CN114388758A - Lithium metal oxide cathode material with novel composite phase structure and preparation method and application thereof - Google Patents
Lithium metal oxide cathode material with novel composite phase structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN114388758A CN114388758A CN202210012536.XA CN202210012536A CN114388758A CN 114388758 A CN114388758 A CN 114388758A CN 202210012536 A CN202210012536 A CN 202210012536A CN 114388758 A CN114388758 A CN 114388758A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ball
- salt
- carbon source
- milling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910021450 lithium metal oxide Inorganic materials 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 10
- 239000011029 spinel Substances 0.000 claims abstract description 10
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011435 rock Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 9
- 229930006000 Sucrose Natural products 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000005720 sucrose Substances 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 150000001868 cobalt Chemical class 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
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 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
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 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
- 238000001914 filtration Methods 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
- 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 239000000696 magnetic material Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000004075 alteration Effects 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium metal oxide positive electrode material with a novel composite structure and a preparation method and application thereof, wherein the positive electrode material at least contains Li, Ni and an element X, wherein the X is one or more of Co, Mn, Fe, Cu, Ti, Mg, Al, B, W, Mo, Nb, Zn, Sn, Zr, Ga, La and V; the shell of the primary particles of the anode material is of a rock salt-spinel structure, and the core is of a layered structure. And ball-milling the nickel-cobalt-manganese precursor and a lithium source, adding a carbon source, ball-milling, heating the obtained mixed material to 150-300 ℃ under oxygen, preserving heat, ball-milling after cooling, heating the obtained pre-sintered material, preserving heat, continuing to heat, preserving heat again, and cooling to obtain the cathode material. According to the method, a carbon source is used as an initiating medium, and a specific feeding step and experimental conditions are combined, so that the obtained positive electrode material can relieve magnetic material resistance, reduce impedance, enlarge lithium ion transmission and has more excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium metal oxide cathode material with a novel composite phase structure, and a preparation method and application thereof.
Background
The positive electrode material is an important component of the lithium ion battery,the prepared positive electrode material with high safety performance, high specific capacity and stable cycle performance has important influence on the development and application of the lithium ion battery. However, the conventional lithium ion battery cathode materials have many limitations. For example, LiNiO2The product with the stoichiometric ratio is difficult to synthesize and the capacity is seriously degraded; LiCoO2High cost, toxicity and long cycle performance under high pressure need to be improved; LiMn2O4Low specific energy and poor cycle stability; LiFePO4Low energy density, etc. At this time, the ternary positive electrode material LiNixCoyMnzO2The (x + y + z ═ 1) material has been widely studied because of the synergistic effect of transition metals, so that the ternary material has the advantages of high specific discharge capacity, high voltage plateau, low cost, low impedance, and the like. Meanwhile, the ternary material has some problems, such as residual alkali problem, cation mixing problem, surface side reaction problem, and the like. In addition, as an important component of an energy storage device, a ternary positive electrode material with high energy density can generate severe side reactions in a high-charge and discharge state, so that structural collapse and capacity attenuation are caused, even battery thermal runaway occurs, and serious safety accidents such as ignition and explosion are caused. Therefore, it is required to develop a ternary cathode material having both thermal stability and excellent electrochemical properties.
In the face of the requirements of high performance and safety of the ternary cathode material, the prior art mainly adopts the technical scheme of surface coating, ion doping and core-shell structure design. CN108365181B discloses a method for modifying a high-nickel layered positive electrode material, which comprises the steps of uniformly mixing a high-nickel layered transition metal oxide material with a precursor containing M-O and M-P, forming a nanoscale and uniformly distributed M-O and M-P coating layer on the surface of an active material through a chemical reaction, and then carrying out heat treatment on the coating layer to obtain a lithium battery anode material of which the surface contains the M-O and/or L-M-O, and the M-P and/or L-M-P coating layers; CN113410458A discloses a cation-doped modified ternary positive electrode material for a lithium ion battery and a preparation method thereof, wherein the method is obtained by uniformly mixing nanoscale metal oxide particles, a ternary material precursor and lithium salt and then roasting at high temperature; CN113314712A discloses a high-nickel anode material with a surface gradient structure, a preparation method and a lithium ion battery, wherein the method comprises the steps of firstly preparing a NiyM '1-yP' coated NixM1-xP core-shell precursor by a mechanofusion method, and then adding lithium salt for synchronous sintering and lithiation to prepare the high-nickel anode material with the surface gradient structure.
However, the technical requirements of the solution are high, the operation cost is high, the production efficiency is low, and the solution is rarely used in actual production. Furthermore, the impact of the properties of the positive electrode material is multifaceted and complex, and while improving one aspect of the properties, it is often necessary to sacrifice the other properties.
Disclosure of Invention
In view of the above, the present invention provides a lithium metal oxide cathode material with a novel composite phase structure, and a preparation method and an application thereof.
The invention provides a lithium metal oxide positive electrode material with a novel composite phase structure, which at least contains Li, Ni and an element X, wherein the X is one or more of Co, Mn, Fe, Cu, Ti, Mg, Al, B, W, Mo, Nb, Zn, Sn, Zr, Ga, La and V;
the shell of the primary particles of the anode material is of a rock salt-spinel structure, and the core of the primary particles of the anode material is of a layered structure.
In the invention, the thickness of the shell of the cathode material is 1-5 nm, preferably 2-3 nm.
The invention provides a preparation method of a lithium metal oxide anode material with a novel composite phase structure, which comprises the following steps:
ball-milling a nickel-cobalt-manganese precursor and a lithium source, adding a carbon source, ball-milling, heating the obtained mixed material to 150-300 ℃ in an oxygen atmosphere, preserving heat, cooling, and ball-milling to obtain a pre-sintered material;
and heating the pre-sintered material to 400-600 ℃, preserving heat, continuing to heat to 700-900 ℃, preserving heat again, and cooling to obtain the lithium metal oxide cathode material with the novel composite phase structure.
In the present invention, the carbon source includes an inorganic carbon source and an organic carbon source, preferably an organic carbon source. In the present invention, the organic carbon source is selected from one or more of sucrose, glucose, starch, citric acid, lactic acid and polyethylene glycol; the inorganic carbon source is selected from one or more of sodium bicarbonate, sodium carbonate and calcium carbonate. In particular embodiments, the carbon source is selected from glucose or sucrose. The invention takes the organic carbon source as an initiating medium, realizes the ordered control of the occupation of lithium nickel ions in the structure synthesis process of the anode material, and solves the problems of serious magnetic material frustration phenomenon, disordered mixed arrangement of lithium and nickel and the like in the traditional synthesis method.
In the invention, the precursor and a lithium source are subjected to ball milling for 2-6 h, and then a carbon source is added for ball milling for 0.5-1.5 h.
In the invention, the molar ratio of the precursor to the lithium source is 1 (1.01-1.08);
the mass ratio of the precursor to the carbon source is 100: (1-8).
According to the invention, the precursor, the lithium source and the carbon source are mixed together, lithiated and calcined, the sintering process is optimized, the high-strength ternary material is prepared, the problem of cracking and pulverization of particles in charging and discharging overcharge is inhibited, the step of shortening the production line is realized, and the problems of long process flow, high equipment investment in a newly-built production line and the like in the traditional modification method are solved.
In the invention, the temperature of the pre-sintering material is raised to 400-600 ℃ at the temperature raising rate of 1-10 ℃;
then, the temperature is increased to 700-900 ℃ at a rate of 1-10 ℃/min.
The method preferably comprises the steps of heating to 150-300 ℃, preserving heat for 1-3 hours, and carrying out ball milling after cooling to obtain a pre-sintered material; and heating the pre-sintering material to 400-600 ℃, preserving heat for 4-10 h, continuing heating to 700-900 ℃, and preserving heat for 6-16 h again.
In the invention, the nickel-cobalt-manganese precursor is prepared by the following method:
adding the mixed salt solution, the alkali solution and the complexing agent into the base solution, keeping the pH value at 10-12 and the temperature at 40-70 ℃, reacting for 30-120 h, and then aging, washing, suction filtering and drying the product to obtain a precursor; the mixed salt solution comprises soluble nickel salt, cobalt salt and manganese salt;
the alkali solution is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate;
the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium tungstate and lithium nitrate;
the complexing agent is selected from one or more of ammonia water, ethylene diamine tetraacetic acid salt and diethanol amine.
In the invention, the nickel salt is one or more of nickel sulfate, nickel chloride and nickel nitrate;
the cobalt salt is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate;
the manganese salt is manganese sulfate.
The invention provides a lithium ion battery, which comprises the anode material with a novel composite phase structure prepared by the preparation method in the technical scheme.
The invention provides a lithium metal oxide positive electrode material with a novel composite structure, which at least contains Li, Ni and an element X, wherein the X is one or more of Co, Mn, Fe, Cu, Ti, Mg, Al, B, W, Mo, Nb, Zn, Sn, Zr, Ga, La and V; the shell of the primary particles of the anode material is of a rock salt-spinel structure, and the core of the primary particles of the anode material is of a layered structure. The positive electrode material provided by the invention is of a composite phase structure, the shell of primary particles is of a rock salt-spinel structure, and the core is of a good layered structure, so that the problems of uncontrollable batteries and potential safety hazards of explosion and ignition caused by material collapse caused by irreversible phase change in the working process of the traditional positive electrode material are solved. The preparation method of the cathode material with the novel composite phase structure comprises the following steps: ball-milling a nickel-cobalt-manganese precursor and a lithium source, adding a carbon source, ball-milling, heating the obtained mixed material to 150-300 ℃ in an oxygen atmosphere, preserving heat, cooling, and ball-milling to obtain a pre-sintered material; and heating the pre-sintered material to 400-600 ℃, preserving heat, continuing to heat to 700-900 ℃, preserving heat again, and cooling to obtain the lithium metal oxide cathode material with the novel composite structure. The method provided by the invention adopts the carbon source as an initiating medium, relieves the magnetic material resistance, reduces the disordered mixed arrangement of lithium and nickel ions, reduces the impedance, enlarges the lithium ion transmission and has more excellent electrochemical performance; the method is simple, suitable for industrial production, simple and convenient in process, low in cost and excellent in performance.
Drawings
Fig. 1 is a process flow diagram of the present invention for preparing a cathode material having a novel composite phase structure;
FIG. 2 is a spherical aberration electron micrograph of the positive electrode material prepared in example 1 of the present invention;
FIG. 3 is a spherical aberration electron micrograph of the positive electrode material prepared in example 2 of the present invention;
FIG. 4 is a spherical aberration electron micrograph of the positive electrode material prepared in example 3 of the present invention;
FIG. 5 is an electron micrograph of a positive electrode material prepared according to comparative example 1 of the present invention;
FIG. 6 is a charge-discharge cycle curve diagram of the positive electrode materials prepared in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
In order to further illustrate the present invention, the following will describe in detail a lithium metal oxide cathode material having a novel composite phase structure, and a method for preparing the same and applications thereof, with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
1: preparing liquid: preparing base solution, salt solution, alkali solution and complexing agent solution required by the preparation of the precursor, wherein the base solution is prepared by mixing 35L of deionized water, 0.4L of 10mol/L NaOH and 2.8L of 16.3mol/L ammonia water. The salt solution is prepared from NiSO4·6H2O，CoSO4·7H2O，MnSO4·H2O is mixed according to the mass ratio of 8: 1:1, pouring the mixture into a salt storage tank after completely dissolving the mixture in deionized water, and respectively putting 10mol/L NaOH and 16.3mol/L ammonia water into an alkali storage tank and a complexing agent storage tank after preparing the mixture.
2: synthesizing a precursor: n is always introduced into the reaction kettle2Injecting the base solution into a reaction kettle, introducing the salt solution, NaOH and ammonia water into the reaction kettle at different flow rates by using a peristaltic pump, and maintainingThe pH was maintained at 11, the temperature was maintained at 55 ℃ with heating and stirring at constant rate. And after 80h of reaction, aging the product, repeatedly cleaning with deionized water, performing suction filtration, and drying for 24h to obtain the final precursor.
3: mixing materials: weighing the dried precursor and LiOH according to a molar ratio of 1:1.05, wherein the mass ratio of the ternary cathode material precursor to sucrose is 100: 1, firstly ball-milling the first two materials for 3 hours, then adding the weighed sucrose and ball-milling for 0.5 hour.
4: pre-burning: heating to 200 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving the temperature for 3 hours, freely cooling, and ball-milling for 0.5 h.
5: synthesizing a positive electrode material: heating the ball-milled pre-sintered material to 600 ℃ at the heating rate of 5 ℃/min for pre-sintering in the oxygen atmosphere, keeping the temperature for 5h, heating to 800 ℃ at the heating rate of 5 ℃/min for 10h, and freely cooling to obtain the ternary cathode material with the molecular formula of LiNi0.8Co0.1Mn0.1O2。
6: and (3) testing: as shown in the spherical aberration electron microscope image shown in fig. 1, the surface of the primary particle of the high-nickel cathode material is characterized in that: the shell of the anode material is a composite spinel/rock salt phase structure phase formed by reconstruction, and the shell is a normal layered structure; and coating the obtained positive electrode material into a pole piece, using the pole piece as a positive electrode, using a lithium piece as a negative electrode, assembling the pole piece into a button cell, and carrying out charging and discharging in a voltage range of 2.3-4.3V, wherein the cycle curve is shown in figure 5, and the retention rate of 200 cycles is 84.5%.
Example 2
1: preparing liquid: preparing a base solution, a salt solution, an alkali solution and a complexing agent solution which are required by the preparation of the precursor, wherein the base solution is prepared by mixing 35L of deionized water, 0.32L of 12mol/L NaOH and 3L of 13.3mol/L ammonia water. The salt solution is prepared from NiSO4·6H2O，CoSO4·7H2O，MnSO4·H2O is prepared according to the mass ratio of 8: 1:1, pouring the mixture into a salt storage tank after completely dissolving the mixture in deionized water, and respectively putting 12mol/L NaOH and 13.3mol/L ammonia water into an alkali storage tank and a complexing agent storage tank after preparing the mixture.
2: synthesis of the precursorBody: n is always introduced into the reaction kettle2Injecting the base solution into a reaction kettle, introducing the salt solution, the alkali solution and the complexing agent into the reaction kettle at different flow rates by using a peristaltic pump, keeping the pH value at 11, heating to keep the temperature at 55 ℃, and stirring at a constant speed. And after the reaction is carried out for 100 hours, aging the product, repeatedly cleaning the product by using deionized water, carrying out suction filtration, and drying the product for 16 hours to obtain the final precursor.
3: mixing materials: weighing the dried precursor and a lithium source according to a molar ratio of 1:1.08, wherein the mass ratio of the precursor of the ternary cathode material to glucose is 100: 2, firstly ball-milling the first two materials for 3 hours, then adding the weighed glucose in proportion and ball-milling for 0.5 hour.
4: pre-burning: heating to 200 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving the temperature for 3 hours, freely cooling, and ball-milling for 0.5 h.
5: synthesizing a positive electrode material: heating the ball-milled pre-sintered material to 500 ℃ at the heating rate of 5 ℃/min for pre-sintering in the oxygen atmosphere, keeping the temperature for 5 hours, heating to 800 ℃ at the heating rate of 5 ℃/min for 10 hours, and freely cooling to obtain the ternary cathode material with the molecular formula of LiNi0.8Co0.1Mn0.1O2。
6: and (3) testing: as shown in the spherical aberration electron microscope image of fig. 3, the surface of the primary particle of the high nickel cathode material is characterized as follows: the shell of the anode material is a composite spinel/rock salt phase structure phase formed by reconstruction, and the shell is a normal layered structure; and coating the obtained positive electrode material into a pole piece, using the pole piece as a positive electrode, using a lithium piece as a negative electrode, assembling the pole piece into a button cell, and performing charge and discharge in a voltage range of 2.3-4.3V, wherein the cycle curve is shown in figure 5, and the retention rate of 200 cycles is 87.6%.
Example 3
1: preparing liquid: preparing a base solution, a salt solution, an alkali solution and a complexing agent solution which are required by the preparation of a precursor, wherein the base solution is prepared by mixing 30L of deionized water, 0.40L of 12.2mol/L NaOH and 2.6L of 13.1mol/L ammonia water. The salt solution is prepared from NiSO4·6H2O，CoSO4·7H2O，MnSO4·H2O is prepared according to the mass ratio of 8: 1:1 after weighing, after detachingAnd pouring the dissolved product into a salt storage tank after the product is completely dissolved in the water, and respectively putting the prepared product into an alkali storage tank and a complexing agent storage tank after 12.2mol/L NaOH and 13.1mol/L ammonia water are prepared.
2: synthesizing a precursor: n is always introduced into the reaction kettle2Injecting the base solution into a reaction kettle, introducing the salt solution, the alkali solution and the complexing agent into the reaction kettle at different flow rates by using a peristaltic pump, keeping the pH value at 11, heating to keep the temperature at 55 ℃, and stirring at a constant speed. And after the reaction is carried out for 100 hours, aging the product, repeatedly cleaning the product by using deionized water, carrying out suction filtration, and drying the product for 16 hours to obtain the final precursor.
3: mixing materials: weighing the dried precursor and a lithium source according to a molar ratio of 1:1.08, wherein the mass ratio of the ternary cathode material precursor to sodium carbonate is 100: 2, firstly ball-milling the first two materials for 3 hours, then adding the weighed glucose in proportion and ball-milling for 0.5 hour.
4: pre-burning: heating to 200 ℃ at a heating rate of 5 ℃/min under an oxygen atmosphere, preserving the temperature for 3 hours, freely cooling, and ball-milling for 0.5 h.
5: synthesizing a positive electrode material: heating the ball-milled pre-sintered material to 500 ℃ at the heating rate of 5 ℃/min for pre-sintering in the oxygen atmosphere, keeping the temperature for 5 hours, heating to 800 ℃ at the heating rate of 5 ℃/min for 10 hours, and freely cooling to obtain the ternary cathode material with the molecular formula of LiNi0.8Co0.1Mn0.1O2。
6: and (3) testing: as shown in the spherical aberration electron microscope image of fig. 4, the surface of the primary particle of the high nickel cathode material is characterized as follows: the shell of the anode material is a composite spinel/rock salt phase structure phase formed by reconstruction, and the shell is a normal layered structure; and coating the obtained positive electrode material into a pole piece, using the pole piece as a positive electrode, using a lithium piece as a negative electrode, assembling the pole piece into a button cell, and performing charge and discharge in a voltage range of 2.3-4.3V, wherein the cycle curve is shown in figure 6, and the retention rate of 200 cycles is 77%.
Comparative example 1
Mixing sucrose and raw materials to form a precursor, and mixing the precursor with a lithium source to synthesize the high-nickel anode material.
1: preparing liquid: configuring the bottom required for preparing the precursorThe base solution is prepared by mixing 35L of deionized water, 0.39L of 12mol/L NaOH and 2.78L of 15mol/L ammonia water. The salt solution is prepared from NiSO4·6H2O，CoSO4·7H2O，MnSO4·H2O is prepared according to the mass ratio of 8: 1:1, pouring the mixture into a salt storage tank after completely dissolving the mixture in deionized water, and respectively putting the mixture into an alkali storage tank, a complexing agent storage tank and a sucrose solution storage tank after preparing 12mol/L NaOH, 15mol/L ammonia water and 0.1mol/L sucrose solution.
2: synthesizing a precursor: n is always introduced into the reaction kettle2Injecting the base solution into a reaction kettle, introducing the salt solution, the alkali solution, the sucrose solution and the complexing agent into the reaction kettle at different flow rates by using a peristaltic pump, keeping the pH value at 12, heating to keep the temperature at 60 ℃, and stirring at a constant speed. And after the reaction is carried out for 100 hours, aging the product, repeatedly cleaning the product by using deionized water, carrying out suction filtration, and drying the product for 24 hours to obtain the final precursor.
3: mixing materials: and weighing the dried precursor and a lithium source according to a molar ratio of 1:1.08, and carrying out ball milling for 3 h.
4: pre-burning: heating to 200 ℃ at a heating rate of 3 ℃/min under an oxygen atmosphere, preserving the temperature for 2 hours, freely cooling, and ball-milling for 0.5 h.
5: synthesizing a positive electrode material: heating the ball-milled pre-sintered material to 500 ℃ at a heating rate of 3 ℃/min for pre-sintering in an oxygen atmosphere, keeping the temperature for 5 hours, heating to 800 ℃ at a heating rate of 5 ℃/min for 10 hours, and freely cooling to obtain the ternary cathode material with the molecular formula of LiNi0.8Co0.1Mn0.1O2。
6: and (3) testing: as shown in the spherical aberration electron microscope image of fig. 4, the surface of the primary particle of the high nickel cathode material is characterized as follows: the anode material is a normal laminated structure; and coating the obtained positive electrode material into a pole piece, using the pole piece as a positive electrode, using a lithium piece as a negative electrode, assembling the button cell, and performing charge and discharge in a voltage range of 2.3-4.3V, wherein the cycle curve is shown in figure 5, and the retention rate of 200 cycles is 70%.
From the above examples, the present invention provides a lithium metal oxide positive electrode material having a novel composite structure, containing at least Li, Ni and an element X, wherein X is one or more of Co, Mn, Fe, Cu, Ti, Mg, Al, B, W, Mo, Nb, Zn, Sn, Zr, Ga, La and V. The shell of the primary particles of the anode material is of a rock salt-spinel structure, and the core of the primary particles of the anode material is of a layered structure. The positive electrode material provided by the invention is of a composite phase structure, the shell is of a rock salt-spinel structure, and the core is of a layered structure, so that the problems of uncontrollable battery and potential safety hazard caused by explosion and ignition due to material collapse caused by irreversible phase change in the working process of the traditional positive electrode material are solved. The invention also provides a preparation method of the cathode material with the novel composite phase structure, which comprises the following steps: ball-milling a nickel-cobalt-manganese precursor and a lithium source, adding a carbon source, ball-milling, heating the obtained mixed material to 150-300 ℃ in an oxygen atmosphere, preserving heat, cooling, and ball-milling to obtain a pre-sintered material; and heating the pre-sintered material to 400-600 ℃, preserving heat, continuing heating to 700-900 ℃, preserving heat again, and cooling to obtain the cathode material. The method provided by the invention adopts the carbon source as an initiating medium, combines specific feeding steps and experimental conditions, can relieve the magnetic material frustration, reduce the disordered mixed arrangement of lithium and nickel ions, reduce the impedance, enlarge the lithium ion transmission, and has more excellent electrochemical performance; the method is simple, suitable for industrial production, simple and convenient in process, low in cost and excellent in performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A lithium metal oxide cathode material with a novel composite structure is characterized in that the cathode material at least contains Li, Ni and an element X, wherein the X is one or more of Co, Mn, Fe, Cu, Ti, Mg, Al, B, W, Mo, Nb, Zn, Sn, Zr, Ga, La and V;
the shell of the primary particles of the anode material is of a rock salt-spinel structure, and the core of the primary particles of the anode material is of a layered structure.
2. A method for preparing a lithium metal oxide positive electrode material having a novel composite phase structure according to claim 1, comprising the steps of:
(1) ball-milling a nickel-cobalt-manganese precursor and a lithium source, adding a carbon source, ball-milling, heating the obtained mixed material to 150-300 ℃ in an oxygen atmosphere, preserving heat, cooling, and ball-milling to obtain a pre-sintered material;
(2) and heating the pre-sintered material to 400-600 ℃, preserving heat, continuing to heat to 700-900 ℃, preserving heat again, and cooling to obtain the lithium metal oxide cathode material with the novel composite phase structure.
3. The production method according to claim 2, wherein the carbon source is selected from the group consisting of an organic carbon source and an inorganic carbon source; the organic carbon source is selected from one or more of sucrose, glucose, starch, citric acid and polyethylene glycol; the inorganic carbon source is selected from one or more of sodium bicarbonate, sodium carbonate and calcium carbonate.
4. The preparation method of claim 2, wherein the precursor and the lithium source are ball-milled for 2-6 h, and then a carbon source is added for ball-milling for 0.5-1.5 h.
5. The preparation method according to claim 2, wherein the molar ratio of the precursor to the lithium source is 1 (1.01-1.08);
the mass ratio of the precursor to the carbon source is 100: (1-8).
6. The preparation method according to claim 2, wherein the pre-sintering material is heated to 400-600 ℃ at a heating rate of 1-10 ℃;
then, the temperature is increased to 700-900 ℃ at a rate of 1-10 ℃/min.
7. The method of claim 2, wherein the nickel cobalt manganese precursor is prepared according to the following method:
adding the mixed salt solution, the alkali solution and the complexing agent into the base solution, keeping the pH value at 10-12 and the temperature at 40-70 ℃, reacting for 30-120 h, and then aging, washing, suction filtering and drying the product to obtain a precursor; the mixed salt solution comprises soluble nickel salt, cobalt salt and manganese salt;
the alkali solution is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate and potassium carbonate;
the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium tungstate and lithium nitrate;
the complexing agent is selected from one or more of ammonia water, ethylene diamine tetraacetic acid salt and diethanol amine.
8. The production method according to claim 2, wherein the nickel salt is one or more of nickel sulfate, nickel chloride and nickel nitrate;
the cobalt salt is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate;
the manganese salt is manganese sulfate.
9. A lithium ion battery comprising the lithium metal oxide cathode material having a novel composite phase structure according to claim 1 or the lithium metal oxide cathode material having a novel composite phase structure prepared by the preparation method according to any one of claims 2 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210012536.XA CN114388758B (en) | 2022-01-06 | 2022-01-06 | Lithium metal oxide positive electrode material with novel composite phase structure, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210012536.XA CN114388758B (en) | 2022-01-06 | 2022-01-06 | Lithium metal oxide positive electrode material with novel composite phase structure, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114388758A true CN114388758A (en) | 2022-04-22 |
| CN114388758B CN114388758B (en) | 2023-12-19 |
Family
ID=81200790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210012536.XA Active CN114388758B (en) | 2022-01-06 | 2022-01-06 | Lithium metal oxide positive electrode material with novel composite phase structure, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114388758B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115140780A (en) * | 2022-07-07 | 2022-10-04 | 安徽富锂新能源科技有限公司 | Ternary positive electrode material of two-phase coherent lithium ion battery and preparation method thereof |
| CN117080535A (en) * | 2023-10-19 | 2023-11-17 | 中创新航科技集团股份有限公司 | Cylindrical battery |
| CN117913215A (en) * | 2024-03-19 | 2024-04-19 | 宁德时代新能源科技股份有限公司 | Secondary battery and electricity utilization device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859888A (en) * | 2010-05-21 | 2010-10-13 | 北京师范大学 | Lithium manganese composite oxide for lithium battery cathode active material and preparation method thereof |
| WO2020258764A1 (en) * | 2019-06-26 | 2020-12-30 | 中国科学院物理研究所 | Positive electrode active material and preparation method therefor, and lithium battery |
| CN112803022A (en) * | 2020-12-31 | 2021-05-14 | 国联汽车动力电池研究院有限责任公司 | Surface structure spinel-rock salt phase integrated lithium-rich material and preparation method thereof |
| CN113140713A (en) * | 2020-01-20 | 2021-07-20 | 中国科学院金属研究所 | LiFePO4/C-coated ternary cathode material and preparation method and application thereof |
| CN113437268A (en) * | 2020-03-23 | 2021-09-24 | 中国科学院物理研究所 | Lithium battery positive electrode material with core-shell structure, preparation method thereof and lithium battery |
-
2022
- 2022-01-06 CN CN202210012536.XA patent/CN114388758B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101859888A (en) * | 2010-05-21 | 2010-10-13 | 北京师范大学 | Lithium manganese composite oxide for lithium battery cathode active material and preparation method thereof |
| WO2020258764A1 (en) * | 2019-06-26 | 2020-12-30 | 中国科学院物理研究所 | Positive electrode active material and preparation method therefor, and lithium battery |
| CN113140713A (en) * | 2020-01-20 | 2021-07-20 | 中国科学院金属研究所 | LiFePO4/C-coated ternary cathode material and preparation method and application thereof |
| CN113437268A (en) * | 2020-03-23 | 2021-09-24 | 中国科学院物理研究所 | Lithium battery positive electrode material with core-shell structure, preparation method thereof and lithium battery |
| CN112803022A (en) * | 2020-12-31 | 2021-05-14 | 国联汽车动力电池研究院有限责任公司 | Surface structure spinel-rock salt phase integrated lithium-rich material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115140780A (en) * | 2022-07-07 | 2022-10-04 | 安徽富锂新能源科技有限公司 | Ternary positive electrode material of two-phase coherent lithium ion battery and preparation method thereof |
| CN115140780B (en) * | 2022-07-07 | 2024-05-10 | 安徽富锂新能源科技有限公司 | Ternary positive electrode material of two-phase coherent lithium ion battery and preparation method thereof |
| CN117080535A (en) * | 2023-10-19 | 2023-11-17 | 中创新航科技集团股份有限公司 | Cylindrical battery |
| CN117080535B (en) * | 2023-10-19 | 2023-12-22 | 中创新航科技集团股份有限公司 | Cylindrical battery |
| CN117913215A (en) * | 2024-03-19 | 2024-04-19 | 宁德时代新能源科技股份有限公司 | Secondary battery and electricity utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114388758B (en) | 2023-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108091843B (en) | Lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof | |
| CN106207138B (en) | A kind of method for preparing anode material of lithium-ion battery and its application | |
| EP2102927B1 (en) | Method for preparing core-shell spinel cathode active materials for lithium secondary batteries | |
| EP3557668A1 (en) | Ternary material and preparation method therefor, battery slurry, positive electrode, and lithium battery | |
| CN107910531B (en) | Preparation method of high-nickel-base ternary cathode material | |
| CN114388758B (en) | Lithium metal oxide positive electrode material with novel composite phase structure, and preparation method and application thereof | |
| WO2024000777A1 (en) | Positive electrode material precursor and positive electrode material and preparation methods therefor, and sodium-ion battery | |
| CN103066261B (en) | The synthetic method of the nickelic multi-element metal oxide positive electrode of high power capacity | |
| KR101217453B1 (en) | Method of producing Ni- composite metal hydroxide, Ni-composite metal hydroxide obtained thereby | |
| CN106910887B (en) | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material | |
| CN113258072B (en) | Nickel-cobalt-manganese positive electrode material and preparation method thereof | |
| CN103325992B (en) | Lithium ion battery positive electrode material precursor nickel-cobalt-manganese hydroxide powder and preparation method thereof | |
| EP3611132A2 (en) | Method for preparing cathode active material | |
| CN109962234B (en) | Concentration gradient single crystal anode material and preparation method thereof | |
| CN108428888B (en) | Spherical surface compact nickel-cobalt-aluminum ternary material, precursor thereof, preparation method and application thereof | |
| CN109879333B (en) | Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method | |
| CN110085845A (en) | A kind of nickel-base anode material and preparation method thereof with core-shell structure | |
| CN111029561A (en) | Ternary lithium battery positive electrode material precursor and preparation method thereof, ternary lithium battery positive electrode material and preparation method and application thereof | |
| CN111592053A (en) | Nickel-based layered lithium ion battery positive electrode material and preparation method and application thereof | |
| CN110504447A (en) | A kind of nickel cobalt manganese presoma of Fluorin doped and the preparation method and application thereof | |
| CN114649525A (en) | Lithium-rich manganese-based @ ternary composite precursor, positive electrode material and preparation method of positive electrode material | |
| CN111170369B (en) | Lithium manganate or lithium nickel manganese material and preparation method and application thereof | |
| CN108467069A (en) | The nickel cobalt aluminium ternary material precursor and its preparation process of a kind of extremely low impurity content and application | |
| CN112694104A (en) | Prussian blue analogue, preparation method thereof, negative electrode material and application | |
| KR100424635B1 (en) | Positive active material for lithium secondary battery and method of preparing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |