CN113161534A - Co-doped modified lithium ion battery ternary cathode material and preparation method thereof - Google Patents
Co-doped modified lithium ion battery ternary cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN113161534A CN113161534A CN202110407022.XA CN202110407022A CN113161534A CN 113161534 A CN113161534 A CN 113161534A CN 202110407022 A CN202110407022 A CN 202110407022A CN 113161534 A CN113161534 A CN 113161534A
- Authority
- CN
- China
- Prior art keywords
- salt
- lithium
- cathode material
- aluminum
- precursor
- 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
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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a codoped modified lithium ion battery ternary cathode material and a preparation method thereof, wherein the chemical general formula of the prepared material is Li (Ni)0.5Co0.2Mn0.3)1‑xAlx/2Lix/2O2‑xFxWherein x is 0-0.06. The method is characterized by comprising the following steps: weighing lithium salt, nickel salt, cobalt salt, manganese salt, aluminum salt and non-metal fluorine salt according to a molar ratio, then weighing citric acid, dissolving, adding into the mixed solution, stirring and evaporating to form sol, drying, pre-sintering to obtain a precursor, and finally calcining at a high temperature to obtain the doped material. The preparation method is simple and convenient, and the obtained Al, Li and F co-doped anode material particles are allThe method has the advantages of uniformity, moderate granularity, high crystallization degree and excellent cycle performance under high temperature and high voltage, can be practically applied to the field of power batteries, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a co-doped modified lithium ion battery ternary cathode material and a preparation method thereof, belonging to the technical field of lithium ion batteries.
Background
In recent years, with the rapid update of electronic equipment and the rapid development of new energy automobile market, the requirements on the performance of lithium ion batteries are higher and higher,the positive electrode material has been the key to limit the development of lithium ion batteries. The anode materials widely used at present mainly comprise lithium cobaltate, lithium manganate, lithium iron phosphate, various ternary materials and the like, wherein the ternary materials are more in a nickel-cobalt-manganese system. Nickel-cobalt-manganese series ternary material (LiNi)xCoyMnzO2) Has higher specific capacity, better safety performance, lower cost and the like, and is considered to be most likely to replace the current commercial anode material LiCoO with the largest use amount2。
LiNi0.5Co0.2Mn0.3O2The anode material has the advantages of high specific discharge capacity, good cycling stability, low cost, environmental friendliness and the like, and thus becomes a research hotspot. However, under the condition of high voltage, due to the aggravation of side reaction of the positive electrode material and the electrolyte, the defects of fast capacity attenuation, reduced cycling stability and the like still exist, and the application of the positive electrode material in the field of high-energy-density lithium ion batteries is limited. Therefore, efforts have been made to overcome these disadvantages, wherein element doping, size control and surface modification have proven to be effective methods and a series of advances have been made.
Element doping is mainly divided into cation doping and anion doping, common cations for doping are A1, Cr, Mg, Ti, Fe and the like, the cations mainly replace transition metals in the ternary anode material, the transition metals have certain influence on the form, structure and electrochemical performance of the material, and the doped cations are beneficial to stabilizing the structure of the anode material, inhibiting cation mixing, reducing first irreversible capacity loss and improving the cycle performance and rate capability of the material; common doping anions are F, C1, S and the like, and the anions with larger electronegativity can improve the specific capacity of the material and improve the crystallinity and electronic conductivity of the material. In addition, researchers substitute the Li site of the positive electrode material with elements such as Na and K, and the like, and have certain improvement effect on the electrochemical performance of the material. However, the single doping strategy does not completely compensate for the defects of the ternary cathode material.
Disclosure of Invention
The invention aims to provide LiNi codoped with Al, Li and F ions0.5Co0.2Mn0.3O2A ternary cathode material and a preparation method thereof. The ternary cathode material of the lithium ion battery prepared by the invention has the advantages of moderate particles, low cation mixing degree, good crystallinity, good structural stability and high-temperature cycle performance.
The invention firstly provides Al, Li and F codoped modified LiNi0.5Co0.2Mn0.3O2The chemical general formula of the cathode material is Li (Ni)0.5Co0.2Mn0.3)1-xAlx/2Lix/2O2-xFxWherein x is 0-0.06.
The invention also provides the Al, Li and F codoped modified LiNi0.5Co0.2Mn0.3O2A method of preparing a positive electrode material, the method comprising the steps of:
(1) weighing lithium salt, nickel salt, cobalt salt, manganese salt, aluminum salt and fluorine salt according to a certain molar ratio, respectively dissolving and mixing, then weighing citric acid with the same amount as the sum of the molar number of the metal salt, dissolving and adding the mixed solution;
(2) adjusting the pH value of the mixed solution to 7-8 by using ammonia water, and stirring and evaporating the mixed solution at 75-85 ℃ until purple sol is formed;
(3) drying the purple sol obtained in the step (2) to obtain a precursor;
(4) pre-sintering the precursor obtained in the step (3) at 400-600 ℃ for 6-9 h, cooling, and grinding for 0.5-1 h to obtain a precursor;
(5) and (3) placing the precursor obtained in the step (4) at 800-950 ℃, calcining at high temperature for 12-24 h under an oxygen-enriched condition or in an air atmosphere, cooling, and grinding for 0.5-1 h again to obtain the Al, Li and F ion co-doped ternary cathode material.
In one embodiment of the present invention, the lithium salt in step (1) is one or more of lithium acetate, lithium nitrate and lithium hydroxide; the nickel salt, the cobalt salt and the manganese salt are one or more of acetate and nitrate; the aluminum salt is one or two of aluminum acetate and aluminum nitrate; the fluorine salt is one or two of lithium fluoride and ammonium fluoride.
In one embodiment of the present invention, the amount of the lithium salt used in step (1) is 5% of the theoretical amount.
In one embodiment of the present invention, when the fluorine salt is lithium fluoride, the molar ratio of the lithium salt, the nickel salt, the cobalt salt, the manganese salt, the aluminum salt and the fluorine salt is: 0.5(1-x) 0.2(1-x) 0.3(1-x) x/2 x, wherein the value of x is 0-0.06.
In one embodiment of the present invention, when the fluorine salt is ammonium fluoride, the molar ratio of the lithium salt, the nickel salt, the cobalt salt, the manganese salt, the aluminum salt, and the fluorine salt is: (1.05+ x/2):0.5(1-x):0.2(1-x):0.3(1-x): x/2: x, wherein the value of x is 0-0.06.
In one embodiment of the invention, in the step (3), the drying is performed at 80-120 ℃ for 10-12 h.
In one embodiment of the invention, the oxygen concentration of the oxygen-enriched conditions in step (5) is greater than 21%.
The invention also provides the Al, Li and F codoped modified LiNi0.5Co0.2Mn0.3O2A lithium ion battery of a positive electrode material.
The invention has the following beneficial effects:
(1) al, Li and F codoped ternary LiNi prepared by the method0.5Co0.2Mn0.3O2The positive electrode material is regular in shape and is similar to a sphere, the particle size distribution is uniform, the surface is smooth, and the crystallinity is good.
(2) Compared with a commercialized laminated structure, the ternary cathode material prepared by the invention has moderate particles and high tap density; the specific surface area is small, the contact area of the material and the electrolyte can be reduced, and the side reaction in the battery circulation process is reduced.
(3) For LiNi0.5Co0.2Mn0.3O2The Al, Li and F ion co-doping is carried out, so that the synergistic advantage brought by the doping of the three ions can be brought, the cation mixed-discharging degree of the material is reduced, and the circulating stability, the coulombic efficiency and the multiplying power performance of the material are improved.
(4) The preparation method of the ternary cathode material has high feasibility, rich raw material storage and low price, and is a lithium ion battery cathode material which has practical application prospect and can be produced in a large scale.
Drawings
(1) FIG. 1 is a diagram showing Li (Ni) as a co-doped cathode material of Al, Li and F prepared in example 30.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04XRD pattern of (a);
(2) FIG. 2 is a diagram showing Li (Ni) as a co-doped cathode material of Al, Li and F prepared in example 30.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04SEM image at 30K magnification;
(3) FIG. 3 is Li (Ni) as a co-doped cathode material of Al, Li and F prepared in example 30.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04The first charge-discharge curve (3.0-4.6V, 0.2C) at normal temperature (25 ℃);
(4) FIG. 4 is Li (Ni) as a co-doped cathode material of Al, Li and F prepared in example 30.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04The first charge-discharge curve (3.0-4.6V, 0.2C) at high temperature (55 ℃);
(5) FIG. 5 is a diagram showing Li (Ni) as a co-doped cathode material of Al, Li and F prepared in example 30.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04Cycle performance curve (3.0-4.6V, 0.2C) at normal temperature (25 ℃);
(6) FIG. 6 is a Co-doped Al, Li and F cathode material Li (Ni) prepared in example 30.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04Cycle performance curves (3.0-4.6V, 0.2C) at high temperature (55 ℃).
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Weighing lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate according to a molar ratio of 1.05:0.5:0.2:0.3, respectively dissolving and mixing, weighing citric acid with the same amount as the sum of the molar number of the metal salt, dissolving and adding the mixed solution;
(2) adjusting the pH value of the mixed solution to 7.5 by using ammonia water, placing the mixed solution in a water bath kettle at 85 ℃, stirring and evaporating until purple sol is formed;
(3) drying the purple sol obtained in the step (2) in a forced air drying oven at 100 ℃ for 12h to obtain a precursor;
(4) transferring the precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, presintering for 6h, cooling to room temperature, and grinding for 1h to obtain a precursor;
(5) placing the precursor in a muffle furnace, heating to 850 ℃ at the heating rate of 6 ℃/min, carrying out high-temperature calcination in the air atmosphere for 16h, cooling to room temperature, and grinding for 0.5h again to obtain the ternary cathode material LiNi0.5Co0.2Mn0.3O2。
(6) The material obtained in example 1 is assembled into a CR2032 type button cell to be subjected to a charge-discharge cycle test. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, respectively weighing the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 80:12:8, grinding and mixing uniformly, coating on a pretreated aluminum foil, and drying in a vacuum drying oven at 80 ℃ to obtain the positive electrode plate. Pure metal lithium sheet as negative pole, polypropylene microporous membrane Celgard 2325 as diaphragm, LB315[ m (DMC): m (EMC): m (EC): 1]The mixed solution of (A) was used as an electrolyte in an argon-filled glove box (H)2Content of O<1ppm) were assembled into button cells.
The button cell is subjected to constant-current cyclic charge-discharge test by using an LAND cell test system, the test voltage is 3.0-4.6V, the first discharge specific capacity is 184.3mAh g at 0.2C and normal temperature (25 ℃), and-1the first coulombic efficiency is 80.3 percent, and the specific discharge capacity after 50 cycles is 159.9mAh g-1The capacity retention rate is 86.8%; test voltage 3.0EThe specific first discharge capacity of the material is 204.7mAh g at 4.6V, 0.2C and high temperature (55℃)-1The first coulombic efficiency is 78.4 percent, and the specific discharge capacity after 50 cycles is 153.7mAh g-1The capacity retention rate was 75.1%.
Example 2
(1) Weighing lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and ammonium fluoride according to a molar ratio of 1.06:0.49:0.196:0.294:0.01:0.02, dissolving and mixing, weighing citric acid which is equal to the sum of the molar number of the metal salt, dissolving and adding the mixed solution;
(2) adjusting the pH value of the mixed solution to 7.5 by using ammonia water, placing the mixed solution in a water bath kettle at 85 ℃, stirring and evaporating until purple sol is formed;
(3) drying the purple sol obtained in the step (2) in a forced air drying oven at 100 ℃ for 12h to obtain a precursor;
(4) transferring the precursor into a muffle furnace, heating to 500 ℃ at the heating rate of 4 ℃/min for presintering for 6h, cooling to room temperature, and grinding for 1h to obtain the precursor;
(5) placing the precursor in a muffle furnace, heating to 850 ℃ at the heating rate of 6 ℃/min, carrying out high-temperature calcination in the air atmosphere for 16h, cooling to room temperature, and grinding for 0.5h again to obtain the ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.98Al0.01Li0.01O1.98F0.02。
(6) The material obtained in example 2 is assembled into a CR2032 type button cell to be subjected to a charge-discharge cycle test. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, respectively weighing the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 80:12:8, grinding and mixing uniformly, coating on a pretreated aluminum foil, and drying in a vacuum drying oven at 80 ℃ to obtain the positive electrode plate. Pure metal lithium sheet as negative pole, polypropylene microporous membrane Celgard 2325 as diaphragm, LB315[ m (DMC): m (EMC): m (EC): 1]The mixed solution of (A) was used as an electrolyte in an argon-filled glove box (H)2Content of O<1ppm) were assembled into button cells.
By LAND cellsThe test system performs constant current circulation charge and discharge test on the button cell, the test voltage is 3.0-4.6V, the first discharge specific capacity is 182.6 mAh.g at 0.2C and normal temperature (25℃)-1The first coulombic efficiency is 84.6 percent, and the specific discharge capacity after 50 cycles is 168.7mAh g-1The capacity retention rate is 92.4%; the first discharge specific capacity is 198.4 mAh.g at the test voltage of 3.0-4.6V and the test temperature of 0.2C and high temperature (55℃)-1The first coulombic efficiency is 81.4 percent, and the specific discharge capacity after 50 cycles is 165.4mAh g-1The capacity retention rate was 83.4%.
Example 3
(1) Weighing lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and lithium fluoride according to a molar ratio of 1.03:0.48:0.192:0.288:0.02:0.04, dissolving and mixing respectively, weighing citric acid which is equal to the sum of the molar number of the metal salt, dissolving and adding the mixed solution;
(2) adjusting the pH value of the mixed solution to 7.5 by using ammonia water, placing the mixed solution in a water bath kettle at 85 ℃, stirring and evaporating until purple sol is formed;
(3) drying the purple sol obtained in the step (2) in a forced air drying oven at 100 ℃ for 12h to obtain a precursor;
(4) transferring the precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, presintering for 6h, cooling to room temperature, and grinding for 1h to obtain a precursor;
(5) placing the precursor in a muffle furnace, heating to 850 ℃ at the heating rate of 6 ℃/min, carrying out high-temperature calcination in the air atmosphere for 16h, cooling to room temperature, and grinding for 0.5h again to obtain the ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.96Al0.02Li0.02O1.96F0.04。
(6) The material obtained in example 3 is assembled into a CR2032 type button cell to be subjected to a charge-discharge cycle test. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, respectively weighing a positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 80:12:8, grinding and mixing uniformly, coating on a pretreated aluminum foil, and putting into a vacuum drying chamberDrying at 80 ℃ in a drying box to obtain the positive plate. Pure metal lithium sheet as negative pole, polypropylene microporous membrane Celgard 2325 as diaphragm, LB315[ m (DMC): m (EMC): m (EC): 1]The mixed solution of (A) was used as an electrolyte in an argon-filled glove box (H)2Content of O<1ppm) were assembled into button cells.
The button cell is subjected to constant-current cyclic charge-discharge test by using an LAND cell test system, the test voltage is 3.0-4.6V, the first discharge specific capacity is 179.2 mAh.g at 0.2C and normal temperature (25℃)-1The first coulombic efficiency is 85.2 percent, and the specific discharge capacity after 50 cycles is 169.7mAh g-1The capacity retention rate is 94.7%; the first discharge specific capacity is 189.0mAh g under the test voltage of 3.0-4.6V and the test temperature of 0.2C and the high temperature (55℃)-1The first coulombic efficiency is 82.6 percent, and the specific discharge capacity after 50 cycles is 163.6 mAh.g-1The capacity retention rate was 86.6%.
Example 4
(1) Weighing lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and lithium fluoride according to a molar ratio of 1.02:0.47:0.188:0.282:0.03:0.06, respectively dissolving and mixing, weighing citric acid which is equal to the sum of the molar number of the metal salt, dissolving and adding the mixed solution;
(2) adjusting the pH value of the mixed solution to 7.5 by using ammonia water, placing the mixed solution in a water bath kettle at 85 ℃, stirring and evaporating until purple sol is formed;
(3) drying the purple sol obtained in the step (2) in a forced air drying oven at 100 ℃ for 12h to obtain a precursor;
(4) transferring the precursor into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, presintering for 6h, cooling to room temperature, and grinding for 1h to obtain a precursor;
(5) placing the precursor in a muffle furnace, heating to 850 ℃ at the heating rate of 6 ℃/min, carrying out high-temperature calcination in the air atmosphere for 16h, cooling to room temperature, and grinding for 0.5h again to obtain the ternary cathode material Li (Ni)0.5Co0.2Mn0.3)0.94Al0.03Li0.03O1.94F0.06。
(6) Examples of the invention4, assembling the obtained material into a CR2032 type button cell to carry out charge-discharge cycle test. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, respectively weighing the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 80:12:8, grinding and mixing uniformly, coating on a pretreated aluminum foil, and drying in a vacuum drying oven at 80 ℃ to obtain the positive electrode plate. Pure metal lithium sheet as negative pole, polypropylene microporous membrane Celgard 2325 as diaphragm, LB315[ m (DMC): m (EMC): m (EC): 1]The mixed solution of (A) was used as an electrolyte in an argon-filled glove box (H)2Content of O<1ppm) were assembled into button cells.
The button cell is subjected to constant-current cyclic charge-discharge test by using an LAND cell test system, the test voltage is 3.0-4.6V, the first discharge specific capacity is 173.5mAh g at 0.2C and normal temperature (25 ℃), and-1the first coulombic efficiency is 82.3 percent, and the specific discharge capacity after 50 cycles is 157.8mAh g-1The capacity retention rate is 90.8%; the first discharge specific capacity of the material is 180.1 mAh.g at a test voltage of 3.0-4.6V and a high temperature (55 ℃) of 0.2C-1The first coulombic efficiency is 80.8 percent, and the specific discharge capacity after 50 cycles is 148.2mAh g-1The capacity retention rate was 82.3%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. Al, Li and F co-doped modified LiNi0.5Co0.2Mn0.3O2The cathode material is characterized in that the chemical general formula of the cathode material is Li (Ni)0.5Co0.2Mn0.3)1-xAlx/2Lix/2O2-xFxWherein x is 0-0.06.
2. The Al, Li and F co-doped modified LiNi of claim 10.5Co0.2Mn0.3O2A method for producing a positive electrode material, characterized by comprising the steps of:
(1) weighing lithium salt, nickel salt, cobalt salt, manganese salt, aluminum salt and fluorine salt according to a certain molar ratio, respectively dissolving and mixing, then weighing citric acid with the same amount as the sum of the molar number of the metal salt, dissolving and adding the mixed solution;
(2) adjusting the pH value of the mixed solution to 7-8 by using ammonia water, and stirring and evaporating the mixed solution at 75-85 ℃ until purple sol is formed;
(3) drying the purple sol obtained in the step (2) to obtain a precursor;
(4) pre-sintering the precursor obtained in the step (3) at 400-600 ℃ for 6-9 h, cooling, and grinding for 0.5-1 h to obtain a precursor;
(5) and (3) placing the precursor obtained in the step (4) at 800-950 ℃, calcining at high temperature for 12-24 h under an oxygen-enriched condition or in an air atmosphere, cooling, and grinding for 0.5-1 h again to obtain the Al, Li and F ion co-doped ternary cathode material.
3. The preparation method according to claim 2, wherein the lithium salt in step (1) is one or more of lithium acetate, lithium nitrate, and lithium hydroxide; the nickel salt, the cobalt salt and the manganese salt are one or more of acetate and nitrate.
4. The production method according to claim 3, wherein the aluminum salt is one or both of aluminum acetate and aluminum nitrate; the fluorine salt is one or two of lithium fluoride and ammonium fluoride.
5. The method according to claim 2, wherein the amount of the lithium salt used in the step (1) is 5% of the theoretical amount.
6. The method according to claim 4, wherein when the fluorine salt is lithium fluoride, the molar ratio of the lithium salt, the nickel salt, the cobalt salt, the manganese salt, the aluminum salt, and the fluorine salt is: 0.5(1-x) 0.2(1-x) 0.3(1-x) x/2 x, wherein the value of x is 0-0.06.
7. The method according to claim 4, wherein when the fluorine salt is ammonium fluoride, the molar ratio of the lithium salt, the nickel salt, the cobalt salt, the manganese salt, the aluminum salt, and the fluorine salt is: (1.05+ x/2):0.5(1-x):0.2(1-x):0.3(1-x): x/2: x, wherein the value of x is 0-0.06.
8. The preparation method according to claim 2, wherein in the step (3), the drying is carried out at 80-120 ℃ for 10-12 h.
9. The method of claim 2, wherein the oxygen concentration of the oxygen-enriched condition in step (5) is greater than 21%.
10. Comprising the Al, Li and F codoped modified LiNi of claim 10.5Co0.2Mn0.3O2A lithium ion battery of a positive electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110407022.XA CN113161534A (en) | 2021-04-15 | 2021-04-15 | Co-doped modified lithium ion battery ternary cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110407022.XA CN113161534A (en) | 2021-04-15 | 2021-04-15 | Co-doped modified lithium ion battery ternary cathode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113161534A true CN113161534A (en) | 2021-07-23 |
Family
ID=76867955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110407022.XA Pending CN113161534A (en) | 2021-04-15 | 2021-04-15 | Co-doped modified lithium ion battery ternary cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113161534A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114291802A (en) * | 2021-12-20 | 2022-04-08 | 安徽博石高科新材料股份有限公司 | Preparation and application of MOFs material modified lithium iron phosphate positive electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104253273A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
| CN105895906A (en) * | 2016-05-11 | 2016-08-24 | 双登集团股份有限公司 | Lithium-doped ternary lithium-ion battery positive electrode material and preparation method thereof |
| CN106654255A (en) * | 2016-12-16 | 2017-05-10 | 江南大学 | Aluminum-doped and modified cathode material for high-capacity lithium ion batteries |
| CN110021752A (en) * | 2019-01-24 | 2019-07-16 | 湖北锂诺新能源科技有限公司 | A kind of lithium, aluminium and fluorin-doped lithium iron phosphate positive material and preparation method |
-
2021
- 2021-04-15 CN CN202110407022.XA patent/CN113161534A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104253273A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
| CN105895906A (en) * | 2016-05-11 | 2016-08-24 | 双登集团股份有限公司 | Lithium-doped ternary lithium-ion battery positive electrode material and preparation method thereof |
| CN106654255A (en) * | 2016-12-16 | 2017-05-10 | 江南大学 | Aluminum-doped and modified cathode material for high-capacity lithium ion batteries |
| CN110021752A (en) * | 2019-01-24 | 2019-07-16 | 湖北锂诺新能源科技有限公司 | A kind of lithium, aluminium and fluorin-doped lithium iron phosphate positive material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 田建坤等: ""锂离子电池正极材料LiNi0.5Co0.2Mn0.3O2的制备与性能研究"", 化工新型材料, vol. 45, no. 9, pages 142 - 144 * |
| 韩学武等: ""烧结温度对Al、F掺杂LiNi0.5Co0.2Mn0.3O2正极材料的影响"", 第30届全国化学与物理电源学术年会论文集, pages 85 - 87 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114291802A (en) * | 2021-12-20 | 2022-04-08 | 安徽博石高科新材料股份有限公司 | Preparation and application of MOFs material modified lithium iron phosphate positive electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103545519B (en) | Coated lithium-rich anode material of a kind of carbon and preparation method thereof | |
| CN110931797A (en) | High-nickel positive electrode material with composite coating layer and preparation method thereof | |
| CN108448109B (en) | Layered lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN102956883B (en) | AnodePositive electrode material of lithium ion battery with porous laminated structure and preparation method thereof | |
| CN107403913A (en) | A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof | |
| CN110492095B (en) | Tin-doped lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN103474646B (en) | A kind of mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof | |
| CN105576231A (en) | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN111463428A (en) | Sodium ion doped ternary cathode material and preparation method thereof | |
| CN111204813B (en) | Preparation method of vanadium-doped lithium-rich manganese-based positive electrode material | |
| CN103943841A (en) | Anion doped modified lithium ion battery (4:4:2) type ternary cathode material and preparing method thereof | |
| CN106450179A (en) | Preparation method of titanium-doping ferric fluoride positive electrode material | |
| CN105826568A (en) | Lithium-rich positive electrode material with hypoxic metallic oxide coating layer structure, preparation method and application | |
| CN113451582A (en) | Tungsten and sulfur co-doped modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN111463427A (en) | Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof | |
| CN113161534A (en) | Co-doped modified lithium ion battery ternary cathode material and preparation method thereof | |
| CN107069026A (en) | A kind of rich lithium manganese oxide anode material of effective stratiform for suppressing capacity/voltage attenuation in cyclic process and its preparation method and application | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN104201346B (en) | A kind of preparation method and application of the non-stoichiometric phosphate cathode material with excellent chemical property | |
| CN102779992A (en) | Lithium ion battery positive electrode material in layer structure and preparation method thereof | |
| CN115764013A (en) | Positive electrode lithium supplement material, preparation method and application thereof | |
| CN112125340B (en) | Lithium manganate and preparation method and application thereof | |
| CN108832086A (en) | The method that solvent assistant reducing agent method prepares graphene composite lithium-rich anode material | |
| CN114864911A (en) | Modified high-nickel ternary cathode material and preparation method and application 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 |