O2。
For the prepared target anode material Li [ Ni ] of lithium ion battery0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2And (3) performing constant current charge and discharge tests, wherein in a room temperature environment, when the constant current charge and discharge multiplying power is 0.2C and the voltage range is 2.75-4.30V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 188.9mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can still reach 176.2mAh/g, and the capacity retention rate is 93.3%. When the constant current charge-discharge rate is 0.5C and the voltage range is 2.75-4.50V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 224.9mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can still reach 190.5mAh/g, and the capacity retention rate is 84.7%; the test result shows that the cathode material has high specific discharge capacity and excellent cycling stability.
Example 2
The preparation method of the doped high-nickel high-voltage NCM cathode material provided by the preferred embodiment of the invention comprises the following steps: dissolving 0.85mol of nickel sulfate and 0.025mol of manganese nitrate in 500mL of deionized water to completely dissolve the nickel sulfate and the manganese nitrate to obtain a solution A; dissolving 0.10mol of cobalt sulfate and 0.025mol of manganese nitrate in 250mL of deionized water to completely dissolve the cobalt sulfate and the manganese nitrate to obtain a solution B; dissolving 2.0mol of NaOH in 500mL of fresh deionized water, and completely dissolving the NaOH to obtain a solution C; dissolving 150mL of concentrated ammonia water into 150mL of fresh deionized water, and completely dissolving to obtain a solution D;
solution A, B, C, D was co-currently fed at a rate of stirring 600rpm with N2Coprecipitation is carried out in a protected reaction kettle, the flow rate of the solution is controlled to ensure that the four solutions are added simultaneously, and the temperature in the reaction kettle is controlled to be 50-80 ℃; after the addition, the pH value of the materials in the reaction tank is adjusted to be about 11.0; aging at room temperature for 12 hr, filtering, washing with 50 deg.C deionized water for several times until no detectable Na is obtained+And SO4 2-Until the end; then the filter cake is dried in a forced air drying oven for 24 hours at the temperature of 105 ℃;
the dried precursor was mixed with 1.646g of yttrium metaphosphate [ Y (PO) ]3)3]And 5-15% excess lithium hydroxide (used as a lithium source) are mixed by a mortar, absolute ethyl alcohol is added for even grinding, drying, pressing and forming by a powder tablet machine, and finally the mixture is placed in a tube furnace for presintering at 550 ℃ of 450-0.85Co0.10Mn0.05]0.995[Y(PO3)3]0.005O2。
The same method can be adopted to prepare the Li [ Ni ] which is a target anode material of the lithium ion battery and has excellent laminated structure0.80Co0.15Mn0.05]0.995[Y(PO3)3]0.005O2。
For the prepared target anode material Li [ Ni ] of lithium ion battery0.85Co0.10Mn0.05]0.995[Y(PO3)3]0.005O2And (3) performing constant current charge and discharge tests, wherein in a room temperature environment, when the constant current charge and discharge multiplying power is 0.5C and the voltage range is 2.75-4.30V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 186.8mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can still reach 174.5mAh/g, and the capacity retention rate is 93.4%. When the constant current charge-discharge rate is 0.2C and the voltage range is 2.75-4.50V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 213.8mAh/g, the discharge specific capacity can still reach 184.5mAh/g after the lithium ion battery anode material is cycled for 101 times, and the capacity retention rate is 86.3%; the test result shows that the cathode material has high specific discharge capacity and excellent cycling stability.
Comparative example 1
Dissolving 0.85mol of nickel sulfate and 0.025mol of manganese nitrate in 500mL of deionized water to completely dissolve the nickel sulfate and the manganese nitrate to obtain a solution A; dissolving 0.10mol of cobalt sulfate and 0.025mol of manganese nitrate in 250mL of deionized water to completely dissolve the cobalt sulfate and the manganese nitrate to obtain a solution B; dissolving NaOH with the proportion amount of 2.0mol in 500mL of fresh deionized water to completely dissolve the NaOH to obtain a solution C; dissolving 150mL of concentrated ammonia water into 150mL of fresh deionized water, and completely dissolving to obtain a solution D;
solution A, B, C, D was co-currently fed at a rate of stirring 600rpm with N2Coprecipitation is carried out in a protected reaction kettle, the flow rate of the solution is controlled to ensure that the four solutions are added simultaneously, and the temperature in the reaction kettle is controlled to be 50-80 ℃; after the addition, the pH value of the materials in the reaction tank is adjusted to be about 11.0; aging at room temperature for 12 hr, filtering, washing with 50 deg.C deionized water for several times until no detectable Na is obtained+And SO4 2-Until the end; then the filter cake is dried for 12 hours in a forced air drying oven at 105 ℃;
mixing the dried precursor with 5-15% excess lithium hydroxide (used as a lithium source) by using a mortar, adding absolute ethyl alcohol, uniformly grinding, drying, performing compression molding by using a powder tablet press, finally presintering in a tube furnace at the low temperature of 550 ℃ for 6h, and then performing 690-820 ℃ in oxygen airflow (400mL/min)Sintering for 20h, and keeping the oxygen partial pressure lower than 200Pa in the sintering process to obtain the target cathode material LiNi of the lithium ion battery with good laminated structure0.85Co0.10Mn0.05O2。
The LiNi which is a target cathode material of the lithium ion battery and has a good laminated structure can be prepared by the same method0.80Co0.15Mn0.05O2。
LiNi which is the target anode material of the prepared lithium ion battery0.85Co0.10Mn0.05O2And (2) performing constant current charge and discharge tests, wherein in a room temperature environment, when the constant current charge and discharge multiplying power is 0.5C and the voltage range is 2.75-4.30V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 193.7mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can only reach 121.6mAh/g, and the capacity retention rate is only 62.8%. Under the room temperature environment, when the constant current charge-discharge multiplying power is 0.2C and the voltage range is 2.75-4.50V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 223.6mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can only reach 116.9mAh/g, and the capacity is only maintained to be 52.3%; the test result shows that the cathode material still has high first discharge specific capacity, but the cycling stability is relatively poor.
Comparative example 2
Dissolving 0.85mol of nickel sulfate and 0.025mol of manganese nitrate in 500mL of deionized water to completely dissolve the nickel sulfate and the manganese nitrate to obtain a solution A; dissolving 0.10mol of cobalt sulfate and 0.025mol of manganese nitrate in 250mL of deionized water to completely dissolve the cobalt sulfate and the manganese nitrate to obtain a solution B; dissolving NaOH with the proportion amount of 2.0mol in 500mL of fresh deionized water to completely dissolve the NaOH to obtain a solution C; dissolving 150mL of concentrated ammonia water into 150mL of fresh deionized water, and completely dissolving to obtain a solution D;
solution A, B, C, D was co-currently fed at a rate of stirring 600rpm with N2Coprecipitation is carried out in a protected reaction kettle, the flow rate of the solution is controlled to ensure that the four solutions are added simultaneously, and the temperature in the reaction kettle is controlled to be 50-80 ℃; after the addition, the pH value of the materials in the reaction tank is adjusted to be about 11.0; aging at room temperature for 12hFiltering, washing with 50 deg.C deionized water for several times until no Na can be detected+And SO4 2-Until the end; then the filter cake is dried in a forced air drying oven for 24 hours at the temperature of 105 ℃;
mixing the dried precursor with 5-15% excess lithium hydroxide (used as a lithium source) by using a mortar, adding absolute ethyl alcohol, uniformly grinding, drying, performing compression molding by using a powder tablet press, finally placing in a tubular furnace, presintering for 7h at the low temperature of 550 ℃ plus materials at 450 ℃, then sintering for 22h at the temperature of 820 ℃ in oxygen airflow (400mL/min), and keeping the oxygen partial pressure at 5000Pa in the sintering process to obtain the target lithium ion battery cathode material LiNi with a good layered structure0.85Co0.10Mn0.05O2。
The LiNi which is a target cathode material of the lithium ion battery and has a good laminated structure can be prepared by the same method0.80Co0.15Mn0.05O2。
LiNi which is the target anode material of the prepared lithium ion battery0.85Co0.10Mn0.05O2And (2) performing constant current charge and discharge tests, wherein in a room temperature environment, when the constant current charge and discharge multiplying power is 0.5C and the voltage range is 2.75-4.30V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 189.8mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can only reach 120.0mAh/g, and the capacity retention rate is only 63.2%. Under the room temperature environment, when the constant current charge-discharge multiplying power is 0.2C and the voltage range is 2.75-4.50V, the first discharge specific capacity of the lithium ion battery anode material with the laminated structure can reach 217.7mAh/g, after the lithium ion battery anode material is cycled for 101 times, the discharge specific capacity can only reach 122.6mAh/g, and the capacity is only kept at 56.3%; the test result shows that the cathode material still has high first discharge specific capacity, but the cycling stability is relatively poor.
Examples of the experiments
For the preparation of the lithium ion battery anode material Li [ Ni ]0.85Co0.10Mn0.05]0.9995[Y(PO3)3]0.0005O2The X-ray diffraction experiment and the scanning electron microscope observation were carried out, as shown in fig. 1 and 2.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A doped high-nickel high-voltage NCM positive electrode material is characterized by comprising the following molecular structure expression: li [ Ni ]1-x-yCoxMny]1-δMδO2Wherein, 0<x≤0.2，0<y≤0.2，0<x+y≤0.4，0<δ is less than or equal to 0.1, M ═ Sc, Y, La, Ti, Zr, B, Mg, Ce, Pr, Sm, Ga, In, Al metaphosphates, phosphites, and hypophosphites.
2. The doped high nickel high voltage NCM positive electrode material of claim 1, comprising a molecular structure expression as follows: li [ Ni ]0.85Co0.05Mn0.10]1-δMδO2Or Li [ Ni ]0.80Co0.10Mn0.10]1-δMδO2And derivatives thereof, 0<δ≤0.1。
3. The method for preparing a doped high nickel high voltage NCM positive electrode material according to claim 1 or 2, characterized by comprising the steps of:
s1, dissolving a nickel source raw material and a manganese source raw material into water according to a molar ratio of Ni to Mn (1-x-y) to (y/2) to obtain a solution A;
s2, dissolving a cobalt source raw material and a manganese source raw material in water according to a molar ratio of Co to Mn to x (y/2) to obtain a solution B;
s3, taking a NaOH solution with the concentration of 4mol/L as a solution C;
s4, dissolving strong ammonia water into water according to the volume ratio of 1:1 to obtain a solution D; wherein the molar ratio (NH)3):(Ni+Co+Mn)＝2.47:1；
S5, enabling solution A, B, C, D with the volume ratio of 5:2.5:5:3 to flow in parallel, and enabling the solution to be at 50-80 ℃ and N2Stirring and coprecipitating under the protection of atmosphere, controlling the flow rate of the solution to ensure that the four solutions are added simultaneously,then adjusting the pH value to 10-12 to obtain a coprecipitation solution;
s6, standing and aging the coprecipitation liquid obtained in the step S5 for 11-13h, filtering, washing and drying to obtain a precursor;
s7, uniformly mixing the precursor obtained in the step S6 with the dopant M and the lithium source raw material, and performing compression molding to obtain a material; wherein the molar ratio of the lithium source raw material, the nickel source raw material, the cobalt source raw material, the manganese source raw material and the dopant M raw material is [ (1.05-1.15) to (1-x-y) to x: y ] to delta to (1-delta) to delta;
s8, pre-sintering the material obtained in the step S7 at 450-550 ℃ for 4-8 h, and sintering in an oxygen airflow at 690-900 ℃ and with oxygen partial pressure not lower than 500Pa for 16-24h to obtain the material.
4. The method for preparing a doped high-nickel high-voltage NCM positive electrode material according to claim 3, wherein: the lithium source raw material is at least one of lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium citrate and lithium oxalate.
5. The method for preparing a doped high-nickel high-voltage NCM positive electrode material according to claim 3, wherein: the nickel source raw material is at least one of nickel nitrate, nickel sulfate, nickel oxide, nickel chloride, nickel hydroxide and nickel acetate.
6. The method for preparing a doped high-nickel high-voltage NCM positive electrode material according to claim 3, wherein: the cobalt source raw material is at least one of cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt chloride, cobalt oxide and cobalt hydroxide.
7. The method for preparing a doped high-nickel high-voltage NCM positive electrode material according to claim 3, wherein: the manganese source raw material is at least one of manganese nitrate, manganese sulfate, manganese acetate, manganese chloride, manganese oxide, manganese hydroxide and manganese oxyhydroxide.
8. The method for preparing a doped high-nickel high-voltage NCM positive electrode material according to claim 3, wherein: after aging in the step S5, the mixture is filtered, washed with water at 50 ℃ for multiple times and dried in vacuum at 105 ℃ for 24-30 h.
9. The method for preparing a doped high-nickel high-voltage NCM positive electrode material according to claim 3, wherein: in the step S8, the flow rate of the oxygen gas flow in the sintering process is 400mL/min, and the oxygen partial pressure is 500-10000 Pa.
10. Use of the doped high nickel high voltage NCM positive electrode material of claim 1 or 2 in a lithium ion battery.
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