CN114551839A - Pre-lithiation of single crystal type cobalt-free high-nickel positive electrode material and preparation method thereof - Google Patents
Pre-lithiation of single crystal type cobalt-free high-nickel positive electrode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 40
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 36
- 239000013078 crystal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006138 lithiation reaction Methods 0.000 title claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910013713 LiNixMnyO2 Inorganic materials 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010699 Li5FeO4 Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000000975 co-precipitation Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000010406 cathode material Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 13
- 239000012716 precipitator Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 229910001868 water Inorganic materials 0.000 description 15
- 229910013716 LiNi Inorganic materials 0.000 description 9
- 229910015973 LiNi0.8Mn0.2O2 Inorganic materials 0.000 description 6
- 229910017288 Ni0.8Mn0.2(OH)2 Inorganic materials 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013729 LiNixMyO2 Inorganic materials 0.000 description 1
- 229910003289 NiMn Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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Abstract
A single crystal type cobalt-free high nickel anode material prelithiation and a preparation method thereof. The invention relates to a single crystal type cobalt-free high-nickel binary anode material with a chemical formula of LiNixMnyO2·mLi3BO3·nLi5FeO4Wherein x, y, m and n are mole numbers, x + y is 1, and x is not less than 0.8<1，0≤y<0.2，0<m≤0.05，0<n is less than or equal to 0.05. The preparation and pre-lithiation method comprises the following steps: firstly, a coprecipitation method is adopted to synthesize Ni with smaller particles, loose appearance and larger specific surface areaxMny(OH)2Precursor body(ii) a Then it is reacted with Li (OH)2·H2O is evenly mixed and then is subjected to high-temperature heat treatment and crushing to obtain the single crystal LiNixMnyO2A cobalt-free binary positive electrode material; finally with Li3BO3And Li5FeO4After being mixed evenly, the mixture is sintered for the second time in the nitrogen atmosphere, and the final product is obtained. The product prepared by the invention has the characteristics of low cost, suitability for the existing production and manufacturing equipment, environmental friendliness, no pollution and the like, and meanwhile, the prelithiation material can participate in offsetting the irreversible capacity loss caused by the SEI film formed by the first charge and discharge of the lithium ion battery, so that the first coulombic efficiency and the charge and discharge cycle performance of the lithium ion battery are greatly improved.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery anode materials, in particular to a single-crystal cobalt-free high-nickel anode material prelithiation and a preparation method thereof.
Background
Under the background of deepening the current energy crisis, electric vehicles and energy storage equipment which adopt storage batteries such as lithium ion batteries and the like as power are rapidly developed. The electric automobile and the clean energy are vigorously developed, the fuel oil substitution process can be accelerated, the exhaust emission is reduced, and the method has important significance for guaranteeing the energy safety, promoting energy conservation and emission reduction, and preventing and treating atmospheric pollution. The positive electrode material is used as a key part influencing the performance of the lithium ion battery, and is the key point of the prior art. And a high nickel layered positive electrode material (LiNi) with high energy density advantage0.8Co0.1Mn0.1O2And LiNi0.8Co0.15Al0.05O2Etc.) have become the mainstream choice for automotive lithium ion power batteries. However, cobalt is distributed unevenly, geopolitically and in small reserves, so that the cobalt price is greatly increased, even exceeding 90000 us dollars per ton. Metallic cobalt has become a key factor that restricts the lithium battery industry. The development of high-performance cobalt-free high-nickel materials is imminent.
The layered cobalt-free positive electrode material generally comprises LiNiO2And doped LiNixMyO2(x + y is 1, M is one or more of Mn, Al, Mg or Ti) and the like, has the characteristics of high reversible specific capacity, low cost and the like, and is considered to be a positive electrode material with great development potential. However, it also has significant disadvantages. Firstly, the layered cobalt-free anode material is usually in a polycrystalline structure, i.e. secondary particles are formed by stacking primary particles, and the content of nickel is too high, so that under a high lithium removal state, the generation of cracks among the primary particles is aggravated by anisotropic shrinkage expansion in the material, and even the primary particles are separated from each other; secondly, in the circulation process, the material has serious phase change and high desorptionThe surface of the material in a lithium state is easy to react with electrolyte violently to generate NiO rock salt phase substances without electrochemical activity, and the cycle performance is seriously influenced. At the same time, like all layered positive electrode materials, Li is deintercalated from the positive electrode during the first charge+An SEI film is easily formed on a negative electrode, so that irreversible capacity is brought, and the problem of low coulombic efficiency for the first time is caused.
Therefore, aiming at the defects of the prior art, the layered cobalt-free cathode material which is high in coulombic efficiency, good in cycle performance and low in cost for the first time is of great significance.
Disclosure of Invention
The invention aims to provide a single-crystal cobalt-free high-nickel cathode material. The material cost is reduced, and meanwhile, the integrity of material particles in the circulation process is effectively improved in a single crystallization mode of the material, so that the circulation performance of the material is improved.
The invention further aims to solve the technical problem of overcoming the common problem of low first coulombic efficiency in the existing layered positive electrode material, and provides a prelithiation method, wherein the first coulombic efficiency of the positive electrode material is improved, and meanwhile, a fast ion conductor coating layer beneficial to lithium ion deintercalation is formed on the surface of the positive electrode material, so that the side reaction at an electrode/electrolyte interface can be further inhibited, and the cycle performance of the material is improved. The preparation method is simple and reasonable, and the cost is low.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a single crystal type cobalt-free high nickel anode material prelithiation and a preparation method thereof. The chemical formula of the cathode material is LiNixMnyO2·mLi3BO3·nLi5FeO4Wherein x, y, m and n are mole numbers, x + y is 1, and x is not less than 0.8<1，0≤y<0.2， 0<m≤0.05，0<n is less than or equal to 0.05. The particle size of the material is about 2-7 μm, and the surface layer has uniform Li3BO3And Li5FeO4A coating layer with a thickness of 3-20 nm.
The technical scheme adopted for further solving the technical problems is as follows:
a single crystal type cobalt-free high nickel anode material prelithiation and a preparation method thereof are prepared by the following steps:
(1) firstly, mixing soluble nickel salt and manganese salt according to a certain stoichiometric ratio, adding the mixture into deionized water to prepare a mixed metal salt solution, adding a precipitator into the deionized water to dissolve the precipitator into a precipitator solution, and diluting a complexing agent to a certain concentration to prepare a complexing agent solution;
(2) then respectively heating the three solutions, injecting the three solutions into a reaction kettle, introducing protective gas, then preserving heat, stirring the three solutions to perform coprecipitation reaction, filtering the hot solution, and finally washing the filtered precipitate by deionized water and performing vacuum drying treatment to obtain the NixMny(OH)2A precursor;
(3) based on mol, mixing a certain proportion of Ni prepared in the step (2)xMny(OH)2Uniformly mixing the precursor with a lithium source, roasting in an oxygen atmosphere, cooling to room temperature, crushing and sieving to obtain LiNixMnyO2A positive electrode material;
(4) reacting LiNixMnyO2Cathode material and Li3BO3And Li5FeO4The materials are mixed evenly, placed in a nitrogen atmosphere for secondary roasting, cooled to room temperature and sieved to prepare the pre-lithiated LiNixMnyO2·mLi3BO3·nLi5FeO4And (3) a positive electrode material.
Further, in the step (1), the nickel salt is one or more of nickel sulfate, nickel nitrate and nickel chloride, and the manganese salt is one or more of manganese sulfate, manganese nitrate and manganese chloride;
further, in the step (1), the precipitator is one or more of sodium hydroxide and potassium hydroxide, and the complexing agent is one or more of ammonia water and oxalic acid;
further, in the metal salt solution in the step (1), the total concentration of metal cations is 3-10moL/L, and a precipitator solution OH-The concentration is 5-7mol/L, and the concentration of the complexing agent solution is 1.5-2 mol/L.
Further, the heating temperature in the step (2)The temperature is 40-80 ℃, and the protective gas is N2And one or more of Ar, the stirring speed is controlled to be 200-500rpm, the pH value is controlled to be 10.5-11.0, and the vacuum drying temperature is 120-180 ℃.
Further, the precursor produced in the step (2) is small particles with loose appearance, large specific surface area and 2-5 mu m particle size.
Further, in the step (3), the lithium source is one or more of lithium hydroxide monohydrate, lithium carbonate and lithium nitrate.
Further, the material mixing conditions in the step (3) are that Li: m is 1-1.2, wherein Li and M are the molar weight of lithium element in the lithium source and the molar weight of metal element in the precursor respectively, the used equipment is a high-speed mixer, the rotating speed is controlled at 200-500Hz, and the mixing time is controlled at 10-60 min.
Further, the sintering condition in the step (3) is that the oxygen concentration is more than or equal to 80 percent; the sintering temperature is 750-850 ℃; the sintering time is 10-16 h.
Further, the crushing condition in the step (3) is that the air pressure of the jet mill is more than or equal to 2 Mpa.
Further, the particle size of the cathode material produced in the step (3) is about 2-7 μm.
Further, the pre-lithiated cladding layer mLi in the step (4)3BO3And nLi5FeO4Are nanoparticles.
Further, the pre-lithiated cladding layer mLi in the step (4)3BO3And nLi5FeO4And positive electrode material LiNixMnyO2In the range of 0 to 0.05.
Further, the atmosphere in the step (4) is one or two of nitrogen and argon.
Further, the secondary sintering temperature in the step (4) is 150-.
Further, the total thickness of the prelithiation coating layer in the step (4) is 3-20 nm.
The invention has the beneficial effects that:
(1) compared with polycrystalline materials, the special structure can effectively inhibit the structural collapse problem caused by huge volume change of particles in the charging and discharging processes, and simultaneously can effectively reduce the contact area of the materials and electrolyte and reduce the occurrence of surface side reactions. Therefore, the nickel-manganese binary material prepared by the method can show better cycle stability.
(2) The invention coats Li on the surface at the same time3BO3And Li5FeO4The aim of pre-lithiation is achieved. The layered positive electrode material generally has the defect of low coulombic efficiency for the first time, and can play a great role in developing a great potential by forming the lithium-conducting coating layer, thereby effectively improving the electrochemical performance of the high-nickel layered oxide. In addition, the double-fast ion conductor coating layer formed on the surface of the anode can effectively promote the diffusion transmission of lithium ions while effectively resisting HF corrosion, so that the transmission rate and the cycle performance of the lithium ions on the surface of the material are obviously improved. In addition, the preparation method has simple flow and low cost, and is suitable for industrial production.
Drawings
FIG. 1 is an SEM image of a single-crystal cobalt-free high-nickel precursor obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a single-crystal cobalt-free high-nickel cathode material obtained in example 1 of the present invention;
fig. 3 is a first charge-discharge curve diagram of the single-crystal cobalt-free high-nickel cathode material obtained in example 1 of the present invention at a voltage of 2.95-4.6V and a magnification of 0.2C.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The invention is described by combining with specific examples, a single crystal type cobalt-free high nickel positive electrode material prelithiation and a preparation method thereof, and the single crystal type cobalt-free high nickel positive electrode material prelithiation and the preparation method thereof are specifically prepared by the following steps:
(1) in terms of molar ratio, 3moL/L of 8moL of NiSO4·6H2O, 2moL MnSO4·H2O (NiMn 8:2) solution was mixed uniformly while adding NaOH solution (4mol/L) and NH as a complexing agent3·H2O solution (2mol/L) is added into the reaction tanks respectively. Adjusting the pH value to 10.5, carrying out coprecipitation reaction, and finally washing and drying by pure water to obtain a precursor Ni0.8Mn0.2(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.06mol of lithium nitrate according to the proportion of (Ni + Mn) ═ 1.06:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.8Mn0.2(OH)2Mixing with lithium nitrate, heating at 2 deg.C/min, burning at 850 deg.C for 14 hr, regulating pressure of jet mill to 4MPa, and crushing to obtain positive electrode material LiNi with particle size of 2-7 μm0.8Mn0.2O2。
(3) 1mol of LiNi is added0.8Mn0.2O2Cathode material and 0.01mol of Li3BO3And 0.01mol of Li5FeO4Uniformly mixing the materials, placing the mixture in a nitrogen atmosphere for secondary roasting at the secondary sintering temperature of 280 ℃ for 12 hours, then cooling the mixture to room temperature and sieving the mixture to obtain the pre-lithiated LiNi0.8Mn0.2O2·0.01Li3BO3·0.01Li5FeO4And (3) a positive electrode material.
The cobalt-free high-nickel precursor and the cobalt-free high-nickel cathode material obtained in the embodiment were characterized and detected, and the composition thereof was LiNi0.8Mn0.2O2·0.01Li3BO3·0.01Li5FeO4The SEM image of the cobalt-free high-nickel precursor is shown in figure 1, the scanning image of the high-nickel cathode material is shown in figure 2, the particle size of the high-nickel cathode material is 2-7 mu m, and a coating layer with uniform thickness is arranged on the surface of the high-nickel cathode material.
The single crystal type cobalt-free high nickel anode material obtained in the embodiment is adopted to assemble the CR2025 button cell. The first discharge gram capacity of the battery reaches 195.1mAh/g, the first coulombic efficiency reaches 89.6 percent (shown in figure 3) within the voltage range of 2.95-4.6V and under the multiplying power of 0.2C, the capacity retention rate reaches 80 percent after the battery is circulated for 50 circles under the multiplying power of 1C.
Example 2
The invention is described by combining with specific examples, a single crystal type cobalt-free high nickel positive electrode material prelithiation and a preparation method thereof, and the single crystal type cobalt-free high nickel positive electrode material prelithiation and the preparation method thereof are specifically prepared by the following steps:
(1) firstly, 3mol/L of 8mol of NiSO4·6H2O, 2mol of MnSO4·H2O (Ni: Mn: 8:2) solution was mixed uniformly, and at the same time, NaOH solution (4mol/L) and NH as a complexing agent were added3·H2O solution (2mol/L) was also added to the reaction tank separately. Adjusting the pH value to 10.5, carrying out coprecipitation reaction, and finally washing and drying by pure water to obtain a precursor Ni0.8Mn0.2(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.06mol of lithium nitrate according to the proportion of (Ni + Mn) ═ 1.06:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.8Mn0.2(OH)2Mixing with lithium nitrate, heating at 2 deg.C/min, calcining at 850 deg.C for 14 hr, regulating pressure of jet mill to 4MPa, and crushing to obtain positive electrode material LiNi with particle size of 2-7 μm0.8Mn0.2O2。
(3) 1mol of LiNi is added0.8Mn0.2O2Cathode material and 0.01mol of Li3BO3And 0.02mol of Li5FeO4Uniformly mixing, placing the mixture in a nitrogen atmosphere for secondary roasting at the temperature of 280 ℃ for 12 hours, cooling to room temperature, and sieving to obtain the pre-lithiated LiNi0.8Mn0.2O2·0.01Li3BO3·0.02Li5FeO4And (3) a positive electrode material.
The single crystal type cobalt-free high nickel anode material obtained in the embodiment is adopted to assemble the CR2025 button cell. The first discharge gram capacity of the battery reaches 194.8mAh/g within the voltage range of 2.95-4.6V and under the multiplying power of 0.2C, the first coulombic efficiency reaches 88.6%, the capacity retention rate reaches 82% after 50 cycles under the multiplying power of 1C.
Example 3
The invention is described by combining with specific examples, a single crystal type cobalt-free high nickel positive electrode material prelithiation and a preparation method thereof, and the single crystal type cobalt-free high nickel positive electrode material prelithiation and the preparation method thereof are specifically prepared by the following steps:
(1) in terms of molar ratio, 3moL/L of 8moL of NiSO4·6H2O, 2moL MnSO4·H2O (Ni: Mn ═ 8:2) solution was uniformly mixed, and at the same time, NaOH solution (4mol/L) and NH as a complexing agent were added3·H2O solution (2mol/L) was also added to the reaction tank separately. Adjusting the pH value to 10.5, carrying out coprecipitation reaction, and finally washing and drying by pure water to obtain a precursor Ni0.8Mn0.2(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.06mol of lithium nitrate according to the proportion of (Ni + Mn) ═ 1.06:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.8Mn0.2(OH)2Mixing with lithium nitrate, heating at 2 deg.C/min, calcining at 850 deg.C for 14 hr, regulating pressure of jet mill to 4MPa, and crushing to obtain positive electrode material LiNi with particle size of 2-7 μm0.8Mn0.2O2。
(3) 1mol of LiNi is added0.8Mn0.2O2Cathode material and 0.02mol of Li3BO3And 0.01mol of Li5FeO4Uniformly mixing the materials, placing the mixture in a nitrogen atmosphere for secondary roasting at the secondary roasting temperature of 280 ℃ for 12 hours, cooling the mixture to room temperature, and sieving the cooled mixture to obtain the pre-lithiated LiNi0.8Mn0.2O2·0.02Li3BO3·0.01Li5FeO4And (3) a positive electrode material.
The single crystal type cobalt-free high nickel anode material obtained in the embodiment is adopted to assemble the CR2025 button cell. The first discharge gram capacity of the battery reaches 193.7mAh/g within the voltage range of 2.95-4.6V and under the multiplying power of 0.2C, and the first coulombic efficiency reaches 89.7%; the capacity retention rate reaches 83 percent after 50 cycles under the multiplying power of 1C.
Example 4
The invention is described by combining with specific examples, a single crystal type cobalt-free high nickel positive electrode material prelithiation and a preparation method thereof, and the single crystal type cobalt-free high nickel positive electrode material prelithiation and the preparation method thereof are specifically prepared by the following steps:
(1) in terms of molar ratio, 3moL/L of 8moL of NiSO4·6H2O, 2moL MnSO4·H2O (Mn ═ 8:2) was uniformly mixed, and at the same time, a NaOH solution (4mol/L) and NH as a complexing agent were added3·H2O solution (2mol/L) was also added to the reaction tank separately. Adjusting the pH value to 10.5, carrying out coprecipitation reaction, and finally washing and drying by pure water to obtain a precursor Ni0.8Mn0.2(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.06mol of lithium nitrate according to the proportion of (Ni + Mn) ═ 1.06:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.8Mn0.2(OH)2Mixing with lithium nitrate, heating at 2 deg.C/min, calcining at 850 deg.C for 14 hr, regulating pressure of jet mill to 4MPa, and crushing to obtain positive electrode material LiNi with particle size of 2-7 μm0.8Mn0.2O2。
(3) 1mol of LiNi is added0.8Mn0.2O2Cathode material and 0.02mol of Li3BO3And 0.02mol of Li5FeO4Uniformly mixing the materials, placing the mixture in a nitrogen atmosphere for secondary roasting at the secondary roasting temperature of 280 ℃ for 12 hours, cooling the mixture to room temperature, and sieving the cooled mixture to obtain the pre-lithiated LiNi0.8Mn0.2O2·0.02Li3BO3·0.02Li5FeO4And (3) a positive electrode material.
The single crystal type cobalt-free high nickel anode material obtained in the embodiment is adopted to assemble the CR2025 button cell. The first discharge gram capacity of the battery reaches 191.7mAh/g within the voltage range of 2.95-4.6V and under the multiplying power of 0.2C, and the first coulombic efficiency reaches 90.7%; the capacity retention rate reaches 77 percent after 50 cycles under the multiplying power of 1C.
Comparative example 1
The preparation method specifically comprises the following steps:
(1) in terms of molar ratio, 3moL/L of 8moL of NiSO4·6H2O, 2moL MnSO4·H2O (Ni: Mn ═ 8:2) was uniformly mixed, and at the same time, a NaOH solution (4mol/L) and NH as a complexing agent were added3·H2O solution (2mol/L) was also added to the reaction tank separately. Adjusting the pH value to 10.5, carrying out coprecipitation reaction, and finally washing and drying by pure water to obtain a precursor Ni0.8Mn0.2(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.06mol of lithium nitrate according to the proportion of (Ni + Mn) ═ 1.06:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.8Mn0.2(OH)2Mixing with lithium nitrate, heating at 2 deg.C/min, calcining at 800 deg.C for 14 hr, regulating pressure of jet mill to 2MPa, and crushing to obtain positive electrode material LiNi0.8Mn0.2O2。
The single crystal type cobalt-free high nickel anode material obtained in the embodiment is adopted to assemble the CR2025 button cell. The first discharge gram capacity of the battery reaches 194.2mAh/g and the first coulombic efficiency is 78.2% within the voltage range of 2.95-4.6V and under the multiplying power of 0.2C; the capacity retention rate is 73 percent after 50 cycles under the multiplying power of 1C.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (7)
1. A single crystal type cobalt-free high nickel anode material is characterized in that: the chemical formula of the anode material is LiNixMnyO2·mLi3BO3·nLi5FeO4The chemical formula of the precursor is NixMny(OH)2Wherein x, y, m and n are mole numbers, x + y is 1, and x is not less than 0.8<1，0≤y<0.2，0<m≤0.05，0<n≤0.05。
2. The method as claimed in claim 1, wherein the positive electrode material is single crystal particles with a particle size of 2-7 μm, the precursor is small particles with a loose morphology, a large specific surface area and a particle size of 2-5 μm, and the prelithiation coating Li is formed by pre-lithiation3BO3And Li5FeO4Is nano-scale particle.
3. A preparation method of a single-crystal cobalt-free high-nickel anode material is characterized by comprising the following steps:
(1) firstly, mixing soluble nickel salt and manganese salt according to a certain stoichiometric ratio, adding the mixture into deionized water, uniformly stirring to obtain a mixed metal salt solution, adding a precipitator into the deionized water to dissolve the precipitator into a precipitator solution, and diluting a complexing agent to a certain concentration to prepare a complexing agent solution;
(2) then respectively heating the three solutions, injecting the three solutions into a reaction kettle, introducing protective gas, then preserving heat, stirring for coprecipitation reaction, filtering while hot, and finally washing the filtered precipitate with deionized water and drying in vacuum to obtain NixMny(OH)2A precursor;
(3) based on mol, a certain proportion of Ni prepared in the step (2)xMny(OH)2Uniformly mixing the precursor with a lithium source, roasting in an oxygen atmosphere, cooling to room temperature, crushing and sieving to obtain LiNixMnyO2A positive electrode material;
(4) reacting LiNixMnyO2Cathode material and Li3BO3And Li5FeO4Uniformly mixing, placing the mixture in a nitrogen atmosphere for secondary roasting, then cooling the mixture to room temperature and sieving the cooled mixture to obtain the pre-lithiated LiNixMnyO2·mLi3BO3·nLi5FeO4And (3) a positive electrode material.
4. The method for preparing the single-crystal cobalt-free high-nickel cathode material according to the specification 3, is characterized in that: in the step (1), the nickel salt is one or more of nickel sulfate, nickel nitrate and nickel chloride, the manganese salt is one or more of manganese sulfate, manganese nitrate and manganese chloride, the precipitator is one or more of sodium hydroxide and potassium hydroxide, the complexing agent is one or more of ammonia water and oxalic acid, the total concentration of metal cations in the metal salt solution is 3-10moL/L, and OH in the precipitator solution-The concentration is 5-7mol/L, and the concentration of the complexing agent solution is 1.5-2 mol/L.
5. The single crystal form of claim 3The preparation method of the cobalt high-nickel cathode material is characterized by comprising the following steps of: the heating temperature in the step (2) is 40-80 ℃, and the protective gas is N2And one or more of Ar, the stirring speed is controlled at 200-500rpm, the pH value is controlled at 10.5-11.0, and the vacuum drying temperature is 120-180 ℃.
6. The method for preparing the single-crystal cobalt-free high-nickel cathode material according to claim 3, wherein the method comprises the following steps: in the step (3), the lithium source is one or more of lithium hydroxide monohydrate, lithium carbonate and lithium nitrate; li: m is 1 (1-1.2), wherein Li and M are the molar weight of lithium element in the lithium source and the molar weight of metal element in the precursor respectively; the oxygen concentration is more than or equal to 80 percent; the sintering temperature is 750-850 ℃; the sintering time is 10-16 h.
7. The method for preparing the single-crystal cobalt-free high-nickel cathode material according to claim 3, wherein the method comprises the following steps: the prelithiation of the coating layer mLi in step (4)3BO3And nLi5FeO4And positive electrode material LiNixMnyO2The molar ratio m and n ranges from 0 to 0.05, the secondary sintering temperature is 150 ℃ and 450 ℃, and the secondary sintering time is 10 to 16 hours.
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