CN112599781A - Double-concentration gradient doped lithium ion battery anode material and preparation method thereof - Google Patents
Double-concentration gradient doped lithium ion battery anode material and preparation method thereof Download PDFInfo
- Publication number
- CN112599781A CN112599781A CN202011484337.6A CN202011484337A CN112599781A CN 112599781 A CN112599781 A CN 112599781A CN 202011484337 A CN202011484337 A CN 202011484337A CN 112599781 A CN112599781 A CN 112599781A
- Authority
- CN
- China
- Prior art keywords
- salt solution
- concentration
- ions
- solution
- ion battery
- 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.)
- Granted
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
- H01M4/50—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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a double-concentration gradient doped lithium ion battery anode material, the chemical formula of which is LiNixCoyMnzM1‑x‑y‑zO2Wherein x is more than 0.3 and less than 0.9, y is more than 0.01 and less than 0.15, z is more than 0.05 and less than 0.2, and M is one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum. The preparation method of the material comprises the steps of preparing a salt solution and a doped salt solution, carrying out primary and secondary coprecipitation reactions, sequentially carrying out centrifugal washing, drying, screening for removing iron, mixing with lithium hydroxide, roasting, cooling, crushing and screening to obtain the double-concentrated solutionAnd (3) preparing the gradient doped lithium ion battery cathode material. The method can obtain the precursor with uniform particle size and high tap density, and then uniformly mix and sinter the hydroxide precursor and the lithium salt to obtain the oxide anode material of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a double-concentration gradient doped lithium ion battery anode material and a preparation method thereof.
Background
Although lithium batteries have been extensively studied over the last decades, they still face significant challenges in meeting the high demands of new applications, such as cost and safety issues for large-scale batteries. The development of new battery materials and the optimization of existing battery materials are two main approaches to improve the performance of lithium batteries and further expand their applications.
Generally, the synthesis process of the lithium ion battery anode material is carried out in two steps: firstly, synthesizing a hydroxide precursor; and uniformly mixing and sintering the hydroxide precursor and lithium salt to obtain the lithium ion battery oxide anode material. The anode material can inherit the appearance and structural characteristics of the precursor, so the structure and preparation process of the precursor have important influence on the performance of the anode material. Therefore, the first step of hydroxide precursor synthesis technology is reported to account for more than 50% of the technical content of the ternary material, and the development of the high-nickel ternary material cannot be promoted without departing from the development of the high-nickel ternary precursor. One of the big problems of the current ternary materials is that 'island' particles generated by the fracture and pulverization of aggregate particles cannot participate in the charging and discharging process, and more side reactions occur in the formed crack new interface, which can cause the reduction of the comprehensive performance of the lithium battery. In order to have a stable grain structure and excellent comprehensive performance, a full-flow system design is carried out from a precursor.
The high nickel layered anode has higher discharge capacity, and when the nickel content is more than 80 percent, the discharge capacity is as high as 200mAh/g cut-off voltage of 4.3V. However, these positive electrodes undergo continuous phase transition during cycling due to structural instability, and their capacities gradually decay during cycling.
Disclosure of Invention
Aiming at the problems in the prior art, the invention improves the production process flow of the precursor, adopts a two-step synthesis method, simultaneously dopes other elements, adjusts the microstructure of precursor particles, obtains the precursor with uniform particle size, good sphericity and high tap density, and then uniformly mixes and sinters the hydroxide precursor and lithium salt to obtain the lithium ion battery oxide anode material.
The invention adopts the following technical scheme:
the double-concentration gradient doped lithium ion battery anode material is characterized in that the chemical formula of the material is LiNixCoyMnzM1-x-y-zO2Wherein x is more than 0.3 and less than 0.9, y is more than 0.01 and less than 0.15, z is more than 0.05 and less than 0.2, and M is one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum.
The preparation method of the double-concentration-gradient doped lithium ion battery cathode material according to claim 1, characterized by comprising the following steps:
(1) preparing a first salt solution, a second salt solution, a third salt solution and a fourth salt solution with the molar ratio of nickel ions, cobalt ions and manganese ions of (85-95), (2-10), (60-80), (10-20), (10-30), (40-85), (5-30) and (30-70), (10-40) and (10-40);
(2) preparing a doping salt solution with the doping element concentration of 0.15-0.50 mol/L;
(3) adding the second salt solution into the first salt solution, stirring to obtain a first mixed solution, and adding the first mixed solution, the doped salt solution, the sodium hydroxide solution and the ammonia water solution into the reaction kettle to perform a first coprecipitation reaction; the rates of adding the first mixed solution and the doped salt solution into the reaction kettle are 4.00-6.00L/h and 2.00-4.00L/h respectively; the technological conditions of the first coprecipitation reaction are as follows: the concentration of ammonium in the reaction kettle is 5-12g/L, the pH value of the reaction is 10-12, and the reaction time is 50-80 h;
(4) when the first coprecipitation reaction is finished, adding a fourth salt solution into a third salt solution, stirring to obtain a second mixed solution, adding the second mixed solution and a doped salt solution into the reaction kettle, and carrying out a second coprecipitation reaction to obtain a solid-liquid mixture; the rates of adding the second mixed solution and the doped salt solution into the reaction kettle are respectively 12.00-14.00L/h and 2.00-4.00L/h; the process conditions of the second coprecipitation reaction are as follows: the concentration of ammonium in the reaction kettle is 7-15g/L, the pH value of the reaction is 10-11.5, and the reaction time is 45-60 h;
(5) and sequentially carrying out centrifugal washing, drying, screening and deironing on the solid-liquid mixture, mixing the solid-liquid mixture with lithium hydroxide according to the molar ratio of 1 (1.05-1.2), roasting, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material.
The preparation method of the double-concentration gradient doped lithium ion battery anode material is characterized in that the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the first salt solution in the step (1) is 2.00-5.00 mol/L; the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the second salt solution is 2.00-5.00 mol/L; the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the third salt solution is 2.00-5.00 mol/L; the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 2.00-5.00 mol/L; the salt solution is one of sulfate solution, nitrate solution and chloride solution.
The preparation method of the double-concentration gradient doped lithium ion battery anode material is characterized in that the doping elements in the doping salt solution in the step (2) are one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum; obtaining a precursor core after the first coprecipitation reaction in the step (3), wherein the chemical formula of the precursor core is NiaCobMncX1-a-b-c(OH)2Wherein a is more than or equal to 0.4 and less than 0.85, b is more than 0.05 and less than 0.08, c is more than 0.06 and less than 0.1, and X is one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum.
The preparation method of the double-concentration gradient doped lithium ion battery anode material is characterized in that the atmosphere in the reaction kettle in the step (3) is nitrogen atmosphere; the concentration of the sodium hydroxide solution is 2-4 mol/L; the concentration of the ammonia water solution is 2-4 mol/L.
The preparation method of the double-concentration-gradient-doped lithium ion battery cathode material is characterized in that in the step (3), the second salt solution is added into the first salt solution at a speed of 1.50-3.00L/h and is uniformly stirred.
The preparation method of the double-concentration gradient doped lithium ion battery cathode material is characterized in that in the step (4), the fourth salt solution is added into the third salt solution at the speed of 4.00-7.00L/h and is uniformly stirred.
The preparation method of the double-concentration gradient doped lithium ion battery anode material is characterized in that the rotation speed of the first coprecipitation reaction is 300-420 rpm; the rotation speed of the second coprecipitation reaction is 300-420 rpm.
The preparation method of the double-concentration gradient doped lithium ion battery anode material is characterized in that the process conditions of centrifugally washing and drying the solid-liquid mixture in the step (5) are as follows: the drying temperature is 100-160 ℃, and the drying time is 8-15 h.
The preparation method of the double-concentration gradient doped lithium ion battery anode material is characterized in that in the step (5), the solid-liquid mixture is sequentially subjected to centrifugal washing, drying, screening for iron removal, then is uniformly mixed with lithium hydroxide, and then is sequentially subjected to primary roasting and secondary roasting, wherein the primary roasting process conditions are as follows: heat treatment is carried out for 0-5h at the temperature of 200-600 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 5h to 15h at the temperature of 600 ℃ to 900 ℃; and keeping an oxygen atmosphere in the whole roasting process.
The invention has the beneficial technical effects that: according to the invention, other elements are synthesized and doped in two steps, the microstructure of precursor particles is adjusted, a precursor with uniform particle size, good sphericity and high tap density is obtained, and then the hydroxide precursor and lithium salt are uniformly mixed and sintered to obtain the double-concentration gradient doped lithium ion battery anode material, wherein the double-concentration gradient enables the nickel-rich particle core to have high capacity, and the insufficient nickel (or manganese-rich) surface to have cycle stability and thermal stability; other elements are doped to play a role in stabilizing the repulsion of nickel ions, increasing the structural stability of the material and reducing the oxygen release, or the shape and the size of primary particles are changed, and the microstructure of positive electrode particles is adjusted to reduce the capacity attenuation. The primary particles have a strong crystal structure. The c-axis of each acicular primary particle is parallel to the transverse axis of the primary particle so that the layers of each primary particle are aligned in the radial direction to facilitate Li migration. The unique microstructure of the positive electrode effectively suppresses the formation of microcracks and significantly improves cycling stability. Having poor cycle stability demonstrates a strong dependence between microcrack formation and microstructure configuration. The nickel-rich layered positive electrode is prepared by introducing boron into the NCM positive electrode and reasonably designing the microstructure, has high energy density and long cycle life, and is suitable for the next generation of EV. During first salt solution was gone into with the constant rate pump to second salt solution, first salt solution tank continuously stirred, and during first salt solution added reation kettle with the constant rate simultaneously, these two kinds of solutions can finish through the accurate control simultaneous feeding of autonomous control, and third salt solution is the same with fourth salt solution feeding mode, also finishes through the accurate control simultaneous feeding of autonomous control, and the material is not wasted.
Drawings
Fig. 1 is an SEM image of the dual concentration gradient doped precursor obtained in example 1.
Detailed Description
The invention relates to a double-concentration gradient doped lithium ion battery anode material, the chemical formula of which is LiNixCoyMnzM1-x-y-zO2Wherein x is more than 0.3 and less than 0.9, y is more than 0.01 and less than 0.15, z is more than 0.05 and less than 0.2, and M is carbon (C), boron (B), magnesium (Mg), calcium (Ca), tungsten (W), molybdenum (Mo), tantalum (Ta), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe) and copper (C)u), zirconium (Zr) and aluminum (Al).
The preparation method of the double-concentration gradient doped lithium ion battery anode material comprises the following steps:
(1) preparing a salt solution of nickel, cobalt and manganese, wherein the salt solution is one of a sulfate solution, a nitrate solution or a chloride solution. The salt solution comprises a first salt solution, a second salt solution, a third salt solution and a fourth salt solution, the molar ratio of nickel ions, cobalt ions and manganese ions in the first salt solution is (85-95) to (2-10), and the sum of the concentrations of the nickel ions, the cobalt ions and the manganese ions in the first salt solution is 2.00-5.00 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is (60-80): 10-20): 10-30, and the sum of the concentrations of the nickel ions, the cobalt ions and the manganese ions in the second salt solution is 2.00-5.00 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the third salt solution is (40-85): 5-30, and the sum of the concentrations of the nickel ions, the cobalt ions and the manganese ions in the third salt solution is 2.00-5.00 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the fourth salt solution is (30-70): (10-40): 10-40), and the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 2.00-5.00 mol/L.
(2) Preparing a doped salt solution, wherein the concentration of doping elements in the doped salt solution is 0.15-0.50 mol/L; the doping element in the doping salt solution is one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum.
(3) Adding the second salt solution into a storage tank of the first salt solution at a speed of 1.50-3.00L/h (Q2) and uniformly stirring to obtain a first mixed solution, adding the first mixed solution into a reaction kettle in a nitrogen atmosphere at a speed of 4.00-6.00L/h (Q1), simultaneously adding the doped salt solution into the reaction kettle in the nitrogen atmosphere at a speed of 2.00-4.00L/h, simultaneously adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle in the nitrogen atmosphere to perform a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is NiaCobMncX1-a-b-c(OH)2Wherein a is more than or equal to 0.4 and less than 0.85, b is more than 0.05 and less than 0.08, and 0.06C is less than 0.1, X is one or more of carbon (C), boron (B), magnesium (Mg), calcium (Ca), tungsten (W), molybdenum (Mo), tantalum (Ta), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr) and aluminum (Al). The concentration of the sodium hydroxide solution is 2-4 mol/L; the concentration of the ammonia water solution is 2-4 mol/L. The technological conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle under the nitrogen atmosphere is 5g/L-12g/L, the reaction pH is 10-12, the reaction time is 50h-80h, and the reaction rotating speed is 300rpm-420 rpm. The ratio of the volume of the first salt solution V1 to the volume of the second salt solution V2 is: V1/V2 ═ Q1-Q2)/Q2.
(4) And (3) when the first coprecipitation reaction is finished, starting an automatic program, namely immediately adding the fourth salt solution into a storage tank of the third salt solution at the speed of 4.00-7.00L/h (Q4) and uniformly stirring to obtain a second mixed solution, pumping the second mixed solution into the reaction kettle in the nitrogen atmosphere in the step (3) at the speed of 12.00-14.00L/h (Q3), simultaneously adding the doped salt solution into the reaction kettle in the nitrogen atmosphere at the speed of 2.00-4.00L/h, and carrying out a 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 under the nitrogen atmosphere is 7g/L-15g/L, the reaction pH is 10-11.5, the reaction time is 45h-60h, and the reaction rotating speed is 300rpm-420 rpm. The ammonium concentration and the pH value of the reaction kettle of the second coprecipitation reaction are maintained by continuously adding 2-4mol/L ammonia water solution and 2-4mol/L sodium hydroxide solution into the reaction kettle. The ratio of the volume V3 of the third salt solution to the volume V4 of the fourth salt solution is V3/V4 ═ Q3-Q4/Q4.
(5) And sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain the double-concentration gradient doped precursor. The chemical formula of the double-concentration gradient doped precursor is NixCoyMnzM1-x-y-z(OH)2Wherein x is more than 0.3 and less than 0.9, y is more than 0.01 and less than 0.15, z is more than 0.05 and less than 0.2, and M is at least more than 1 additive element of carbon (C), boron (B), magnesium (Mg), calcium (Ca), tungsten (W), molybdenum (Mo), tantalum (Ta), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr) and aluminum (Al). The drying temperature is 100-160 ℃, and the drying time is 8-15 h.
(6) Uniformly mixing the double-concentration gradient doped precursor and lithium hydroxide according to the molar ratio of 1: 1.05-1.2, roasting in a muffle furnace, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material. The whole roasting process is kept in an oxygen atmosphere, the roasting comprises primary roasting and secondary roasting which are sequentially carried out, and the primary roasting process conditions are as follows: heat treatment is carried out for 0-5h at the temperature of 200-600 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 5 to 15 hours at the temperature of 600 to 900 ℃.
(7) And testing the tap density, the discharge specific capacity, the capacity retention rate after circulation, the decomposition temperature, the heat release and the high-temperature circulation retention rate of the double-concentration gradient doped lithium ion battery anode material.
Example 1
Preparing sulfate solutions of nickel, cobalt and manganese in 4 proportions respectively; the salt solutions of nickel, cobalt and manganese with 4 proportions are respectively a first salt solution, a second salt solution, a third salt solution and a fourth salt solution. The molar ratio of nickel ions, cobalt ions and manganese ions in the first salt solution is 90: 5: 5, the total concentration of nickel ions, cobalt ions and manganese ions in the first salt solution is 2.00mol/L, and the molar ratio of the nickel ions, the cobalt ions and the manganese ions in the second salt solution is 80: 10: 10, the total concentration of nickel ions, cobalt ions and manganese ions in the second salt solution is 2.00mol/L, and the molar ratio of the nickel ions, the cobalt ions and the manganese ions in the third salt solution is 85: 10: 5, the total concentration of nickel ions, cobalt ions and manganese ions in the third salt solution is 2.00mol/L, and the molar ratio of the nickel ions, the cobalt ions and the manganese ions in the fourth salt solution is 70: 10: and 20, the total concentration of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 2.00 mol/L.
And preparing a doped salt solution, wherein the concentration of boron ions in the doped salt solution is 0.15mol/L, and the doping element in the doped salt solution is boron (B).
Adding 100L of second salt solution into a storage tank containing 150L of first salt solution at the speed of 2.00L/h, uniformly stirring to obtain a first mixed solution, simultaneously adding the first mixed solution into a reaction kettle in a nitrogen atmosphere at the speed of 5.00L/h, simultaneously adding a doping salt solution into the reaction kettle at the speed of 2.00L/h, and simultaneously adding a reverse reaction solutionAdding sodium hydroxide solution and ammonia water solution into a reaction kettle to carry out a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.83Co0.07Mn0.07B0.03(OH)2(ii) a The concentration of the sodium hydroxide solution is 4.00mol/L, the concentration of the ammonia water solution is 3.00mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 10g/L and 12g/L, the pH value of the reaction is between 11.6 and 12.0, the reaction time is 50h, and the rotating speed of the reaction is 420 rpm.
When the first coprecipitation reaction is finished, an automatic program is started, namely 240L of fourth salt solution is added into a storage tank containing 480L of third salt solution at the speed of 4.00L/h and is uniformly stirred to obtain a second mixed solution, the second mixed solution is pumped into the reaction kettle in the nitrogen atmosphere at the speed of 12.00L/h, simultaneously, a doping salt solution is added into the reaction kettle at the speed of 2.00L/h, and the second coprecipitation reaction is carried out 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 13g/L and 15g/L, the pH value of the reaction is between 11.0 and 11.4, the reaction time is 60 hours, and the rotating speed of the reaction is 400 rpm.
Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a double-concentration gradient doped precursor Ni0.80Co0.09Mn0.09B0.02(OH)2(ii) a The drying temperature is 110 ℃, and the drying time is 14 h.
Uniformly mixing the double-concentration gradient doped precursor and lithium hydroxide according to the molar ratio of 1: 1.08, roasting in a muffle furnace, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material. The whole roasting process is kept in an oxygen atmosphere, the roasting comprises primary roasting and secondary roasting which are sequentially carried out, and the primary roasting process conditions are as follows: heat treatment is carried out for 1h at the temperature of 600 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 15h at 900 ℃.
The tap density, the specific discharge capacity, the capacity retention rate after cycling, the decomposition temperature, the heat release and the high-temperature cycle retention rate of the double-concentration gradient doped lithium ion battery anode material are tested, and the test results are shown in tables 1 and 2.
Example 2
Preparing sulfate solutions of nickel, cobalt and manganese in 4 proportions respectively; the salt solutions of nickel, cobalt and manganese with 4 proportions are respectively a first salt solution, a second salt solution, a third salt solution and a fourth salt solution. The molar ratio of nickel ions, cobalt ions and manganese ions in the first salt solution is 95: 3: 2, the total concentration of nickel ions, cobalt ions and manganese ions in the first salt solution is 2.00mol/L, and the molar ratio of the nickel ions, the cobalt ions and the manganese ions in the second salt solution is 70: 10: 20, the total concentration of nickel ions, cobalt ions and manganese ions in the second salt solution is 2.00mol/L, and the molar ratio of the nickel ions, the cobalt ions and the manganese ions in the third salt solution is 75: 15: 10, the total concentration of nickel ions, cobalt ions and manganese ions in the third salt solution is 2.00mol/L, and the molar ratio of the nickel ions, the cobalt ions and the manganese ions in the fourth salt solution is 70: 15: 15, the total concentration of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 2.00 mol/L.
And preparing a doped salt solution, wherein the concentration of aluminum ions in the doped salt solution is 0.20mol/L, and the doping element in the doped salt solution is aluminum (Al).
Adding 150L of second salt solution into a storage tank containing 210L of first salt solution at the speed of 2.50L/h, uniformly stirring to obtain a first mixed solution, simultaneously adding the first mixed solution into a reaction kettle in a nitrogen atmosphere at the speed of 6.00L/h, simultaneously adding a doping salt solution into the reaction kettle at the speed of 2.50L/h, simultaneously adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle for carrying out a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.77Co0.05Mn0.09Al0.09(OH)2(ii) a The concentration of the sodium hydroxide solution is 3.50mol/L, the concentration of the ammonia water solution is 4.00mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 10.5g/L and 11.5g/L, the pH value of the reaction is between 11.4 and 11.8, the reaction time is 60 hours, and the rotating speed of the reaction is 400 rpm.
When the first coprecipitation reaction is finished, an automatic program is started, namely 350L of fourth salt solution is added into a storage tank containing 300L of third salt solution at the speed of 7.00L/h and is uniformly stirred to obtain a second mixed solution, meanwhile, the second mixed solution is pumped into the reaction kettle in the nitrogen atmosphere at the speed of 13.00L/h, simultaneously, a doping salt solution is added into the reaction kettle at the speed of 2.50L/h, and the second coprecipitation reaction is carried out 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 12g/L and 14g/L, the pH value of the reaction is between 10.8 and 11.2, the reaction time is 50h, and the rotating speed of the reaction is 370 rpm.
Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a double-concentration gradient doped precursor Ni0.72Co0.11Mn0.11Al0.06(OH)2(ii) a The drying temperature is 120 ℃, and the drying time is 11 h.
Uniformly mixing the double-concentration gradient doped precursor with lithium hydroxide according to the molar ratio of 1: 1.1, roasting in a muffle furnace, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material. The whole roasting process is kept in an oxygen atmosphere, the roasting comprises primary roasting and secondary roasting which are sequentially carried out, and the primary roasting process conditions are as follows: heat treatment is carried out for 5 hours at 200 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 10h at 700 ℃.
The tap density, the specific discharge capacity, the capacity retention rate after cycling, the decomposition temperature, the heat release and the high-temperature cycle retention rate of the double-concentration gradient doped lithium ion battery anode material are tested, and the test results are shown in tables 1 and 2.
Example 3
Preparing sulfate solutions of nickel, cobalt and manganese in 4 proportions respectively; the salt solutions of nickel, cobalt and manganese with 4 proportions are respectively a first salt solution, a second salt solution, a third salt solution and a fourth salt solution. The molar ratio of nickel ions, cobalt ions and manganese ions in the first salt solution is 92: 5: 3, the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the first salt solution is 2.17 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is 78: 12: 10, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the second salt solution is 2.56 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the third salt solution is 82: 10: 8, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the third salt solution is 2.44 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 65: 15: and 20, the total concentration of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 3.10 mol/L.
And preparing a doped salt solution, wherein the concentration of magnesium ions in the doped salt solution is 0.25mol/L, and the doping element in the doped salt solution is magnesium (Mg).
Adding 216L of second salt solution into a storage tank containing 180L of first salt solution at the speed of 3.00L/h, uniformly stirring to obtain a first mixed solution, simultaneously adding the first mixed solution into a reaction kettle in a nitrogen atmosphere at the speed of 5.50L/h, simultaneously adding a doping salt solution into the reaction kettle at the speed of 3.00L/h, simultaneously adding a sodium hydroxide solution and an ammonia water solution into the reaction kettle for carrying out a first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.74Co0.08Mn0.06Mg0.12(OH)2(ii) a The concentration of the sodium hydroxide solution is 2.55mol/L, the concentration of the ammonia water solution is 3.55mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 10.8 and 12.0g/L, the pH value of the reaction is 11.1 to 11.7, the reaction time is 72 hours, and the rotating speed of the reaction is 360 rpm.
When the first coprecipitation reaction is finished, an automatic program is started, namely 270L of fourth salt solution is added into a storage tank containing 360L of third salt solution at the speed of 6.00L/h and is uniformly stirred to obtain a second mixed solution, meanwhile, the second mixed solution is pumped into the reaction kettle at the speed of 14.00L/h, simultaneously, a doping salt solution is added into the reaction kettle at the speed of 3.00L/h, and a second coprecipitation reaction is carried out 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 11g/L and 12.5g/L, the pH value of the reaction is between 10.4 and 11.0, the reaction time is 45h, and the rotating speed of the reaction is 350 rpm.
Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a double-concentration gradient doped precursor Ni0.72Co0.10Mn0.11Mg0.07(OH)2(ii) a The drying temperature is 160 ℃, and the drying time is 8 h.
Uniformly mixing the double-concentration gradient doped precursor with lithium hydroxide according to the molar ratio of 1: 1.05, roasting in a muffle furnace, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material. The whole roasting process is kept in an oxygen atmosphere, the roasting comprises primary roasting and secondary roasting which are sequentially carried out, and the primary roasting process conditions are as follows: heat treatment is carried out for 4 hours at 300 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 12h at 650 ℃.
The tap density, the specific discharge capacity, the capacity retention rate after cycling, the decomposition temperature, the heat release and the high-temperature cycle retention rate of the double-concentration gradient doped lithium ion battery anode material are tested, and the test results are shown in tables 1 and 2.
Example 4
Sulfate solutions of nickel, cobalt and manganese with 4 proportions are prepared respectively, and salt solutions of nickel, cobalt and manganese with 4 proportions are respectively a first salt solution, a second salt solution, a third salt solution and a fourth salt solution. The molar ratio of nickel ions, cobalt ions and manganese ions in the first salt solution is 86: 7: 7, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the first salt solution is 2.33 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the second salt solution is 60: 15: 25, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the second salt solution is 3.33 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the third salt solution is 70: 10: 20, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the third salt solution is 2.86 mol/L; the molar ratio of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 40: 30: 30, the total concentration of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 5.00 mol/L.
And preparing a doped salt solution, wherein the concentration of chromium ions in the doped salt solution is 0.25mol/L, and the doping element in the doped salt solution is chromium (Cr).
Adding 120L of second salt solution into a storage tank containing 200L of first salt solution at the speed of 1.50L/h, uniformly stirring to obtain a first mixed solution, simultaneously adding the first mixed solution into a reaction kettle in a nitrogen atmosphere at the speed of 4.00L/h, simultaneously adding a doping salt solution into the reaction kettle at the speed of 4.00L/h, and simultaneously adding the doping salt solution into the reaction kettleAdding sodium hydroxide solution and ammonia water solution into the kettle to carry out first coprecipitation reaction to obtain a precursor core part, wherein the molecular formula of the precursor core part is Ni0.40Co0.05Mn0.08Cr0.47(OH)2(ii) a The concentration of the sodium hydroxide solution is 2.55mol/L, the concentration of the ammonia water solution is 3.55mol/L, and the process conditions of the first coprecipitation reaction are as follows: the ammonium concentration in the reaction kettle is kept between 5.5g/L and 10.0g/L, the pH value of the reaction is between 10.5 and 11.5, the reaction time is 80h, and the rotating speed of the reaction is 340 rpm.
When the first coprecipitation reaction is finished, starting an automatic program, namely immediately adding 325L of fourth salt solution into a storage tank containing 350L of third salt solution at the speed of 6.50L/h and uniformly stirring to obtain a second mixed solution, simultaneously pumping the second mixed solution into the reaction kettle at the speed of 13.50L/h, simultaneously adding a doped salt solution into the reaction kettle at the speed of 4.00L/h, and carrying out a 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 9.0g/L, the pH value of the reaction is between 10.5 and 11.4, the reaction time is 50h, and the rotating speed of the reaction is 320 rpm.
Sequentially carrying out centrifugal washing, drying and screening on the solid-liquid mixture for removing iron to obtain a double-concentration gradient doped precursor Ni0.42Co0.14Mn0.18Cr0.26(OH)2(ii) a The drying temperature is 140 ℃, and the drying time is 9.5 h.
Uniformly mixing the double-concentration gradient doped precursor with lithium hydroxide according to the molar ratio of 1: 1.06, roasting in a muffle furnace, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material. The whole roasting process is kept in an oxygen atmosphere, the roasting comprises primary roasting and secondary roasting which are sequentially carried out, and the primary roasting process conditions are as follows: heat treatment is carried out for 2.5h at 400 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 11h at 850 ℃.
The tap density, the specific discharge capacity, the capacity retention rate after cycling, the decomposition temperature, the heat release and the high-temperature cycle retention rate of the double-concentration gradient doped lithium ion battery anode material are tested, and the test results are shown in tables 1 and 2.
Comparative example 1
Preparing a salt solution containing nickel sulfate, cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions in the salt solution is 8: 1: and 1, the sum of the concentration of nickel ions, the concentration of cobalt ions and the concentration of manganese ions in the salt solution is 2 mol/L.
Adding 1100L of salt solution into a reaction kettle with a nitrogen atmosphere and a rotating speed of 330rpm at a speed of 10L/h, adding 9.00mol/L ammonia water serving as a complexing agent into the reaction kettle, simultaneously pumping 4mol/L NaOH solution into the reaction kettle, adjusting the flow rate of the alkali solution, keeping the pH value between 10.5 and 11.5, and carrying out coprecipitation reaction for 110h to obtain a precursor solid-liquid mixture.
Centrifugally separating and washing the solid-liquid mixture after reaction to be neutral, and drying for 15h at 120 ℃ to obtain a precursor Ni0.8Co0.1Mn0.1(OH)2。
Uniformly mixing the precursor and lithium hydroxide according to the molar ratio of 1: 1.15, roasting for 14 hours in a muffle furnace at 750 ℃, crushing and sieving the roasted material to obtain uniform LiNi0.8Co0.1Mn0.1O2A ternary material.
Testing LiNi0.8Co0.1Mn0.1O2The tap density, specific discharge capacity, capacity retention rate after cycling, decomposition temperature, heat release and high-temperature cycle retention rate of the ternary material are shown in tables 1 and 2.
The physical properties of the double-concentration gradient doped lithium ion battery anode materials obtained in examples 1 to 4 and the common ternary material obtained in comparative example 1 after calcination are compared, and the detection results are as follows:
table 1 physical properties of positive electrode materials for batteries obtained in examples 1 to 4 and comparative example 1
| pH | BET(m2/g) | Moisture (ppm) | Tap density (g/cm)3) | |
| Example 1 | 11.7 | 0.53 | 255.3 | 2.4 |
| Example 2 | 11.5 | 0.49 | 241.8 | 2.1 |
| Example 3 | 11.2 | 0.46 | 236.7 | 2.3 |
| Example 4 | 11.6 | 0.50 | 248.5 | 2.1 |
| Comparative example 1 | 10.8 | 0.55 | 273.3 | 1.9 |
From table 1, it can be derived: examples 1-4 had lower moisture than the comparative example 1 sample, while examples 1-4 had a higher pH than the comparative example 1 sample. Generally, the pH value of the lithium ion battery anode material is lower than 11, and lithium precipitation is likely to be caused during the charge and discharge test of the material, so that capacity attenuation is further caused; the higher tap densities of the samples of examples 1-4 compared to the comparative sample indicate a higher cell capacity.
Assembling a button cell and detecting:
the positive electrode materials of the double-concentration gradient doped lithium ion batteries obtained in the examples 1 to 4 and the common ternary material obtained in the comparative example 1 are used as the positive electrode and the metal lithium sheet is used as the negative electrode, and are respectively assembled into 5 button batteries to carry out charge-discharge comparative tests, 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: by adopting the dual-concentration gradient doped lithium ion battery anode material obtained in the embodiments 1 to 4 as an anode and a metal lithium sheet as a cathode to assemble a button battery for charge-discharge comparative test, the first discharge specific capacity can reach 205.4mAh/g under 0.1C multiplying power, the capacity retention rate can reach 99.8% after 100 charge-discharge cycles, the capacity retention rate can still reach 95.9% after 50 ℃ high-temperature cycles, while the first discharge specific capacity of the common high-nickel anode material is 189.3mAh/g, the capacity retention rate is 93.2% after 100 charge-discharge cycles, and the capacity retention rate is 85.4% after 50 ℃ high-temperature cycles; therefore, the specific discharge capacity and the cycle performance of the battery prepared from the doped double-concentration gradient lithium ion battery anode material obtained by the invention are superior to those of the battery prepared from the conventional high-nickel battery anode material.
Claims (10)
1. The double-concentration gradient doped lithium ion battery anode material is characterized in that the chemical formula of the material is LiNixCoyMnzM1-x-y-zO2Wherein x is more than 0.3 and less than 0.9, y is more than 0.01 and less than 0.15, z is more than 0.05 and less than 0.2, and M is one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum.
2. The preparation method of the double-concentration-gradient doped lithium ion battery cathode material according to claim 1, characterized by comprising the following steps:
(1) preparing a first salt solution, a second salt solution, a third salt solution and a fourth salt solution with the molar ratio of nickel ions, cobalt ions and manganese ions of (85-95), (2-10), (60-80), (10-20), (10-30), (40-85), (5-30) and (30-70), (10-40) and (10-40);
(2) preparing a doping salt solution with the doping element concentration of 0.15-0.50 mol/L;
(3) adding the second salt solution into the first salt solution, stirring to obtain a first mixed solution, and adding the first mixed solution, the doped salt solution, the sodium hydroxide solution and the ammonia water solution into the reaction kettle to perform a first coprecipitation reaction; the rates of adding the first mixed solution and the doped salt solution into the reaction kettle are 4.00-6.00L/h and 2.00-4.00L/h respectively; the technological conditions of the first coprecipitation reaction are as follows: the concentration of ammonium in the reaction kettle is 5-12g/L, the pH value of the reaction is 10-12, and the reaction time is 50-80 h;
(4) when the first coprecipitation reaction is finished, adding a fourth salt solution into a third salt solution, stirring to obtain a second mixed solution, adding the second mixed solution and a doped salt solution into the reaction kettle, and carrying out a second coprecipitation reaction to obtain a solid-liquid mixture; the rates of adding the second mixed solution and the doped salt solution into the reaction kettle are respectively 12.00-14.00L/h and 2.00-4.00L/h; the process conditions of the second coprecipitation reaction are as follows: the concentration of ammonium in the reaction kettle is 7-15g/L, the pH value of the reaction is 10-11.5, and the reaction time is 45-60 h;
(5) and sequentially carrying out centrifugal washing, drying, screening and deironing on the solid-liquid mixture, mixing the solid-liquid mixture with lithium hydroxide according to the molar ratio of 1 (1.05-1.2), roasting, cooling, crushing and sieving to obtain the double-concentration gradient doped lithium ion battery anode material.
3. The preparation method of the double-concentration-gradient-doped lithium ion battery cathode material according to claim 2, wherein the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the first salt solution in the step (1) is 2.00-5.00 mol/L; the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the second salt solution is 2.00-5.00 mol/L; the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the third salt solution is 2.00-5.00 mol/L; the sum of the concentrations of nickel ions, cobalt ions and manganese ions in the fourth salt solution is 2.00-5.00 mol/L; the salt solution is one of sulfate solution, nitrate solution and chloride solution.
4. The preparation method of the double concentration gradient doped lithium ion battery cathode material according to claim 2, wherein the doping elements in the doping salt solution in the step (2) are one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum; obtaining a precursor core after the first coprecipitation reaction in the step (3), wherein the chemical formula of the precursor core is NiaCobMncX1-a-b-c(OH)2Wherein a is more than or equal to 0.4 and less than 0.85, b is more than 0.05 and less than 0.08, c is more than 0.06 and less than 0.1, and X is one or more of carbon, boron, magnesium, calcium, tungsten, molybdenum, tantalum, strontium, barium, titanium, vanadium, chromium, iron, copper, zirconium and aluminum.
5. The preparation method of the double-concentration-gradient doped lithium ion battery cathode material according to claim 2, wherein the atmosphere in the reaction kettle in the step (3) is a nitrogen atmosphere; the concentration of the sodium hydroxide solution is 2-4 mol/L; the concentration of the ammonia water solution is 2-4 mol/L.
6. The preparation method of the dual concentration gradient doped lithium ion battery cathode material as claimed in claim 2, wherein the second salt solution is added into the first salt solution at a rate of 1.50-3.00L/h in the step (3) and stirred uniformly.
7. The preparation method of the dual concentration gradient doped lithium ion battery cathode material as claimed in claim 2, wherein the fourth salt solution is added into the third salt solution at a rate of 4.00-7.00L/h in the step (4) and stirred uniformly.
8. The method for preparing the dual-concentration-gradient doped lithium ion battery anode material as claimed in claim 2, wherein the rotation speed of the first co-precipitation reaction is 300-420 rpm; the rotation speed of the second coprecipitation reaction is 300-420 rpm.
9. The preparation method of the double-concentration-gradient doped lithium ion battery cathode material according to claim 2, wherein the process conditions of centrifugally washing and drying the solid-liquid mixture in the step (5) are as follows: the drying temperature is 100-160 ℃, and the drying time is 8-15 h.
10. The preparation method of the double-concentration-gradient-doped lithium ion battery cathode material according to claim 2, wherein in the step (5), the solid-liquid mixture is sequentially subjected to centrifugal washing, drying, screening for iron removal, then is uniformly mixed with lithium hydroxide, and then is sequentially subjected to primary roasting and secondary roasting, wherein the primary roasting process conditions are as follows: heat treatment is carried out for 0-5h at the temperature of 200-600 ℃, and the secondary roasting process conditions are as follows: heat treatment is carried out for 5h to 15h at the temperature of 600 ℃ to 900 ℃; and keeping an oxygen atmosphere in the whole roasting process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011484337.6A CN112599781B (en) | 2020-12-15 | 2020-12-15 | Double-concentration gradient doped lithium ion battery anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011484337.6A CN112599781B (en) | 2020-12-15 | 2020-12-15 | Double-concentration gradient doped lithium ion battery anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112599781A true CN112599781A (en) | 2021-04-02 |
| CN112599781B CN112599781B (en) | 2022-05-13 |
Family
ID=75196172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011484337.6A Active CN112599781B (en) | 2020-12-15 | 2020-12-15 | Double-concentration gradient doped lithium ion battery anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112599781B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113772749A (en) * | 2021-11-15 | 2021-12-10 | 中南大学 | Double-gradient-structure nickel-cobalt-manganese ternary positive electrode material precursor, preparation method thereof and ternary positive electrode material |
| CN113860321A (en) * | 2021-08-23 | 2021-12-31 | 中南大学 | Preparation method of regenerated precursor material of waste lithium cobaltate battery |
| CN114408983A (en) * | 2021-12-24 | 2022-04-29 | 合肥国轩电池材料有限公司 | Lithium transition metal oxide and preparation method and application thereof |
| CN114455647A (en) * | 2022-01-24 | 2022-05-10 | 浙江格派钴业新材料有限公司 | Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material |
| CN114530588A (en) * | 2022-04-21 | 2022-05-24 | 浙江帕瓦新能源股份有限公司 | Multi-element concentration gradient doped precursor material, preparation method thereof and anode material |
| CN114843504A (en) * | 2022-06-08 | 2022-08-02 | 中南大学 | Single-crystal-morphology lithium ion battery ternary positive electrode material and preparation method and application thereof |
| CN115340133A (en) * | 2022-08-10 | 2022-11-15 | 宁波容百新能源科技股份有限公司 | Molybdenum-doped nickel-rich ternary precursor and preparation method thereof |
| CN115385390A (en) * | 2022-08-08 | 2022-11-25 | 南通金通储能动力新材料有限公司 | Method for regulating section aperture structure of high-nickel anode material |
| CN116314731A (en) * | 2023-05-24 | 2023-06-23 | 浙江帕瓦新能源股份有限公司 | Sodium ion battery anode material, precursor thereof, preparation method and application |
| CN116646518A (en) * | 2023-07-25 | 2023-08-25 | 深圳海辰储能控制技术有限公司 | Positive electrode active material, preparation method, pole piece, energy storage device and power utilization device |
| WO2024171689A1 (en) * | 2023-02-16 | 2024-08-22 | 株式会社田中化学研究所 | Metal complex compound, and positive electrode active material using metal complex compound as precursor |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017037713A (en) * | 2015-08-06 | 2017-02-16 | トヨタ自動車株式会社 | Method of manufacturing positive electrode active material for nonaqueous electrolyte secondary battery |
| CN109411718A (en) * | 2018-09-28 | 2019-03-01 | 佛山市德方纳米科技有限公司 | The preparation method of the tertiary cathode material of doping vario-property |
| CN109585845A (en) * | 2018-11-30 | 2019-04-05 | 林奈（中国）新能源有限公司 | NCM-NCMA positive electrode, preparation method and purposes |
| CN109626447A (en) * | 2018-12-13 | 2019-04-16 | 南开大学 | Nickelic anode material for lithium-ion batteries of a kind of concentration gradient magnesium doping and preparation method thereof |
| CN110112399A (en) * | 2019-05-22 | 2019-08-09 | 武汉理工大学 | A kind of effective method of modifying for promoting business tertiary cathode material cyclical stability |
| CN110518220A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | A kind of nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode and preparation method |
| CN110518219A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method |
| CN110540254A (en) * | 2019-07-29 | 2019-12-06 | 中南大学 | Boron-magnesium co-doped gradient nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN110828817A (en) * | 2019-11-18 | 2020-02-21 | 中科(马鞍山)新材料科创园有限公司 | High-nickel-concentration gradient lithium battery ternary precursor and preparation method and application thereof |
| CN111628149A (en) * | 2020-06-02 | 2020-09-04 | 格林美股份有限公司 | Gradient-doped high-nickel ternary positive electrode material and preparation method thereof |
-
2020
- 2020-12-15 CN CN202011484337.6A patent/CN112599781B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017037713A (en) * | 2015-08-06 | 2017-02-16 | トヨタ自動車株式会社 | Method of manufacturing positive electrode active material for nonaqueous electrolyte secondary battery |
| CN109411718A (en) * | 2018-09-28 | 2019-03-01 | 佛山市德方纳米科技有限公司 | The preparation method of the tertiary cathode material of doping vario-property |
| CN109585845A (en) * | 2018-11-30 | 2019-04-05 | 林奈（中国）新能源有限公司 | NCM-NCMA positive electrode, preparation method and purposes |
| CN109626447A (en) * | 2018-12-13 | 2019-04-16 | 南开大学 | Nickelic anode material for lithium-ion batteries of a kind of concentration gradient magnesium doping and preparation method thereof |
| CN110112399A (en) * | 2019-05-22 | 2019-08-09 | 武汉理工大学 | A kind of effective method of modifying for promoting business tertiary cathode material cyclical stability |
| CN110540254A (en) * | 2019-07-29 | 2019-12-06 | 中南大学 | Boron-magnesium co-doped gradient nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN110518220A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | A kind of nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode and preparation method |
| CN110518219A (en) * | 2019-09-04 | 2019-11-29 | 中南大学 | The nickelic gradient nickel cobalt manganese aluminium quaternary positive electrode of core-shell structure and preparation method |
| CN110828817A (en) * | 2019-11-18 | 2020-02-21 | 中科(马鞍山)新材料科创园有限公司 | High-nickel-concentration gradient lithium battery ternary precursor and preparation method and application thereof |
| CN111628149A (en) * | 2020-06-02 | 2020-09-04 | 格林美股份有限公司 | Gradient-doped high-nickel ternary positive electrode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴宇平等编著: "《锂离子电池—应用与实践》", 31 January 2012 * |
| 董生德，周园，海春喜: ""锂离子电池镍钴锰三元正极材料研究进展"", 《电池》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113860321A (en) * | 2021-08-23 | 2021-12-31 | 中南大学 | Preparation method of regenerated precursor material of waste lithium cobaltate battery |
| CN113772749A (en) * | 2021-11-15 | 2021-12-10 | 中南大学 | Double-gradient-structure nickel-cobalt-manganese ternary positive electrode material precursor, preparation method thereof and ternary positive electrode material |
| CN114408983A (en) * | 2021-12-24 | 2022-04-29 | 合肥国轩电池材料有限公司 | Lithium transition metal oxide and preparation method and application thereof |
| CN114455647A (en) * | 2022-01-24 | 2022-05-10 | 浙江格派钴业新材料有限公司 | Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material |
| CN114530588A (en) * | 2022-04-21 | 2022-05-24 | 浙江帕瓦新能源股份有限公司 | Multi-element concentration gradient doped precursor material, preparation method thereof and anode material |
| CN114843504A (en) * | 2022-06-08 | 2022-08-02 | 中南大学 | Single-crystal-morphology lithium ion battery ternary positive electrode material and preparation method and application thereof |
| CN115385390B (en) * | 2022-08-08 | 2023-11-14 | 南通金通储能动力新材料有限公司 | Method for regulating and controlling section pore diameter structure of high-nickel positive electrode material |
| CN115385390A (en) * | 2022-08-08 | 2022-11-25 | 南通金通储能动力新材料有限公司 | Method for regulating section aperture structure of high-nickel anode material |
| CN115340133A (en) * | 2022-08-10 | 2022-11-15 | 宁波容百新能源科技股份有限公司 | Molybdenum-doped nickel-rich ternary precursor and preparation method thereof |
| CN115340133B (en) * | 2022-08-10 | 2023-11-10 | 宁波容百新能源科技股份有限公司 | Molybdenum-doped nickel-rich ternary precursor and preparation method thereof |
| WO2024171689A1 (en) * | 2023-02-16 | 2024-08-22 | 株式会社田中化学研究所 | Metal complex compound, and positive electrode active material using metal complex compound as precursor |
| CN116314731B (en) * | 2023-05-24 | 2023-08-15 | 浙江帕瓦新能源股份有限公司 | Sodium ion battery anode material, precursor thereof, preparation method and application |
| CN116314731A (en) * | 2023-05-24 | 2023-06-23 | 浙江帕瓦新能源股份有限公司 | Sodium ion battery anode material, precursor thereof, preparation method and application |
| CN116646518A (en) * | 2023-07-25 | 2023-08-25 | 深圳海辰储能控制技术有限公司 | Positive electrode active material, preparation method, pole piece, energy storage device and power utilization device |
| CN116646518B (en) * | 2023-07-25 | 2024-03-01 | 深圳海辰储能控制技术有限公司 | Positive electrode active material, preparation method, pole piece, energy storage device and power utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112599781B (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112599781B (en) | Double-concentration gradient doped lithium ion battery anode material and preparation method thereof | |
| CN111916687B (en) | Positive electrode material, preparation method thereof and lithium ion battery | |
| CN115000399B (en) | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN112164784B (en) | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof | |
| CN112928253B (en) | Nickel-manganese-titanium composite material and preparation method and application thereof | |
| CN106257718B (en) | A kind of BN cladding is without cobalt Ni-Mn solid solution nickel hydroxide base anode materials | |
| CN102683645A (en) | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN114349068B (en) | Preparation method of large-particle-size nickel-cobalt-aluminum ternary positive electrode material precursor | |
| CN113644272A (en) | Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof | |
| WO2024178793A1 (en) | Modified sodium-ion battery positive electrode precursor, and preparation method therefor and use thereof | |
| WO2024055519A1 (en) | Preparation method and use of lithium manganese iron phosphate | |
| CN111106343A (en) | Lanthanum and fluorine co-doped high-nickel ternary cathode material and preparation method and application thereof | |
| CN114162881A (en) | Preparation method of anion in-situ doped high-nickel ternary cathode material | |
| CN114873657B (en) | Preparation method and application of modified lithium-rich manganese-based positive electrode material | |
| CN116282228A (en) | Sodium ion precursor material and preparation method and application thereof | |
| CN117133906A (en) | Coated oxygen-site doped modified sodium ion battery positive electrode material and preparation method thereof | |
| CN117219751A (en) | Nickel-iron-manganese-based layered positive electrode material of radial sodium ion battery, preparation method of nickel-iron-manganese-based layered positive electrode material and sodium ion battery | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN114031127B (en) | Mg-Ti co-doped high-nickel cobalt-free precursor and preparation method thereof | |
| CN114906881A (en) | Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material | |
| CN108232185B (en) | Synthetic method of liquid-phase doped ternary precursor | |
| CN113845154B (en) | Positive electrode solid solution material precursor, and preparation method and application thereof | |
| CN113471423B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN115231626B (en) | Cobalt-free high-nickel NMA ternary positive electrode 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |