CN115557543B - Surface in-situ coating type positive electrode lithium supplementing material and preparation method thereof - Google Patents
Surface in-situ coating type positive electrode lithium supplementing material and preparation method thereof Download PDFInfo
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- CN115557543B CN115557543B CN202211269170.0A CN202211269170A CN115557543B CN 115557543 B CN115557543 B CN 115557543B CN 202211269170 A CN202211269170 A CN 202211269170A CN 115557543 B CN115557543 B CN 115557543B
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- divalent metal
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- 239000000463 material Substances 0.000 title claims abstract description 98
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 60
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 50
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 31
- 239000010452 phosphate Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 18
- 239000011149 active material Substances 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000007086 side reaction Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000002427 irreversible effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910018068 Li 2 O Inorganic materials 0.000 description 6
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229910018661 Ni(OH) Inorganic materials 0.000 description 3
- -1 and at this time Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/265—General methods for obtaining phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 relates to the field of positive electrode lithium supplementing materials of lithium batteries, in particular to a surface in-situ coating type positive electrode lithium supplementing material and a preparation method thereof, and the method comprises the following steps: 1) Coating a compound comprising phosphate on the surface of a precursor compound of Ni, and preparing powder A; 2) Uniformly mixing the powder with a precursor compound of Li by a solid phase method to obtain powder B; 3) Calcining the powder B in inert atmosphere to obtain the surface in-situ coated positive electrode lithium supplementing material xLi 2 NiO 2 @yLi 3 PO 4 . The method is simple, the coated anode lithium supplementing material can be prepared through one-step reaction, and the prepared material has excellent performance and good stability.
Description
Technical Field
The invention relates to a positive electrode lithium supplementing material of a lithium battery, in particular to a surface in-situ coating type positive electrode lithium supplementing material and a preparation method thereof.
Background
Lithium ion batteries with high energy density, long service life and no memory effect have been widely used in various fields such as portable electronic devices and electric automobiles since commercialization. Lithium ion batteries are currently the mainstream secondary batteries, which are peculiar in that their energy storage and release process is accompanied by Li + Reversible deintercalation between positive and negative electrodes, therefore Li capable of reversible deintercalation in battery system + The number will directly determine the capacity of the battery. However, in general, in the first charge and discharge process of the lithium ion battery, the organic solvent undergoes a reduction reaction at the negative electrode and forms a lithium-containing SEI film, and the process partially consumes the reversibly deintercalated active Li in the battery + Thereby adversely affecting the initial discharge capacity and cycle life of the battery. In particular, for a high specific energy lithium ion battery using a high capacity low first-effect negative electrode, the initial cycle activity Li + The loss phenomenon becomes more serious.
To alleviate the above problems, it is necessary to supplement active Li in a battery system in advance + This can be achieved by supplementing lithium to the positive electrode or the negative electrode, respectively. The lithium supplementing of the negative electrode often involves the use of metallic lithium, so that the experimental process is complex and has certain potential safety hazard; the lithium supplementing of the positive electrode can be achieved simply by introducing the positive electrode lithium supplementing additive into the slurry during the homogenization process. The positive electrode lithium supplement additive is an active material with high capacity and low first effect, and can irreversibly remove a large amount of Li in the first cycle process + Thereby counteracting the active Li consumed by SEI film formation + . In a plurality of positive electrode lithium supplementing additives, li with irreversible capacity of 250-300 mAh/g can be provided in a conventional voltage interval 2 NiO 2 The material (Immm structure) has a high volume specific capacity although the mass specific capacity is not very outstanding, and does not generate a large amount of air during use as other positive electrode lithium supplement additives (such as sacrificial lithium salt, oxides and nitrides of Li)The material is, more importantly, compatible with the solvents used in the existing homogenization steps and is therefore a lithium supplementing material that is promising for large-scale applications. However Li 2 NiO 2 Materials often have a heterogeneous phase during synthesis, which can lead to a decrease in initial capacity; in addition, the surface structure of the material is extremely easy to be H in the air 2 O and CO 2 Side reactions occur, which can lead to an increase in the amount of residual alkali and further affect the capacity of the product. Chinese patent (application No. 202010494986.8) discloses a doped type of Li 2 NiO 2 Materials, synthesized products (chemical formula is xLi 2 O·yNiO·zM a O b M is Al, co, ti, mn), the problem of instability of the material surface structure in air is not improved, although the purity is significantly improved. To improve the stability of materials in air, the use of Al has been reported in the literature (J. Mater. Chem.,2008,18,5880-5887) 2 O 3 For Li 2 NiO 2 The strategy of coating the surface of the material is also disclosed in China patent (application No. 202110336830.1) which discloses ZrO with a more stable surface structure 2 /B 2 O 3 Double-coated Li 2 NiO 2 A material. However, the above-mentioned coated Li 2 NiO 2 The material is obtained in two steps, i.e. Li is first synthesized 2 NiO 2 The material is then introduced to the surface of the material by a liquid or solid phase method. The experimental procedure is not only cumbersome, but also because the coating object is Li with poor stability in air 2 NiO 2 The finished material, therefore, also needs to avoid side reactions of the material during the process, which undoubtedly increases the coated Li 2 NiO 2 The preparation of the material is difficult.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides an in situ method for producing Li 2 NiO 2 A method for preparing a coating on a surface of a material, comprising the steps of:
1) Coating a compound comprising phosphate on the surface of a precursor compound of Ni, and preparing powder A;
2) Uniformly mixing the powder with a precursor compound of Li by a solid phase method to obtain powder B;
3) Calcining the powder B in inert atmosphere to obtain the surface in-situ coated positive electrode lithium supplementing material xLi 2 NiO 2 @yLi 3 PO 4 。
Preferably, the method of the present invention further comprises an operation of adding a divalent metal M, comprising the steps of:
coating the surface of a precursor compound of Ni with phosphate containing divalent metal M, salt of phosphate and divalent metal M or oxide of phosphate and divalent metal M in the step 1);
the xLi is prepared in the step 3) 2 Ni 1-z M z O 2 @yLi 3 PO 4 。
Preferably, the phosphate is an ammonium phosphate salt when no compound comprising a metal ion M is added;
further preferably (NH) 4 ) 3 PO 4 ，(NH 4 ) 2 HPO 4 ，NH 4 H 2 PO 4 One or more of them. Anions in the ammonium phosphate salt can react with the Li source in a subsequent sintering process to produce lithium phosphate, while cations in the ammonium phosphate salt can react with the Li source in a subsequent sintering process to produce volatile byproducts, so that impurities are not introduced into the final product.
Preferably, the divalent metal M is Zn 2+ 、Ba 2+ 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Mn 2+ Or Fe (Fe) 2+ The method comprises the steps of carrying out a first treatment on the surface of the Divalent metal ions are added, and 2-valent M ions positioned on the outer surface of the precursor of Ni can be inwards diffused in the subsequent sintering process, and Li with higher M content outside particles is formed 2 Ni 1-z M z O 2 An active material.
Preferably, the salt of the divalent metal M is one or more of sulfate, chloride or nitrate of the divalent metal M;
preferably, when a salt of a divalent metal M (non-phosphate) is added, the phosphate is an ammonium phosphate salt or a sodium phosphate salt; when the metal ion M is added, sulfate and chloride in the sulfate and chloride corresponding to M cannot be decomposed into gases during the subsequent heat treatment, and thus the formation of the target product is affected, and the metal ion M exists as impurities in the final product, and therefore, the metal ion M needs to be removed by washing with water, and at this time, na ions still exist in the liquid phase in the precipitation method, and thus, can be removed together with the washing with water.
Preferably, when the divalent metal M is added in the form of an oxide, the phosphate is an ammonium phosphate salt.
Further preferably, the ammonium phosphate salt is (NH) 4 ) 3 PO 4 、(NH 4 ) 2 HPO 4 、NH 4 H 2 PO 4 One or more of the following;
further preferably, the soluble sodium phosphate salt Na 3 PO 4 、Na 2 HPO 4 、NaH 2 PO 4 One or more of the following. The ammonium phosphate and the sodium phosphate have the characteristics of easy dissolution, low cost, small environmental pollution and the like.
Preferably, in the step 1), the phosphate is coated on the surface of the precursor compound of Ni by a vapor method or a solid phase method.
Preferably, the steaming method comprises: firstly, dissolving phosphate, phosphate of divalent metal M, precursor compounds of phosphate, divalent metal M salt and Ni in water to form an aqueous solution, and then evaporating the solution;
preferably, the solid phase method is to ball mill ammonium phosphate solid and precursor compound of oxide and Ni corresponding to divalent metal M through a ball mill, fully mix the solid phosphate and the precursor compound of Ni through a high-speed mixer or mix the solid phosphate and the precursor compound of Ni in a mechanical fusion machine.
Preferably, the solid phase method in step 2) includes: ball milling by a ball mill, full mixing by a high-speed mixer or mixing in a mechanical fusion machine.
As a preferable operation mode, the specific parameters of the ball milling of the ball mill are that the rotational speed of the ball mill is 200-800r/min, the ball milling time is 1-72h, and the weight ratio of ball materials is 5-50:1, a step of;
the specific operation parameters of the high-speed mixer for fully mixing are that the rotating speed of the high-speed mixer is 500-10000r/min and the mixing time is 1-72h;
the specific operation parameters of the mixing in the mechanical fusion machine are that the rotating speed of the mechanical fusion machine is 500-10000r/min and the mixing time is 1-72h.
Preferably, the calcination temperature in the step 3) is 450-700 ℃ and the calcination time is 5-25 h.
As a preferable operation mode, the inert atmosphere is nitrogen atmosphere, argon atmosphere or mixed atmosphere of nitrogen and argon.
Preferably, the ratio of the amounts of Li in the precursor compound of Li, ni in the precursor compound of Ni, and phosphorus in the phosphate is 1:0.4 to 0.5: 0.005-0.05;
the ratio of the amounts of Li in the Li precursor compound, ni in the Ni precursor compound, divalent metal M and phosphorus in the phosphate is 1: 0.004-0.495: 0.004-0.495: 0.005-0.05. In the present invention, the precursor compound of Ni is Ni (OH) 2 ，NiO，NiCO 3 One or more of the following;
the Li compound is selected from LiOH, liOH.H 2 O、Li 2 And one or more of O and lithium nitrate.
The invention also protects the surface in-situ coating type positive electrode material prepared by the method;
preferably, the general formula of the surface in-situ coating type positive electrode material is as follows: xLi 2 NiO 2 @yLi 3 PO 4 Or xLi 2 Ni 1- z MzO 2 @yLi 3 PO 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x+y=1, y is 0.01 to 0.1, and z is 0.01 to 0.99.
The invention also protects a lithium ion battery anode or a lithium ion battery containing the surface in-situ coated anode lithium supplementing material.
The preparation method of the lithium ion battery positive electrode is carried out according to the conventional technology, namely the surface in-situ coated positive electrode lithium supplementing material, a positive electrode active substance, a conductive agent and a binder are uniformly mixed and dissolved in an organic solvent to form positive electrode slurry, and the positive electrode slurry is coated on a support body to prepare the positive electrode of the lithium ion battery. Wherein, the addition amount of the surface in-situ coating type positive electrode lithium supplementing material accounts for 0.5-5% of the total mass of the positive electrode active material.
The preparation method of the lithium ion battery is carried out according to the conventional technology, and the positive electrode of the lithium ion battery is required to be included.
The invention has the following beneficial effects:
xLi according to the invention 2 NiO 2 @yLi 3 PO 4 In the preparation process of the surface in-situ coated positive electrode lithium supplementing material, inert Li on the outer surface 3 PO 4 Coating layer and Li inside 2 NiO 2 The active material is formed simultaneously during the high temperature sintering step. As reported in the prior literature and invention, for Li 2 NiO 2 Compared with the subsequent liquid phase or solid phase coating of the finished material, the surface in-situ coated positive electrode lithium supplementing material disclosed by the invention does not comprise the subsequent secondary coating step, so that Li can be effectively avoided 2 NiO 2 The active material may be oxidized or combined with H during this process 2 O and CO 2 And side reactions are carried out, so that the preparation difficulty of the material is reduced.
In addition, the material prepared by the in-situ surface coating mode has the following advantages: (1) Contributing to the improvement of inert Li 3 PO 4 The coating layer is uniformly distributed on the outer surface of the primary particles of the material, thereby further relieving Li 2 NiO 2 Side reactions occur as a result of the active material contacting air and the electrolyte during storage and use; (2) Li formed on the outer surface of the material 3 PO 4 The active material primary particles can play a role in inhibiting the growth of the active material primary particles in the sintering process, and the reduction of the particle size of the active material is beneficial to the capacity improvement; (3) Li formed on the outer surface of the material at the initial stage of sintering 3 PO 4 The coating layer can effectively inhibit trace O in the inert atmosphere and during sintering of the active material 2 And CO 2 Thereby facilitating the contact of Li 2 NiO 2 And the purity of the active material is improved.
xLi according to the invention 2 Ni 1-z M z O 2 @yLi 3 PO 4 The 2-valent M ions located on the outer surface of the precursor of Ni can diffuse inwards and form Li with higher M content outside the particles 2 Ni 1-z M z O 2 Active materials, materials of this structure have the following advantages: (1) Enrichment of 2-valent M ions on the surface of the material is beneficial to preventing Ni inside 2+ Trace amounts of O during sintering 2 Oxidized, thereby improving the purity of the product; (2) Since the irreversible oxidation of lattice oxygen in the material begins at the particle outer surface, some specific M ions (e.g. Cu 2+ ，Zn 2+ ) The enrichment of the lithium ion battery is beneficial to increasing the irreversible oxidation degree of lattice oxygen during the first charge, so that the irreversible capacity of the lithium ion battery material is improved; (3) Enrichment of 2-valent M ions on the particle surface is beneficial to reducing Ni formed by the active material in a high-charge state 3+ Contact with the electrolyte and side reactions that result. In addition, the material also contains the inert Li 3 PO 4 In-situ cladding provides advantages.
The two surface in-situ coating type positive electrode lithium supplementing materials do not use expensive elements, and the preparation process flow is simple, so that the method is suitable for large-scale industrial production.
Drawings
FIG. 1 shows a surface in-situ coated positive electrode lithium supplementing material xLi 2 NiO 2 @yLi 3 PO 4 (A in FIG. 1) and xLi 2 Ni 1- z Cu z O 2 @yLi 3 PO 4 Schematic of (B in fig. 1).
FIG. 2 is an X-ray diffraction (XRD) pattern of the materials prepared in examples 1-2 and comparative example 1.
FIG. 3 is a graph showing the first charge-discharge curves of the materials prepared in examples 1-2 and comparative example 1.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments. These examples are only for aiding in the understanding of the invention, and the scope of the invention is to be determined by the claims and not limited by these examples.
Example 1
The surface in-situ coating type positive electrode lithium supplementing material 0.95Li 2 NiO 2 @0.05Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.95Li 2 NiO 2 @0.05Li 3 PO 4 Is measured by the mole ratio of elements of Li 2 O, niO and (NH) 4 ) 2 HPO 4 。
(2) To be soluble (NH) 4 ) 2 HPO 4 Dissolving in deionized water, dispersing NiO in the solution, and evaporating the solvent under continuous stirring at 80 ℃ to obtain powder A.
(3) Powder A was mixed with Li previously weighed 2 O is N 2 Ball milling and mixing are carried out for 6 hours under the atmosphere (the rotating speed is 300rpm/min, the ball-material ratio is 50:1), and the powder B is obtained.
(4) Sintering the mixture at 600 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 10 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.95Li 2 NiO 2 @0.05Li 3 PO 4 。
Example 2
The surface in-situ coating type positive electrode lithium supplementing material 0.95Li 2 Ni 0.95 Cu 0.05 O 2 @0.05Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.95Li 2 Ni 0.95 Cu 0.05 O 2 @0.05Li 3 PO 4 Is measured by the mole ratio of elements of Li 2 O、NiO、CuSO 4 And (NH) 4 ) 2 HPO 4 。
(2) CuSO is performed 4 Dissolved in deionized water, followed by dispersing NiO in the above solution, to give liquid phase mixture 1.
(3) Will (NH) 4 ) 2 HPO 4 Dissolving in deionized water, and slowly adding into liquid phase mixture 1 under stirring at 350rpmAnd then carrying out suction filtration, water washing twice and drying at 100 ℃ for 6 hours on the liquid phase mixture to obtain powder A.
(4) Powder A was mixed with Li previously weighed 2 O is N 2 Ball milling and mixing are carried out for 6 hours under the atmosphere (the rotating speed is 300r/min, the ball-material ratio is 50:1), and the powder B is obtained.
(5) Sintering the mixture at 600 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 10 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.95Li 2 Ni 0.95 Cu 0.05 O 2 @0.05Li 3 PO 4 。
Example 3
The surface in-situ coating type positive electrode lithium supplementing material 0.9Li 2 NiO 2 @0.1Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.9Li 2 NiO 2 @0.1Li 3 PO 4 Weighing LiOH, ni (OH) according to the element molar ratio of (2) 2 And (NH) 4 ) 2 HPO 4 。
(2) To be soluble (NH) 4 ) 2 HPO 4 Dissolving in deionized water, followed by Ni (OH) 2 Dispersing in the above solution, and evaporating the solvent under continuous stirring at 80deg.C to obtain powder A.
(3) Powder A was mixed with LiOH in N 2 Ball milling and mixing are carried out for 8 hours under the atmosphere (the rotating speed is 200rpm/min, the ball-material ratio is 50:1), and the powder B is obtained.
(4) Sintering the mixture at 620 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 12 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.9Li 2 NiO 2 @0.1Li 3 PO 4 。
Example 4
The surface in-situ coating type positive electrode lithium supplementing material 0.9Li 2 Ni 0.9 Cu 0.1 O 2 @0.1Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.9Li 2 Ni 0.9 Cu 0.1 O 2 @0.1Li 3 PO 4 Is measured by the mole ratio of elements of Li 2 O、Ni(OH) 2 、CuCl 2 And Na (Na) 2 HPO 4 。
(2) Na is mixed with 2 HPO 4 Dissolving in deionized water, followed by Ni (OH) 2 Dispersed in the above solution to give a liquid phase mixture 1.
(3) CuCl is added 2 Dissolving in deionized water, slowly adding into the liquid phase mixture 1 under the condition of stirring at 350rpm, and then carrying out suction filtration, water washing twice and drying at 100 ℃ for 6 hours to obtain powder A.
(4) Powder A was mixed with Li previously weighed 2 O is N 2 Ball milling and mixing are carried out for 4 hours under the atmosphere (the rotating speed is 400r/min, the ball-material ratio is 50:1), and the powder B is obtained.
(5) Sintering the mixture at 550 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 15 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.9Li 2 Ni 0.9 Cu 0.1 O 2 @0.1Li 3 PO 4 。
Example 5
The surface in-situ coating type positive electrode lithium supplementing material 0.97Li 2 Ni 0.9 Zn 0.1 O 2 @0.03Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.97Li 2 Ni 0.9 Zn 0.1 O 2 @0.03Li 3 PO 4 Is measured by the mole ratio of elements of Li 2 O、Ni(OH) 2 、ZnCl 2 And NaH 2 PO 4 。
(2) NaH is processed by 2 PO 4 Dissolving in deionized water, followed by Ni (OH) 2 Dispersed in the above solution to give a liquid phase mixture 1.
(3) ZnCl 2 Dissolved in deionized water and slowly added to the liquid phase mixture 1 with stirring at 350rpm, followed byAnd carrying out suction filtration and water washing on the liquid phase mixture for two times, and drying at 100 ℃ for 6 hours to obtain powder A.
(4) Powder A was mixed with Li previously weighed 2 O is N 2 Ball milling and mixing are carried out for 4 hours under the atmosphere (the rotating speed is 200r/min, the ball-material ratio is 50:1), and the powder B is obtained.
(5) Sintering the mixture at 550 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 15 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.97Li 2 Ni 0.9 Zn 0.1 O 2 @0.03Li 3 PO 4 。
Example 6
The surface in-situ coating type positive electrode lithium supplementing material 0.95Li 2 Ni 0.85 Fe 0.15 O 2 @0.05Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.95Li 2 Ni 0.85 Fe 0.15 O 2 @0.05Li 3 PO 4 Is measured by the mole ratio of elements of Li 2 O、Ni(OH) 2 、FeCl 2 And (NH) 4 ) 2 HPO 4 。
(2) Will (NH) 4 ) 2 HPO 4 Dissolving in deionized water, followed by Ni (OH) 2 Dispersed in the above solution to give a liquid phase mixture 1.
(3) FeCl is added 2 Dissolving in deionized water, slowly adding into the liquid phase mixture 1 under the condition of stirring at 350rpm, and then carrying out suction filtration, water washing twice and drying at 100 ℃ for 6 hours to obtain powder A.
(4) Powder A was mixed with Li previously weighed 2 O is N 2 Ball milling and mixing are carried out for 4 hours under the atmosphere (the rotating speed is 400r/min, the ball-material ratio is 50:1), and the powder B is obtained.
(5) Sintering the powder B at 550 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 15 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.95Li 2 Ni 0.85 Fe 0.15 O 2 @0.05Li 3 PO 4 。
Example 7
The surface in-situ coating type positive electrode lithium supplementing material 0.99Li 2 Ni 0.85 Mn 0.15 O 2 @0.01Li 3 PO 4 The preparation method comprises the following specific steps:
(1) According to 0.99Li 2 Ni 0.85 Mn 0.15 O 2 @0.01Li 3 PO 4 Weighing LiOH, ni (OH) according to the element molar ratio of (2) 2 MnO and (NH) 4 ) 2 HPO 4 。
(2) MnO and (NH) are fused by a mechanical fusion machine 4 ) 2 HPO 4 Pre-coated with Ni (OH) 2 The surface of the precursor is provided with powder A. Powder A was mixed with LiOH in N 2 Ball milling and mixing are carried out for 8 hours under the atmosphere (the rotating speed is 200rpm/min, the ball-material ratio is 50:1), and the powder B is obtained.
(3) Sintering the powder B at 600 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 12 hours, and then naturally cooling to room temperature to obtain the surface in-situ coated positive electrode lithium supplementing material 0.99Li 2 Ni 0.85 Mn 0.15 O 2 @0.01Li 3 PO 4 。
Comparative example 1
The positive electrode lithium supplementing material Li of this comparative example 2 NiO 2 The preparation method comprises the following specific steps:
(1) According to Li 2 NiO 2 Is measured by the mole ratio of elements of Li 2 O and NiO, and in N 2 Ball milling and mixing (rotation speed 300rpm/min, ball-to-material ratio 50:1) were carried out under atmosphere for 6 hours.
(2) Sintering the mixture at 600 ℃ in argon atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation time is 10 hours, and then naturally cooling to room temperature to obtain Li with an Immm structure 2 NiO 2 And a positive electrode lithium supplementing material.
Experimental example
The materials prepared in examples 1-2 and comparative example 1 above were subjected to structural morphology characterization and electrochemical performance testing, respectively.
FIG. 2 is an X-ray diffraction pattern of the material described in example 2, except that Li is visible in FIG. 2 2 Ni 0.95 Cu 0.05 O 2 Besides the corresponding strong diffraction peak, the attribution to Li can also be observed 3 PO 4 Is marked #), which indicates the (NH) introduced during the synthesis of the material described in example 2 4 ) 2 HPO 4 Is indeed capable of forming Li after sintering 3 PO 4 。
The materials prepared in examples 1 to 7 and comparative example 1 above were respectively subjected to 400 mesh sieving, and used as a positive electrode active material with a binder (PVDF) and a conductive agent (Super P) in a mass ratio of 8:1:1, preparing a positive electrode plate, then assembling a button cell by taking a lithium plate as a negative electrode material in a glove box, and performing constant-current charge and discharge test at 25 ℃ with the following voltage ranges: 3-4.3V and defining a current density of 150mA/g of 1C, the test results are shown in FIG. 3 and Table 1.
TABLE 1
The first charge and discharge test data in table 1 shows that: (1) Since the surface in-situ coated materials of examples 1 to 7 were inhibited from forming an impurity phase and from growing primary particles during the preparation, their primary charge capacities were significantly higher than those of comparative example 1; (2) 0.95Li in example 2 2 Ni 0.95 Cu 0.05 O 2 @0.05Li 3 PO 4 The material has a relatively highest first charge capacity but a relatively lowest first discharge capacity due to Cu 2+ The introduction of the lithium ion battery increases the irreversible oxidation degree of lattice oxygen during the first charge, so that the irreversible capacity of the positive electrode lithium supplementing material is obviously improved. As can be seen from the first charge-discharge curve in FIG. 3, the first charge-discharge curve shape of the material in example 2 is significantly changed compared with that of comparative example 1 and example 1, further illustrating the introduction of Cu 2+ Has successfully replaced Ni 2+ Into the crystal latticeAnd form Li 2 Ni 0.95 Cu 0.05 O 2 Solid solution active materials. Furthermore, as shown by the cyclic test data in Table 1, due to the in-situ coated inert Li on the material surface in examples 1-7 3 PO 4 Side reactions between the internal active material and the electrolyte are suppressed, and thus the cycle performance is also greatly improved.
To examine the stability in air of the materials prepared in examples 1-2 and comparative example 1, each freshly prepared material was further left in air for 12 hours, followed by formation of a button cell as described above, and constant current charge and discharge test was performed. The test results are shown in Table 2, and the positive electrode lithium supplementing material Li in comparative example 1 2 NiO 2 Due to H in the air 2 O and CO 2 Serious side reactions occur, so that the initial capacity of the material and the capacity retention rate after recycling are greatly reduced. However, for the materials in examples 1-2, inert Li was uniformly surface 3 PO 4 The in-situ coating layer is present to obviously inhibit the side reaction, so that the initial capacity and the cycle stability of the positive electrode lithium-supplementing material coated on the surface in-situ are obviously reduced after being placed in the air for a long time. Due to influence on the lithium supplementing material Li of the positive electrode 2 NiO 2 One of the main problems of popularization and application is that the poor air stability greatly increases the difficulty of material storage and use, and the surface in-situ coating preparation strategy adopted by the invention can obviously improve the short plate, which is helpful for the practical application of the positive electrode lithium supplementing material.
TABLE 2
The test data show that the inert Li3PO4 coated on the surface in situ is beneficial to improving the purity of the internal active positive electrode lithium supplementing material, and can obviously inhibit side reactions of the lithium supplementing material in the storage and use processes, and the enrichment of divalent metal ions on the surface layer of the active material can further improve the irreversible capacity of the lithium supplementing material, so that the surface in situ coated positive electrode lithium supplementing material shown in the figure 1 prepared by the invention has excellent initial electrochemical performance and extremely high air stability, and the simple one-step sintering preparation process is suitable for large-scale production and application.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
1. The preparation method of the surface in-situ coated positive electrode lithium supplementing material is characterized by comprising the following steps of:
1) Coating a compound comprising phosphate on the surface of a precursor compound of Ni, and preparing powder A; the phosphate is ammonium phosphate;
2) Uniformly mixing the powder A and the precursor compound of Li by a solid phase method to obtain powder B;
3) Calcining the powder B in inert atmosphere to obtain the surface in-situ coated positive electrode lithium supplementing material;
in the step 1), a phosphate containing a divalent metal M, a mixture of the phosphate and the salt of the divalent metal M, or a mixture of the phosphate and the oxide of the divalent metal M is coated on the surface of a precursor compound of Ni;
the xLi is prepared in the step 3) 2 Ni 1-z M z O 2 @yLi 3 PO 4 The method comprises the steps of carrying out a first treatment on the surface of the x+y=1, y is 0.01 to 0.1, and z is 0.01 to 0.99;
the ratio of the amounts of Li in the Li precursor compound, ni in the Ni precursor compound, and phosphorus in the phosphate is 1:0.4 to 0.5: 0.005-0.05; or, the ratio of the amounts of Li in the precursor compound of Li, ni in the precursor compound of Ni, the divalent metal M and the phosphorus in the phosphate is 1: 0.004-0.495: 0.004-0.495: 0.005-0.05.
2. The method according to claim 1, wherein the phosphate is (NH 4 ) 3 PO 4 ，(NH 4 ) 2 HPO 4 ，NH 4 H 2 PO 4 One or more of them.
3. The method according to claim 1, wherein the divalent metal M is Zn 2+ 、Ba 2+ 、Mg 2+ 、Ca 2+ 、Cu 2+ 、Mn 2+ Or Fe (Fe) 2+ ；
And/or the salt of the divalent metal M is one or more of sulfate, chloride or nitrate of the divalent metal M,
and/or the phosphate is ammonium phosphate or sodium phosphate.
4. A production method according to any one of claims 1 to 3, wherein the compound including a phosphate is coated on the surface of the precursor compound of Ni by a vapor-phase method or a solid-phase method in step 1).
5. The method according to claim 4, wherein the steaming method comprises: dissolving phosphate, phosphate of divalent metal M or mixture of phosphate and salt of divalent metal M and precursor compound of Ni in water to obtain water solution, and evaporating the solution;
the solid phase method is to coat the phosphate on the surface of the precursor compound of Ni by ball milling of ammonium phosphate solid and the precursor compound of the oxide corresponding to divalent metal M and Ni through a ball mill, full mixing of a high-speed mixer or mixing of a mechanical fusion machine.
6. A method according to any one of claims 1 to 3, wherein the solid phase method in step 2) comprises: fully mixing by a ball mill and a high-speed mixer or mixing in a mechanical fusion machine;
and/or the calcining temperature in the step 3) is 450-700 ℃ and the calcining time is 5-25 h.
7. The surface in-situ coated positive electrode lithium supplementing material prepared by the method of any one of claims 1-6.
8. A positive electrode of a lithium ion battery, comprising the surface in-situ coated positive electrode lithium supplementing material of claim 7.
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