CN112366317B - High-nickel composite material, preparation method thereof and lithium ion battery - Google Patents
High-nickel composite material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN112366317B CN112366317B CN202011165007.0A CN202011165007A CN112366317B CN 112366317 B CN112366317 B CN 112366317B CN 202011165007 A CN202011165007 A CN 202011165007A CN 112366317 B CN112366317 B CN 112366317B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 31
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 229910001453 nickel ion Inorganic materials 0.000 claims description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002738 chelating agent Substances 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 238000009766 low-temperature sintering Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 abstract description 6
- 239000011229 interlayer Substances 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 25
- 239000010406 cathode material Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
- 239000011654 magnesium acetate Substances 0.000 description 4
- 235000011285 magnesium acetate Nutrition 0.000 description 4
- 229940069446 magnesium acetate Drugs 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 2
- 229940009827 aluminum acetate Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- SFKQQYOXXWIJSA-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[O--].[Al+3].[Mn++].[Co++].[Ni++] Chemical compound [Li+].[O--].[O--].[O--].[O--].[O--].[Al+3].[Mn++].[Co++].[Ni++] SFKQQYOXXWIJSA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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 provides a high-nickel composite material, which is composed of a high-nickel anode material and layered LiNi coated on the surface of the high-nickel anode material x M 1‑x O 2 Material composition; the application also provides a preparation method of the high-nickel composite material; the application also provides a lithium ion battery. The present application provides a high nickel composite material in which layered LiNi is present x M 1‑x O 2 The material is used as a coating layer, has stable structure and higher interlayer spacing and allows Li + The high nickel composite material is smooth to pass, so that the high nickel composite material can be used as the anode material of the lithium ion battery to improve the cycle and effectively improve the rate performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-nickel composite material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries have been widely used in many fields due to their high energy density, long service life, low self-discharge rate, and no memory effect. With the continuous expansion of the application field of lithium ion batteries, the positive electrode materials of the lithium ion batteries are also diversified, and besides lithium cobaltate, various positive electrode materials such as lithium manganate, lithium iron phosphate, lithium nickel cobalt manganese (aluminum) oxide and the like are applied in different fields by respective advantages.
In the field of electric automobiles, the continuous improvement of the requirement on the endurance mileage promotes the technical innovation of the high-nickel anode material, and the high-nickel anode material can be corroded by electrolyte or subjected to other side reactions in the long-term use process of a lithium battery so as to increase polarization, reduce capacity and prolong the cycle life. Current solutions typically coat the positive electrode material to avoid direct contact of the electrolyte with the surface of the positive electrode material to reduce these deleterious phenomena. However, the mainstream coating agent currently used is usually Li + The difficult-to-shuttle metal oxide increases the surface polarization of the material to a certain extent, and in addition, the pure nano metal oxide is easy to agglomerate, so that the coating on the surface of the positive electrode material is uneven, and the impedance of the battery is increased. Therefore, the temperature of the molten metal is controlled,it is necessary to find a proper coating agent to improve the cycle performance and rate capability of the cathode material.
Disclosure of Invention
The invention aims to provide a high-nickel composite material, and the high-nickel composite material provided by the application as a positive electrode material of a lithium ion battery can improve the cycle performance and rate capability of the lithium ion battery.
In view of the above, the present application provides a high nickel composite material, which comprises a high nickel positive electrode material and a layered LiNi coated on a surface of the high nickel positive electrode material x M 1-x O 2 Material composition;
wherein x is 0.2-0.8;
m is one or more selected from Al, Ti, Mg, Zr, Fe, Mn, Zn, Cr, Co and Nb.
Preferably, the layered LiNi x M 1-x O 2 The thickness of the material is 50-200 nm.
Preferably, the layered LiNi x M 1-x O 2 The lattice layer spacing of the material is
The application also provides a preparation method of the high-nickel composite material, which comprises the following steps:
mixing chelating agent, nickel salt, M salt and potassium source, drying, heating the obtained solid powder to obtain coating precursor KNi x M 1-x O 2 ；
Carrying out dry coating on the coating precursor, ammonium salt and a high-nickel anode material with residual lithium ions on the surface, and sintering the obtained mixture at low temperature to obtain a high-nickel composite material;
the molar ratio of M ions in the M salt to nickel ions in the nickel salt is (1-x): x, the ratio of the mole number of potassium ions in the potassium source to the total mole number of M ions in the M salt and nickel ions in the nickel salt is (1.02-1.06): 1;
m is selected from one or more of Al, Ti, Mg, Zr, Fe, Mn, Zn, Cr, Co and Nb;
x is 0.2 to 0.8.
Preferably, the chelating agent is selected from one or more of citric acid, sodium citrate, sodium tripolyphosphate, sodium polyphosphate, sodium hexametaphosphate, pyrophosphoric acid and sodium pyrophosphate; the nickel salt is nickel acetate, the M salt is acetic acid M, and the potassium source is KNO 3 、KCl、KBr、KI、KF、KOH、K 2 O、K 2 CO 3 、K 2 SO 4 And CH 3 One or more of COOK.
Preferably, in the step of obtaining the coating precursor, the drying mode is stirring in a constant-temperature water bath, the temperature of the constant-temperature water bath is 50-100 ℃, and the heating temperature is 650-900 ℃.
Preferably, the ammonium salt is selected from NH 4 Cl、NH 4 F、NH 4 Br、(NH 4 ) 3 PO 4 And (NH) 4 ) 2 HPO 4 The mass ratio of the ammonium salt to the coating precursor is (2-6): 1.
preferably, the molar ratio of potassium ions to lithium ions in the coating precursor is (0.6-1): 1.
preferably, the low-temperature sintering temperature is 300-600 ℃, and the time is 1-9 h.
The application also provides a lithium ion battery which comprises a positive electrode and a negative electrode, wherein the positive electrode is made of the high-nickel composite material or the high-nickel composite material prepared by the preparation method.
The application provides a high-nickel composite material which is composed of a high-nickel positive electrode material and LiNi coated on the surface of the high-nickel positive electrode material x M 1-x O 2 Material composition; coating layer LiNi of the present application x M 1-x O 2 The material has stable structure and higher lattice layer spacing, and can allow lithium ions to pass smoothly, so that the high-nickel composite material can improve the cycle performance and rate capability of the high-nickel composite material as a positive electrode material of a lithium ion battery.
Furthermore, the application also provides a preparation method of the high-nickel composite materialThe preparation method comprises using K with large ionic radius + Synthesis of nanosized layered KNi with high c-value lattice by high temperature x M 1-x O 2 Then the nano-scale KNi is applied x M 1-x O 2 The particles and ammonium salt are dispersed and coated on the surface of the high-nickel anode material, high-residual lithium on the surface of the high-nickel anode material is used as a lithium source, and LiNi with high lattice layer spacing is generated on the surface of the high-nickel anode material at low temperature by an ion exchange method x M 1-x O 2 A coating layer having a stable structure and a high interlayer spacing allowing Li + The rate capability of the nickel cathode material is effectively improved while the cycle is improved.
Drawings
FIG. 1 is an SEM photograph of a high nickel composite prepared in example 1 of the present invention;
fig. 2 is a graph of rate capacity for positive electrode materials prepared in example 1 of the present invention and comparative example 1;
fig. 3 is a graph showing cycle performance of the cathode materials prepared in example 2 of the present invention and comparative example 2;
fig. 4 is a capacity graph of the positive electrode materials prepared in example 3 of the present invention and comparative example 2.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the characteristics that lithium ions on a coating layer on the surface of the current high-nickel cathode material are difficult to shuttle and the structure is unstable, the application provides the high-nickel composite material, and the high-nickel composite material has stable structure due to the introduction of the nanoscale high-spacing coating layer and is beneficial to the passing of the lithium ions. Specifically, the embodiment of the invention discloses a high-nickel composite material which comprises a high-nickel positive electrode material and layered LiNi coated on the surface of the high-nickel positive electrode material x M 1-x O 2 Material composition;
wherein x is 0.2-0.8;
m is one or more selected from Al, Ti, Mg, Zr, Fe, Mn, Zn, Cr, Co and Nb.
The coated material in the high nickel composite material described herein is a high nickel positive electrode material, which may be a high nickel positive electrode material well known to those skilled in the art, and more specifically, the high nickel positive electrode material is selected from a nickel cobalt lithium aluminate (NCA) material or LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The layered LiNi coated on the surface of the high-nickel cathode material x M 1-x O 2 The material is used as a coating layer and is a nanoscale layered material with high lattice layer spacing, and the lattice layer spacing is specifically
The thickness of the film is 50-200 nm. The layered LiNi x M 1-x O 2 The material may be LiNi 0.5 Mg 0.5 O 2 Or LiNi 0.5 Al 0.5 O 2 Other materials can be selected according to performance requirements.
The application also provides a preparation method of the high-nickel composite material, which comprises the following steps:
mixing chelating agent, nickel salt, M salt and potassium source, drying, heating the obtained solid powder to obtain coating precursor KNi x M 1-x O 2 ；
Carrying out dry coating on the coating precursor, ammonium salt and a high-nickel anode material with residual lithium ions on the surface, and sintering the obtained mixture at low temperature to obtain a high-nickel composite material;
the molar ratio of M ions in the M salt to nickel ions in the nickel salt is (1-x): x, the ratio of the mole number of potassium ions in the potassium source to the total mole number of M ions in the M salt and nickel ions in the nickel salt is (1.02-1.06): 1;
m is selected from one or more of Al, Ti, Mg, Zr, Fe, Mn, Zn, Cr, Co and Nb;
x is 0.2 to 0.8.
In the process of preparing the high-nickel composite material, in order to fully mix the raw materials, the methodFirstly, dissolving a chelating agent, nickel salt and M salt in deionized water according to a ratio to obtain an initial solution, adding a potassium source into the initial solution, and stirring in a constant-temperature water bath until the solvent is completely evaporated. In the above process, the nickel salt is specifically selected from nickel acetate; the M salt is selected from M acetate; the potassium source is KNO 3 、KCl、KBr、KI、KF、KOH、K 2 O、K 2 CO 3 、K 2 SO 4 And CH 3 One or more of COOK, in particular embodiments the potassium source is selected from potassium nitrate or potassium chloride; the chelating agent is selected from one or more of citric acid, sodium citrate, sodium tripolyphosphate, sodium polyphosphate, sodium hexametaphosphate, pyrophosphoric acid, and sodium pyrophosphate, and in particular embodiments, the chelating agent is selected from citric acid or pyrophosphoric acid, and the chelating agent is configured to form a metal ion gel to promote uniform mixing between the metal atoms. And the temperature of the constant-temperature water bath is 50-100 ℃, so that the solvent is completely evaporated to dryness to obtain solid powder. The molar ratio of M ions in the M salt to nickel ions in the nickel salt is (1-x): x, the ratio of the mole number of potassium ions in the potassium source to the total mole number of M ions in the M salt and nickel ions in the nickel salt is (1.02-1.06): 1, the molar ratio of the M ions to the nickel ions needs to ensure the matching relationship of the finally obtained coating material, the ratio of the mole number of the potassium ions to the total mole number of the M ions and the nickel ions ensures that a complete layered crystal structure is finally obtained, a complete crystal structure cannot be formed below the ratio relationship, and more K becomes impurities above the ratio relationship.
According to the invention, the solid powder is heated and cooled to obtain the precursor of the coating. The above process is specifically a complex exchange of various metal ions to make the distribution of various metal ions more uniform. The heating temperature is 650-900 ℃, and in a specific embodiment, the heating temperature is 700-800 ℃.
The coating precursor is mixed with ammonium salt and a high-nickel anode material with residual lithium ions on the surface to carry out dry coating, so as to obtain a mixture. In the process, the ammonium salt acts as a fluxing agentAgents, in particular selected from NH 4 Cl、NH 4 F、NH 4 Br、(NH 4 ) 3 PO 4 And (NH) 4 ) 2 HPO 4 In particular embodiments, the ammonium salt is selected from ammonium chloride. The dry coating is specifically a ball-milling dry coating. The mass ratio of the ammonium salt to the coating precursor is (2-6): in a specific embodiment, the mass ratio of the ammonium salt to the coating precursor is (3-5): 1. the molar ratio of potassium ions to lithium ions in the coating precursor is (0.6-1): 1. the high-nickel cathode material with the residual lithium ions on the surface is a calcined high-nickel cathode material, namely the surface layer of the high-nickel cathode material contains unreacted lithium ions, but the lithium ions are not lithium of the high-nickel cathode material body.
According to the invention, finally, the obtained mixture is sintered at low temperature to obtain the high-nickel composite material, specifically, the mixture and high-purity oxygen are heated to 300-600 ℃ in an atmosphere, and the temperature is kept for 1-9 h to enable the coating precursor and lithium ions remained on the surface of the high-nickel cathode material to perform sufficient ion exchange reaction to obtain LiNi x M 1-x O 2 And (4) coating materials. In a specific embodiment, the low-temperature sintering temperature is 400-500 ℃, and the heat preservation time is 3-6 h.
The application also provides a lithium ion battery which comprises a positive electrode and a negative electrode, wherein the material of the positive electrode is specifically selected from the high-nickel composite material in the scheme or the high-nickel composite material prepared by the preparation method in the scheme.
For further understanding of the present invention, the high nickel composite material and the preparation method thereof provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
Weighing 50g of nickel acetate, adding the nickel acetate into deionized water, weighing aluminum acetate according to the molar ratio of Ni/Al to 1, adding the aluminum acetate into the solution, and stirring the solution at normal temperature until the solution is clear; weighing 20g of citric acid, dissolving in the prepared metal solution, and stirring until the solution is clear; adding 58.36g of potassium nitrate into the solution, and stirring the solution in a constant-temperature water bath at 80 ℃ for 12 hours until the solvent is evaporated, and collecting solid powder; heating the solid powder in a kiln to 900 ℃ at the heating rate of 1 ℃/min, preserving the heat for 8 hours, cooling to room temperature, and crushing by using a universal crusher to obtain a coating precursor;
weighing 100g of a calcined NCA positive electrode material with the surface free lithium content of 0.6 wt%, adding the material into a ball milling tank, then weighing 8.82g of a coating precursor and 32g of ammonium chloride respectively, adding the materials into the ball milling tank, and carrying out ball milling and dry packaging for 1 h; placing the ball-milled material in a kiln, introducing high-purity oxygen, heating to 400 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 4 hours to enable the coating precursor and residual lithium on the NCA surface to perform sufficient ion exchange reaction, cooling to room temperature, washing the material with deionized water for three times, and drying in a vacuum drying box to obtain the material coated with the nano LiNi on the surface 0.5 Al 0.5 O 2 The NCA positive electrode material of (1).
The surface prepared by the embodiment is coated with nano LiNi 0.5 Al 0.5 O 2 The scanning electron micrograph of the NCA positive electrode material of (1) is shown in fig. 1. The electrochemical performance of the button cell prepared from the cathode material is tested, and the result is shown in figure 2.
Comparative example 1
100g of NCA positive electrode material was charged into a ball mill, followed by 0.2g of Al 2 O 3 And (3) starting ball milling and dry packaging of the nano particles for 2 hours, and heating the ball grinding materials in a kiln, wherein the heating system is as follows: the room temperature is heated to 400 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 6h, then the mixture is cooled, and oxygen is introduced in the whole heating process. The electrochemical performance of the button cell prepared from the cathode material is tested, and the result is shown in figure 2.
Example 2
Weighing 40g of nickel acetate, adding the nickel acetate into deionized water, stirring for dissolving, weighing magnesium acetate according to the molar ratio Ni/Mg of 1, adding the magnesium acetate into the solution, and stirring at normal temperature until the solution is clear; adding 20g of pyrophosphoric acid, stirring, adding 35.44g of potassium chloride, stirring the solution into gel, placing the gel in a constant-temperature water bath kettle, stirring at the temperature of 90 ℃ until the solvent is completely evaporated, heating the solid powder obtained after evaporation to 800 ℃ in a kiln at the heating rate of 2 ℃/min, keeping the temperature for 12 hours, and grinding and crushing the cooled solid powder by a sand mill to obtain a coating precursor;
100g of LiNi having 0.7 wt% of surface residual lithium was weighed 0.8 Co 0.1 Mn 0.1 O 2 9.08g of the coating precursor and 36g of ammonium chloride are added into a ball milling tank for ball milling and dry packaging for 1 hour; heating the dry-coated material to 450 ℃ in a kiln at a heating rate of 1 ℃/min, preserving heat for 6 hours, carrying out ion exchange reaction, cooling the furnace temperature, washing the solid powder with deionized water for three times, and drying to obtain the LiNi coated with the nano-particles 0.5 Mg 0.5 O 2 LiNi of (2) 0.8 Co 0.1 Mn 0.1 O 2 And (3) a positive electrode material.
The electrochemical performance of the button cell prepared from the cathode material is tested, and the result is shown in fig. 3.
Comparative example 2
100g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the positive electrode material into a ball mill, then adding 0.3g of MgO nano particles, starting the ball mill to dry and pack for 2 hours, and heating the ball grinding material in a kiln, wherein the heating system is as follows: the room temperature is heated to 450 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 6h and then the mixture is cooled, and oxygen is introduced in the whole heating process. The electrochemical performance of the button cell prepared from the cathode material is tested, and the result is shown in fig. 3.
Comparative example 3
Weighing 40g of nickel acetate, adding the nickel acetate into deionized water, stirring for dissolving, weighing magnesium acetate according to the molar ratio of Ni/Mg to 1, adding the magnesium acetate into the solution, and stirring at normal temperature until the solution is clear; adding 20g of pyrophosphoric acid, stirring, adding 16.85g of potassium chloride, stirring the solution to form gel, placing the gel in a constant-temperature water bath kettle, stirring at the temperature of 90 ℃ until the solvent is completely evaporated, heating the solid powder obtained after evaporation to 800 ℃ in a kiln at the heating rate of 2 ℃/min, preserving heat for 12 hours, and grinding and crushing the cooled solid powder by a sand mill to obtain a coating precursor;
100g of LiNi having 0.7 wt% of surface-remaining lithium was weighed 0.8 Co 0.1 Mn 0.1 O 2 12.4g of coating precursor and 36g of ammonium chloride are added into a ball milling tank for ball milling and dry packaging for 1 hour; heating the dry-coated materials in a kiln at a heating rate of 1 ℃/min to 450 ℃ and preserving heat for 6h, carrying out ion exchange reaction, and cooling the furnace temperatureThen washing the solid powder with deionized water for three times and drying to obtain the product with the surface coated with nano LiNi 0.5 Mg 0.5 O 2 LiNi of (2) 0.8 Co 0.1 Mn 0.1 O 2 And (3) a positive electrode material. The electrochemical performance of the button cell prepared by the cathode material is tested, fig. 4 is a capacity comparison curve of the example 2 and the comparative example 3, and as can be seen from fig. 4, the capacity of the cathode material prepared in the comparative example 3 is obviously lower than that of the cathode material prepared in the example 2, so that the capacity of the cathode material is obviously influenced by the reduction of the potassium content in the high-nickel composite material.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of a high-nickel composite material comprises the following steps:
mixing chelating agent, nickel salt, M salt and potassium source, drying, heating the obtained solid powder to obtain coating precursor KNi x M 1-x O 2 ；
Carrying out dry coating on the coating precursor, ammonium salt and a high-nickel anode material with residual lithium ions on the surface, and sintering the obtained mixture at low temperature to obtain a high-nickel composite material;
the molar ratio of M ions in the M salt to nickel ions in the nickel salt is (1-x): x, the ratio of the mole number of potassium ions in the potassium source to the total mole number of M ions in the M salt and nickel ions in the nickel salt is (1.02-1.06): 1;
the high-nickel composite material is composed of a high-nickel anode material and layered LiNi coated on the surface of the high-nickel anode material x M 1- x O 2 Material composition;
the layered LiNi x M 1-x O 2 The lattice layer spacing of the material is
M is selected from one or more of Al, Ti, Mg, Zr, Fe, Mn, Zn, Cr, Co and Nb;
x is 0.2 to 0.8.
2. The method of claim 1, wherein said layered LiNi is x M 1-x O 2 The thickness of the material is 50-200 nm.
3. The method according to claim 1, wherein the chelating agent is selected from one or more of citric acid, sodium citrate, sodium tripolyphosphate, sodium polyphosphate, sodium hexametaphosphate, pyrophosphoric acid, and sodium pyrophosphate; the nickel salt is nickel acetate, the M salt is acetic acid M, and the potassium source is KNO 3 、KCl、KBr、KI、KF、KOH、K 2 O、K 2 CO 3 、K 2 SO 4 And CH 3 One or more of COOK.
4. The method according to claim 1, wherein the drying is performed by stirring in a thermostatic waterbath at a temperature of 50 to 100 ℃ and at a temperature of 650 to 900 ℃ in the step of obtaining the coating precursor.
5. The method according to claim 1, wherein the ammonium salt is selected from NH 4 Cl、NH 4 F、NH 4 Br、(NH 4 ) 3 PO 4 And (NH) 4 ) 2 HPO 4 The mass ratio of the ammonium salt to the coating precursor is (2-6): 1.
6. the preparation method according to claim 1, wherein the molar ratio of potassium ions to lithium ions in the coating precursor is (0.6-1): 1.
7. the preparation method according to claim 1, wherein the low-temperature sintering temperature is 300-600 ℃ and the time is 1-9 h.
8. A lithium ion battery comprises a positive electrode and a negative electrode, and is characterized in that the material of the positive electrode is the high-nickel composite material prepared by the preparation method of any one of claims 1 to 7.
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