CN113889615A - Cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and preparation method thereof - Google Patents
Cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN113889615A CN113889615A CN202111000234.2A CN202111000234A CN113889615A CN 113889615 A CN113889615 A CN 113889615A CN 202111000234 A CN202111000234 A CN 202111000234A CN 113889615 A CN113889615 A CN 113889615A
- Authority
- CN
- China
- Prior art keywords
- concentration
- reaction
- concentration gradient
- ions
- ternary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000011258 core-shell material Substances 0.000 title claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 25
- 239000010406 cathode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000012266 salt solution Substances 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 40
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 32
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 239000010405 anode material Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 37
- 238000000975 co-precipitation Methods 0.000 claims description 31
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 26
- 229910001437 manganese ion Inorganic materials 0.000 claims description 26
- 229910001453 nickel ion Inorganic materials 0.000 claims description 26
- -1 tungsten ions Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- 239000008139 complexing agent Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910015973 LiNi0.8Mn0.2O2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/11—Powder tap density
-
- 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
- C01P2006/12—Surface area
-
- 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
-
- 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
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery anode material and a preparation method thereof. The chemical formula of the anode material is Li [ Ni ]xMn1‑x‑yWy]O2Wherein x and y are mole numbers, x is more than or equal to 0.8 and less than 1, and y is more than 0 and less than or equal to 0.1. The preparation method comprises the following steps: adding a first salt solution containing nickel, manganese and tungsten, a sodium hydroxide solution and an ammonia water solution into a reaction kettle for reaction to form a precursor core, adding second salt solutions containing nickel, manganese and tungsten in different proportions into the reaction kettle, performing full reaction, performing centrifugal washing, drying, screening for deironing, mixing with lithium hydroxide, and roasting to obtain a ternary concentration gradient core-shell structureA lithium ion battery anode material. The concentration gradient cathode material has a better crystal structure and higher tap density, and a battery prepared by taking the concentration gradient cathode material as the cathode material has excellent electrochemical performance; the preparation method is simple and controllable, has low cost and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery anode material and a preparation method thereof.
Background
The NCM ternary cathode material has the advantages of high capacity, long service life, low cost, rich raw material sources and the like, is widely applied to the field of small lithium ion batteries and power batteries, and is a lithium ion battery cathode material with application prospect. The cobalt element in the ternary cathode material mainly has the functions of improving the crystal conductivity and stabilizing the layered structure of the material so as to improve the cycle and rate performance of the material, so that the cobalt element has an important function in the high-nickel cathode material. However, the shortage of cobalt ore resources in the global resource range at present, the storage capacity is only 687.5 ten thousand tons, and the higher price of raw material cost is one of the main reasons for hindering the wide application of the high nickel anode material. Therefore, the search for a transition metal element which has high resource storage capacity and low price and does not influence the electrochemical performance of the high-nickel cathode material to replace cobalt is a hot point problem which is commonly concerned by the commercial industry and the academic industry at present.
Therefore, the invention develops a novel positive electrode material Li [ Ni ] with high cycle stability by using W to replace CoxMn1-x-yWy]O2. The preparation method is convenient to operate, simple in process and suitable for industrial production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and a preparation method thereof. The battery assembled by the positive electrode material has excellent cycle stability and good high-pressure resistance; the preparation method is simple and reasonable, and the cost is low.
The invention adopts the following technical scheme:
the cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery anode material is characterized in that the chemical formula of the anode material is Li [ Ni ]xMn1-x-yWy]O2X and y are mole numbers, wherein，0.8≤x＜1，0＜y≤1。
The preparation method of the ternary concentration gradient core-shell lithium ion battery cathode material is characterized by comprising the following steps of:
(1) preparing a first salt solution containing nickel, manganese and tungsten, wherein the molar ratio of nickel ions to manganese ions to tungsten ions is (90-100): (10-20): (0-10), wherein the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the first salt solution is 2.00-4.00 mol/L; preparing a second salt solution containing nickel, manganese and tungsten, wherein the molar ratio of nickel ions to manganese ions to tungsten ions is (60-70): (30-40): (0-10), wherein the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the second salt solution is 2.00-4.00 mol/L;
(2) adding the first salt solution into a reaction kettle in a nitrogen atmosphere at the speed of 2.5L/h-5L/h, simultaneously adding a sodium hydroxide solution serving as a precipitator and an ammonia water solution serving as a complexing agent into the reaction kettle, and carrying out a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is [ Ni ]mMn1-m-nWn](OH)2Wherein m is more than or equal to 0.9 and less than 1, and n is more than 0 and less than or equal to 0.1; the concentration of the sodium hydroxide solution is 2-4 mol/L, and the concentration of the ammonia water solution is 1-4 mol/L; the technological conditions of the first coprecipitation reaction are as follows: the ammonia concentration in the reaction kettle is kept between 4g/L and 12g/L, the reaction PH is between 10 and 12, the reaction time is between 20 and 50 hours, and the rotating speed is between 300 and 450 rpm;
(3) when the reaction time of the first coprecipitation reaction is reached, immediately pumping the second salt solution into the reaction kettle at the speed of 9L/h-12L/h, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5g/L and 15g/L, the pH value of the reaction is between 10 and 12, the reaction time is between 50 and 60 hours, and the rotating speed of the reaction is between 300 and 450 rpm;
(4) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a ternary concentration gradient precursor with a chemical formula of [ Ni ]xMn1-x-yWy](OH)2Wherein x is more than 0.8 and less than or equal to 1, and y is more than 0 and less than or equal to 0.1; the baking is carried outThe drying temperature is 100-150 ℃, and the drying time is 8-10 h;
(5) uniformly mixing the ternary concentration gradient precursor with lithium hydroxide according to the molar ratio of 1: 1.05-1.2, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the ternary concentration gradient core-shell structure lithium ion battery anode material.
The preparation method of the ternary concentration gradient core-shell structure lithium ion battery anode material is characterized in that the first salt solution is one of sulfate solution, nitrate solution and chloride solution; the second saline solution is one of a sulfate solution, a nitrate solution and a chloride solution.
The preparation method of the ternary concentration gradient core-shell structure lithium ion battery anode material is characterized in that in the step (5), the roasting process keeps an oxygen atmosphere, the roasting process comprises a first-stage roasting process and a second-stage roasting process which are sequentially carried out, and the process conditions of the first-stage roasting process are as follows: heat treatment is carried out for 1h-5h at the temperature of 250 ℃ to 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 5h to 12h at the temperature of 500 ℃ to 900 ℃.
The invention has the beneficial effects that:
(1) in order to solve the problem that the material cost is higher due to high cobalt price in the traditional ternary cathode material, the invention provides a cobalt-free concentration gradient core-shell structure lithium ion battery cathode material which is synthesized by replacing cobalt with tungsten elements with rich reserves and low cost and adopting a composition gradual change method. The particle core is enriched with nickel element, while the nickel content of the gradient layer is gradually reduced, and the manganese content is increased. Through the design of the gradual concentration gradient material, the capacity advantage of a high-nickel core can be exerted, and the internal stress can be remarkably relieved, so that the mechanical stability of the fine particles after repeated circulation is effectively improved; meanwhile, the Ni generated by the high-nickel material in the lithium-deficient state is increased due to the increase of the manganese content in the outer layer concentration gradient material4+The material is not easy to contact with electrolyte to react to release a large amount of gas, and the circulation stability of the material is improved. In addition, the preparation method is simple to operate, low in cost and suitable for industrial production.
(2) The cobalt-free high-nickel cathode material is of a single crystal structure, the particle diameter is 2-6 mu m, and the cobalt-free high-nickel cathode material has excellent cycle stability and good high-pressure resistance.
Drawings
FIG. 1 shows a concentration gradient ternary material Li [ Ni ] prepared in example 1 of the present invention0.8Mn0.195W0.005]O2SEM picture of (1);
FIG. 2 shows a concentration gradient ternary material Li [ Ni ] prepared in example 1 of the present invention0.8Mn0.195W0.005]O2XRD pattern of (a);
FIG. 3 shows a concentration gradient ternary material Li [ Ni ] prepared in example 1 of the present invention0.8Mn0.195W0.005]O2The prepared battery has a cycle performance diagram of 50 charge-discharge cycles within a voltage range of 2.7-4.6V and under a multiplying power of 1C;
FIG. 4 shows LiNi, a cobalt-free high-nickel binary material prepared in comparative example 1 of the present invention0.8Mn0.2O2SEM picture of (1);
FIG. 5 shows LiNi, a cobalt-free high-nickel binary material prepared in comparative example 1 of the present invention0.8Mn0.2O2The prepared battery has a cycle performance diagram of 50 charge-discharge cycles within a voltage range of 2.7-4.6V and under a multiplying power of 1C.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, manganese sulfate and tungsten chloride, wherein the molar ratio of nickel ions to manganese ions to tungsten ions in the first salt solution is 95: 4.5: 0.5, and the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the first salt solution is 2.00 mol/L. The molar ratio of nickel ions, manganese ions and tungsten ions in the second salt solution is 65: 34.5: 0.5, and the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the second salt solution is 2.00 mol/L.
(2) 150L of the first salt solution was added to a reaction vessel under a nitrogen atmosphere at a rate of 5L/h, and simultaneously added to the reaction vesselAdding sodium hydroxide solution and ammonia water solution to perform a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is [ Ni ]0.95Mn0.045W0.005](OH)2(ii) a The concentration of the sodium hydroxide solution is 4mol/L, the concentration of the ammonia water solution is 4mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7 and 8g/L, the pH value of the reaction is between 11.2 and 12, the reaction time is 30 hours, and the rotating speed of the reaction is 400 rpm.
(3) When the coprecipitation reaction is carried out for 30 hours, immediately pumping 150L of second salt solution into the reaction kettle at the rate of 3L/h, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7.5g/L and 8.5g/L, the pH value of the reaction is 11 to 11.8, the reaction time is 50h, and the rotating speed of the reaction is 380 rpm.
(4) Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a ternary concentration gradient precursor with a chemical formula of [ Ni ]0.8Mn0.195W0.005](OH)2(ii) a The drying temperature is 140 ℃ and the drying time is 8 h.
(5) Uniformly mixing the ternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.18, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain Li [ Ni ] with a chemical formula0.8Mn0.195W0.005]O2The ternary concentration gradient core-shell lithium ion battery anode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 2h at 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 12h at 800 ℃.
(6) And testing the pH, the specific surface area, the moisture, the tap density, the discharge specific capacity, the capacity retention rate after circulation and the like of the ternary concentration gradient core-shell lithium ion battery anode material.
Example 2
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, manganese sulfate and tungsten chloride, wherein the molar ratio of nickel ions to manganese ions to tungsten ions in the first salt solution is 95: 4: and 1, the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the first salt solution is 2.00 mol/L. The molar ratio of nickel ions, manganese ions and tungsten ions in the second salt solution is 65: 34: 1, the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the second salt solution is 2.00 mol/L.
(2) Adding 150L of first salt solution into a reaction kettle in nitrogen atmosphere at the speed of 5L/h, and simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle to carry out primary coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is [ Ni ]0.95Co0.04W0.01](OH)2(ii) a The concentration of the sodium hydroxide solution is 4mol/L, the concentration of the ammonia water solution is 4mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7 and 8g/L, the pH value of the reaction is between 11.2 and 12, the reaction time is 30 hours, and the rotating speed of the reaction is 400 rpm.
(3) When the coprecipitation reaction is carried out for 30 hours, immediately pumping 150L of second salt solution into the reaction kettle at the rate of 3L/h, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7.5g/L and 8.5g/L, the pH value of the reaction is 11 to 11.8, the reaction time is 50h, and the rotating speed of the reaction is 380 rpm.
(4) Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a ternary concentration gradient precursor with a chemical formula of [ Ni ]0.8Mn0.19W0.01](OH)2(ii) a The drying temperature is 140 ℃ and the drying time is 8 h.
(5) Uniformly mixing the ternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.18, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain Li [ Ni ] with a chemical formula0.8Mn0.19W0.01]O2The ternary concentration gradient core-shell lithium ion battery anode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 2h at 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 12h at 800 ℃.
(6) And testing the pH, the specific surface area, the moisture, the tap density, the discharge specific capacity, the capacity retention rate after circulation and the like of the ternary concentration gradient core-shell lithium ion battery anode material.
Example 3
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, manganese sulfate and tungsten chloride, wherein the molar ratio of nickel ions to manganese ions to tungsten ions in the first salt solution is 95: 3: and 2, the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the first salt solution is 2.00 mol/L. The molar ratio of nickel ions, manganese ions and tungsten ions in the second salt solution is 65: 33: 2, the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the second salt solution is 2.00 mol/L.
(2) Adding 150L of first salt solution into a reaction kettle in nitrogen atmosphere at the speed of 5L/h, and simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle to carry out primary coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is [ Ni ]0.95Mn0.03W0.02](OH)2(ii) a The concentration of the sodium hydroxide solution is 4mol/L, the concentration of the ammonia water solution is 4mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7 and 8g/L, the pH value of the reaction is between 11.2 and 12, the reaction time is 30 hours, and the rotating speed of the reaction is 400 rpm.
(3) When the coprecipitation reaction is carried out for 30 hours, immediately pumping 150L of second salt solution into the reaction kettle at the rate of 3L/h, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7.5g/L and 8.5g/L, the pH value of the reaction is 11 to 11.8, the reaction time is 50h, and the rotating speed of the reaction is 380 rpm.
(4) Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a ternary concentration gradient precursor with a chemical formula of [ Ni ]0.8Mn0.18W0.02](OH)2(ii) a The drying temperature is 140 ℃ and the drying time is 8 h.
(5) Uniformly mixing the ternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.18, and then adding the mixture into a muffleRoasting in furnace, cooling, crushing and sieving to obtain Li Ni0.8Mn0.18W0.02]O2The ternary concentration gradient core-shell lithium ion battery anode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 2h at 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 12h at 800 ℃.
(6) And testing the pH, the specific surface area, the moisture, the tap density, the discharge specific capacity, the capacity retention rate after circulation and the like of the ternary concentration gradient core-shell lithium ion battery anode material.
Example 4
(1) Preparing a first salt solution and a second salt solution containing nickel sulfate, manganese sulfate and tungsten chloride, wherein the molar ratio of nickel ions to manganese ions to tungsten ions in the first salt solution is 95: 2: and 3, the sum of the concentration of the nickel ions, the concentration of the manganese ions and the concentration of the tungsten ions in the first salt solution is 2.00 mol/L. The molar ratio of nickel ions, manganese ions and tungsten ions in the second salt solution is 65: 32: and 3, the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the second salt solution is 2.00 mol/L.
(2) Adding 150L of first salt solution into a reaction kettle in nitrogen atmosphere at the speed of 5L/h, and simultaneously adding sodium hydroxide solution and ammonia water solution into the reaction kettle to carry out primary coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is [ Ni ]0.95Mn0.02W0.03](OH)2(ii) a The concentration of the sodium hydroxide solution is 4mol/L, the concentration of the ammonia water solution is 4mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7 and 8g/L, the pH value of the reaction is between 11.2 and 12, the reaction time is 30 hours, and the rotating speed of the reaction is 400 rpm.
(3) When the coprecipitation reaction is carried out for 30 hours, immediately pumping 150L of second salt solution into the reaction kettle at the rate of 3L/h, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 7.5g/L and 8.5g/L, the pH value of the reaction is 11 to 11.8, the reaction time is 50h, and the rotating speed of the reaction is 380 rpm.
(4) Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a ternary concentration gradient precursor with a chemical formula of [ Ni ]0.8Mn0.17W0.03](OH)2(ii) a The drying temperature is 140 ℃ and the drying time is 8 h.
(5) Uniformly mixing the ternary concentration gradient precursor and lithium hydroxide according to the molar ratio of 1: 1.18, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain Li [ Ni ] with a chemical formula0.8Mn0.17W0.03]O2The ternary concentration gradient core-shell lithium ion battery anode material; the whole roasting process is kept in an oxygen atmosphere, the roasting comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, and the process conditions of the first-stage roasting are as follows: heat treatment is carried out for 2h at 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 12h at 800 ℃.
(6) And testing the pH, the specific surface area, the moisture, the tap density, the discharge specific capacity, the capacity retention rate after circulation and the like of the ternary concentration gradient core-shell lithium ion battery anode material.
Comparative example 1
(1) Preparing a salt solution containing nickel sulfate and manganese sulfate, wherein the molar ratio of nickel ions to manganese ions in the salt solution is 8: and 2, the sum of the concentration of nickel ions and the concentration of manganese ions in the salt solution is 2 mol/L.
(2) Adding 400L of salt solution into a reaction kettle with nitrogen atmosphere and 350rpm at the speed of 10L/h, adding 4mol/L ammonia water serving as a complexing agent into the reaction kettle, pumping 4mol/L NaOH solution into the reaction kettle, adjusting the flow rate of the alkali solution, keeping the pH value between 10.4 and 11.8, and carrying out coprecipitation reaction for 40h to obtain a precursor.
(3) And centrifugally separating and washing the solid-liquid mixture after reaction to be neutral, and drying for 10-12h at 130 ℃.
(4) Uniformly mixing the reacted precursor with lithium hydroxide according to the molar ratio of 1: 1.1, roasting for 12 hours in a muffle furnace at 800 ℃, crushing and sieving the roasted material to obtain uniform LiNi0.8Mn0.2O2A ternary material.
(5) And testing the pH, the specific surface area, the moisture, the tap density, the discharge specific capacity, the capacity retention rate after circulation and the like of the ternary concentration gradient core-shell lithium ion battery anode material.
The physical properties of the ternary concentration gradient core-shell structure lithium ion battery anode material obtained in the embodiments 1 to 4 are compared with those of the common ternary material obtained in the comparative example 1, and the detection results are as follows:
table 1 physical properties of the positive electrode materials for batteries obtained in examples 1 to 4
| PH | BET(m2/g) | Moisture (ppm) | Tap density (g/cm)3) | |
| Example 1 | 11.5 | 0.45 | 232.5 | 2.18 |
| Example 2 | 11.3 | 0.48 | 220.4 | 2.21 |
| Example 3 | 11.6 | 0.42 | 237.3 | 2.24 |
| Example 4 | 11.5 | 0.46 | 228.5 | 2.14 |
| Comparative example 1 | 10.9 | 0.52 | 248.3 | 1.90 |
From table 1, it can be derived: examples 1-4 had lower moisture relative to the comparative example 1 sample, while examples 1-4 had a higher pH than the comparative example 1 sample; examples 1-4 the tap densities of the samples were all above 2g/cm3The higher tap density compared to the sample of comparative example 1 indicates a higher battery capacity.
The lithium ion battery anode material with ternary concentration gradient core-shell structure obtained in the examples 1-4 and the common ternary material obtained in the comparative example 1 are used as the anode and the metal lithium sheet is used as the cathode, and are respectively assembled into a button cell to carry out charge-discharge comparative test, and the detection results are as follows:
table 2 specific discharge capacity test data of the battery positive electrode materials of examples 1 to 4 and comparative example 1
From table 2, it can be derived: the ternary concentration gradient core-shell lithium ion battery anode material obtained in the embodiments 1 to 4 is used as an anode, a button battery is assembled by using a metal lithium sheet as a cathode, and a charge-discharge comparison test is carried out, so that the first discharge specific capacity can reach 188.6mAh/g to the maximum under the 1C multiplying power, the capacity retention rate after 50 charge-discharge cycles reaches 90.3%, the first discharge specific capacity of the common cobalt-free binary high-nickel anode material in the comparative example is 174.1mAh/g, and the capacity retention rate after 50 charge-discharge cycles is 76.9%. Therefore, the discharge specific capacity of the battery prepared from the ternary concentration gradient core-shell lithium ion battery anode material obtained by the invention is higher than that of the battery prepared from the common cobalt-free binary high-nickel anode material; and the optimum amount of doped tungsten within the concentration gradient in the present invention is 1%.
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 (4)
1. The cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery anode material is characterized in that the chemical formula of the anode material is Li [ Ni ]xMn1-x-yWy]O2X and y are mole numbers, wherein x is more than or equal to 0.8 and less than 1, and y is more than 0 and less than or equal to 0.1.
2. A method for preparing the ternary concentration gradient core-shell lithium ion battery cathode material according to claim 1, wherein the method comprises the following steps:
(1) preparing a first salt solution containing nickel, manganese and tungsten, wherein the molar ratio of nickel ions to manganese ions to tungsten ions is (90-100): (10-20): (0-10), wherein the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the first salt solution is 2.00-4.00 mol/L; preparing a second salt solution containing nickel, manganese and tungsten, wherein the molar ratio of nickel ions to manganese ions to tungsten ions is (60-70): (30-40): (0-10), wherein the sum of the concentration of nickel ions, the concentration of manganese ions and the concentration of tungsten ions in the second salt solution is 2.00-4.00 mol/L;
(2) will be firstAdding a salt solution into a reaction kettle in a nitrogen atmosphere at the speed of 2.5L/h-5L/h, simultaneously adding a sodium hydroxide solution as a precipitator and an ammonia water solution as a complexing agent into the reaction kettle, and carrying out a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is [ Ni ]mMn1-m-nWn](OH)2Wherein m is more than or equal to 0.9 and less than 1, and n is more than 0 and less than or equal to 0.1; the concentration of the sodium hydroxide solution is 2-4 mol/L, and the concentration of the ammonia water solution is 1-4 mol/L; the technological conditions of the first coprecipitation reaction are as follows: the ammonia concentration in the reaction kettle is kept between 4g/L and 12g/L, the reaction PH is between 10 and 12, the reaction time is between 20 and 50 hours, and the rotating speed is between 300 and 450 rpm;
(3) when the reaction time of the first coprecipitation reaction is reached, immediately pumping the second salt solution into the reaction kettle at the speed of 9L/h-12L/h, and carrying out the second coprecipitation reaction to obtain a solid-liquid mixture; the process conditions of the second coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5g/L and 15g/L, the pH value of the reaction is between 10 and 12, the reaction time is between 50 and 60 hours, and the rotating speed of the reaction is between 300 and 450 rpm;
(4) sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a ternary concentration gradient precursor with a chemical formula of [ Ni ]xMn1-x-yWy](OH)2Wherein x is more than or equal to 0.8 and less than 1, and y is more than 0 and less than or equal to 0.1; the drying temperature is 150-250 ℃, and the drying time is 8-10 h;
(5) uniformly mixing the ternary concentration gradient precursor with lithium hydroxide according to the molar ratio of 1: 1.05-1.2, roasting in a muffle furnace, cooling, crushing and sieving after roasting to obtain the ternary concentration gradient core-shell structure lithium ion battery anode material.
3. The preparation method of the ternary concentration gradient core-shell structure lithium ion battery cathode material according to claim 2, wherein the first salt solution is one of a sulfate solution, a nitrate solution and a chloride solution; the second saline solution is one of a sulfate solution, a nitrate solution and a chloride solution.
4. The preparation method of the ternary concentration gradient core-shell structure lithium ion battery anode material according to claim 2, wherein in the step (5), the roasting process is carried out in an oxygen atmosphere, the roasting process comprises a first-stage roasting process and a second-stage roasting process which are sequentially carried out, and the process conditions of the first-stage roasting process are as follows: heat treatment is carried out for 1h-5h at the temperature of 250 ℃ to 500 ℃, and the process conditions of the secondary roasting are as follows: heat treatment is carried out for 10h to 16h at the temperature of 500 ℃ to 900 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111000234.2A CN113889615A (en) | 2021-08-30 | 2021-08-30 | Cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111000234.2A CN113889615A (en) | 2021-08-30 | 2021-08-30 | Cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113889615A true CN113889615A (en) | 2022-01-04 |
Family
ID=79011586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111000234.2A Pending CN113889615A (en) | 2021-08-30 | 2021-08-30 | Cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113889615A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114497537A (en) * | 2022-02-25 | 2022-05-13 | 中南大学 | Cobalt-free high-nickel ternary cathode material and preparation method thereof |
| CN114520318A (en) * | 2022-01-27 | 2022-05-20 | 北京理工大学 | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method thereof |
| CN114551837A (en) * | 2022-03-25 | 2022-05-27 | 中南大学 | Quick-charging type cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery positive electrode material and preparation method thereof |
| CN114551862A (en) * | 2022-02-28 | 2022-05-27 | 宜宾锂宝新材料有限公司 | Cobalt-free binary single crystal material and preparation method thereof |
| CN114551838A (en) * | 2022-02-25 | 2022-05-27 | 中南大学 | Modified single crystal type cobalt-free high-nickel ternary positive electrode material and preparation method thereof |
| CN114590846A (en) * | 2022-02-16 | 2022-06-07 | 广东邦普循环科技有限公司 | Precursor for inhibiting microcrack of anode material and preparation method and application thereof |
| CN114649521A (en) * | 2022-03-30 | 2022-06-21 | 宁波容百新能源科技股份有限公司 | Hollow porous concentration gradient cathode material and preparation method thereof |
| CN114843468A (en) * | 2022-05-07 | 2022-08-02 | 广东工业大学 | Cobalt-free high-nickel ternary gradient lithium ion battery cathode material and preparation method thereof |
| CN115663198A (en) * | 2022-12-29 | 2023-01-31 | 宜宾锂宝新材料有限公司 | Cobalt-free cathode material, preparation method thereof, cathode and lithium ion battery |
| WO2024000777A1 (en) * | 2022-06-29 | 2024-01-04 | 荆门市格林美新材料有限公司 | Positive electrode material precursor and positive electrode material and preparation methods therefor, and sodium-ion battery |
| CN117558904A (en) * | 2024-01-11 | 2024-02-13 | 河南科隆新能源股份有限公司 | Cobalt-free positive electrode material with porous core-shell structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108199027A (en) * | 2018-01-09 | 2018-06-22 | 江西理工大学 | A kind of niobium doping is without cobalt nickel-base anode material and preparation method thereof |
| CN111646522A (en) * | 2020-06-02 | 2020-09-11 | 格林美股份有限公司 | Cobalt-free precursor for lithium ion battery, positive electrode material and preparation method of cobalt-free precursor |
| CN112164784A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof |
| CN113060776A (en) * | 2021-03-31 | 2021-07-02 | 蜂巢能源科技有限公司 | Layered cobalt-free cathode material, preparation method thereof and lithium ion battery |
-
2021
- 2021-08-30 CN CN202111000234.2A patent/CN113889615A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108199027A (en) * | 2018-01-09 | 2018-06-22 | 江西理工大学 | A kind of niobium doping is without cobalt nickel-base anode material and preparation method thereof |
| CN111646522A (en) * | 2020-06-02 | 2020-09-11 | 格林美股份有限公司 | Cobalt-free precursor for lithium ion battery, positive electrode material and preparation method of cobalt-free precursor |
| CN112164784A (en) * | 2020-08-27 | 2021-01-01 | 荆门市格林美新材料有限公司 | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof |
| CN113060776A (en) * | 2021-03-31 | 2021-07-02 | 蜂巢能源科技有限公司 | Layered cobalt-free cathode material, preparation method thereof and lithium ion battery |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114520318A (en) * | 2022-01-27 | 2022-05-20 | 北京理工大学 | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method thereof |
| CN114520318B (en) * | 2022-01-27 | 2024-01-26 | 北京理工大学 | High-nickel cobalt-free nickel tungsten lithium manganate positive electrode material for power battery and preparation method |
| WO2023155541A1 (en) * | 2022-02-16 | 2023-08-24 | 广东邦普循环科技有限公司 | Precursor for suppressing micro-cracks in positive electrode material, method for preparing same, and use thereof |
| CN114590846A (en) * | 2022-02-16 | 2022-06-07 | 广东邦普循环科技有限公司 | Precursor for inhibiting microcrack of anode material and preparation method and application thereof |
| CN114551838A (en) * | 2022-02-25 | 2022-05-27 | 中南大学 | Modified single crystal type cobalt-free high-nickel ternary positive electrode material and preparation method thereof |
| CN114497537A (en) * | 2022-02-25 | 2022-05-13 | 中南大学 | Cobalt-free high-nickel ternary cathode material and preparation method thereof |
| CN114551862A (en) * | 2022-02-28 | 2022-05-27 | 宜宾锂宝新材料有限公司 | Cobalt-free binary single crystal material and preparation method thereof |
| CN114551837A (en) * | 2022-03-25 | 2022-05-27 | 中南大学 | Quick-charging type cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery positive electrode material and preparation method thereof |
| CN114649521A (en) * | 2022-03-30 | 2022-06-21 | 宁波容百新能源科技股份有限公司 | Hollow porous concentration gradient cathode material and preparation method thereof |
| CN114843468B (en) * | 2022-05-07 | 2023-09-01 | 广东工业大学 | Cobalt-free high-nickel ternary gradient lithium ion battery anode material and preparation method thereof |
| CN114843468A (en) * | 2022-05-07 | 2022-08-02 | 广东工业大学 | Cobalt-free high-nickel ternary gradient lithium ion battery cathode material and preparation method thereof |
| WO2024000777A1 (en) * | 2022-06-29 | 2024-01-04 | 荆门市格林美新材料有限公司 | Positive electrode material precursor and positive electrode material and preparation methods therefor, and sodium-ion battery |
| CN115663198B (en) * | 2022-12-29 | 2023-04-14 | 宜宾锂宝新材料有限公司 | Cobalt-free cathode material, preparation method thereof, cathode and lithium ion battery |
| CN115663198A (en) * | 2022-12-29 | 2023-01-31 | 宜宾锂宝新材料有限公司 | Cobalt-free cathode material, preparation method thereof, cathode and lithium ion battery |
| CN117558904A (en) * | 2024-01-11 | 2024-02-13 | 河南科隆新能源股份有限公司 | Cobalt-free positive electrode material with porous core-shell structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113889615A (en) | Cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery cathode material and preparation method thereof | |
| CN112164784B (en) | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof | |
| CN107123792B (en) | Ternary cathode material with double-layer composite structure and preparation method thereof | |
| CN112758991B (en) | Preparation method of core-shell structure ternary cathode material precursor | |
| CN115196691A (en) | Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN114477312B (en) | Method for preparing ternary positive electrode material precursor by layered doping | |
| CN112447962A (en) | Precursor for doped lithium ion battery, positive electrode material and preparation methods of precursor and positive electrode material | |
| CN113620354A (en) | Surface-coated lithium ion battery anode material precursor and preparation method thereof | |
| CN112993243A (en) | Preparation method of high-density aluminum-doped cobalt oxide | |
| CN114551837A (en) | Quick-charging type cobalt-free high-nickel ternary concentration gradient core-shell structure lithium ion battery positive electrode material and preparation method thereof | |
| CN114835173A (en) | Positive electrode material precursor, preparation method thereof and positive electrode material | |
| CN113582254B (en) | Layered positive electrode material and preparation method and application thereof | |
| CN117342630B (en) | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery | |
| CN109678217B (en) | High tap density Ni0.8Co0.1Mn0.1(OH)2Preparation method and application of material | |
| CN112194194A (en) | Method for preparing single crystal NCMA precursor material | |
| CN115084503B (en) | Positive electrode material and preparation method and application thereof | |
| CN115403076A (en) | Porous spherical ternary precursor and preparation method thereof, ternary positive electrode material, positive electrode plate and battery | |
| CN114906881A (en) | Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material | |
| CN113860379A (en) | Positive electrode material precursor, positive electrode material, and preparation method and application thereof | |
| CN111416117A (en) | Preparation method of CdTe quantum dot modified lithium battery positive electrode material | |
| CN115676913B (en) | Zinc-doped core-shell structure high-nickel ternary precursor and preparation method thereof | |
| CN109616662A (en) | Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery | |
| CN118084086B (en) | Core-shell structured high-nickel lithium battery anode material with high capacity and long cycle life and preparation method thereof | |
| CN113443660B (en) | Agglomerated precursor of coral-like lithium-rich manganese-based solid solution cathode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |