CN112467127A - Coating modified lithium ion ternary cathode material and preparation method thereof - Google Patents
Coating modified lithium ion ternary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a coating modified lithium ion single crystal ternary anode material and a preparation method thereof, wherein a carbon material with high conductivity is coated on the surface of the single crystal ternary anode material, and the method comprises the following steps: firstly, mixing a single crystal ternary cathode material with a carbon material with high conductivity according to a certain proportion, carrying out solvent evaporation induced self-assembly coating, and sintering to obtain a coating modified single crystal ternary cathode material. According to the invention, a conductive network is formed on the surface of the substrate in a liquid mixed coating mode for modifying the single crystal anode material of the lithium ion battery, so that the electrochemical performance of the single crystal ternary anode material is obviously improved.
Description
Technical Field
The invention belongs to the field of lithium battery materials, and particularly relates to a coating modified lithium ion ternary cathode material and a preparation method thereof.
Background
With the cost pressure brought by the new subsidy policy on the improvement of high energy density, high driving mileage and safety performance and the subsidy grade withdrawal, various new energy vehicle enterprises accelerate the replacement of the power battery of the original system, namely a high-nickel low-cobalt ternary power battery and a regression lithium iron phosphate power battery for safety consideration. At present, the market of power batteries mainly focuses on the development of medium-nickel and low-cobalt materials, such as ternary 613 series single crystals, 613 series secondary ball products, 712 series single crystal products and the like, but the power battery materials require higher energy density, excellent overcharge resistance, long cycle performance and the like. Therefore, the research on the practical application of the medium and high nickel single crystal ternary material with high voltage, high capacity and good long cycle stability in the lithium ion battery has very important significance.
The invention is prepared by reacting LicNiaCobMn1-a-bMfO2Doping and coating modification are carried out, the layered structure of the material is stabilized through a series of preparation methods, the phase change of the material in the process of multiple charging and discharging is inhibited, and the single crystal anode material with high capacity and long cycle stability is provided.
Disclosure of Invention
In view of the above, the invention provides a coating modified lithium ion single crystal ternary cathode material and a preparation method thereof, the lithium ion single crystal ternary cathode material provided by the invention has the advantages of small primary particle, good roundness, narrow diameter distance and good conductivity of the material, and a lithium ion battery prepared from the coating modified single crystal ternary cathode material has higher capacity and long cycle stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a coating modified lithium ion ternary positive electrode material comprises a positive electrode material core and a coating agent coated on the surface of the positive electrode material core, wherein the coating agent accounts for 0.5-5% of the total weight of the positive electrode material core;
the chemical general formula of the anode material core is LicNiaCobMn1-a-bMfO2Wherein c is more than or equal to 0.9 and less than or equal to 1.2, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and a + b<F is more than or equal to 1, 0.01 and less than or equal to 0.10; m is a doping element;
the coating agent is obtained by mixing a solution containing a carbon source and a template agent, wherein the carbon source accounts for 50-70% of the weight of the template agent.
Preferably, the coating-modified lithium ion ternary positive electrode material is formed by mixing primary single crystal particles, secondary particles formed by aggregating the primary single crystal particles, and aggregated primary particles.
Preferably, the doping element is a composite of any one of Zr, Ti, Mg, Zn, La, Y, B, V, Ca, or Al and another metal element, or a mixture of one or more of an oxide, a hydroxide, a metallo-organic compound, and a phosphate containing the same.
More preferably, the doping element is an oxide containing Zr, Ti, Mg, or Al.
Preferably, the carbon source is one or a mixture of glucose, polyacrylonitrile, sucrose and phenolic resin;
more preferably, the carbon source is a phenol resin or polyacrylonitrile.
Preferably, the solvent in the solution is one or a mixture of more of deionized water, alcohols, dimethylformamide and ethylene carbonate;
more preferably, the solvent in the solution is ethanol or dimethylformamide.
Preferably, the template agent is one or a mixture of more of a polystyrene colloidal crystal template, P123 and F127;
more preferably, the template is P123 or F127.
The preparation method of the coating modified lithium ion ternary cathode material comprises the following steps:
(1) primary sintering: lithium source, monocrystal precursor and doping element are mixed according to the chemical general formula LicNiaCobMn1-a- bMfO2Mixing the materials according to the ratio, then placing the materials into a furnace for sintering, and carrying out the procedures of crushing, sieving and deironing on the sintered materials to obtain a primary sintering material;
(2) coating and sintering: ultrasonically mixing a solution containing a carbon source and a template agent to obtain a coating agent, putting a primary sintering material into a stirring kettle containing the solvent, uniformly stirring and mixing, performing suction filtration and drying to obtain an anode material core, adding the coating agent into the anode material core, stirring and dispersing to obtain mixed slurry, then performing a solvent evaporation induction self-assembly process on the mixed slurry at 50-70 ℃ under a vacuum condition to obtain a primary product, and finally sintering the primary product to obtain the coating modified lithium ions.
Preferably, the sintering temperature in the step (1) is 800-950 ℃, the time is 6-15h, and the sintering atmosphere is a mixed atmosphere or air with 30-70% of oxygen volume.
Preferably, the lithium source in step (1) comprises a mixture of one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium oxalate.
Preferably, the solvent in the stirring kettle in the step (2) is 20-50 wt% ethanol water solution or deionized water.
Preferably, the ultrasonic mixing in the step (2) is carried out, the ultrasonic power is 35W, and the ultrasonic time is 15 min.
Preferably, the sintering of the primary product in the step (2) specifically includes: firstly, carrying out pre-oxidation treatment at the pre-oxidation temperature of 90-320 ℃ for 1.5-3.5h, then carrying out pre-carbonization treatment at the pre-carbonization temperature of 550 ℃ and the pre-carbonization time of 1.5-3.5h, and then carrying out carbonization treatment at the carbonization temperature of 550 ℃ and 800 ℃ for 1-3 h.
Preferably, the pre-oxidation atmosphere is an air atmosphere containing 3 to 12% by volume of oxygen, and the pre-carbonization and carbonization atmosphere is a nitrogen or argon atmosphere.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
in the invention, the single crystal anode material reduces the phenomenon of cation mixing and discharging by doping elements in the primary sintering stage, thereby stabilizing the material structure; after the surface of the single crystal anode material is treated, the carbon coating modification of the single crystal ternary anode material is completed by utilizing the solvent evaporation self-assembly process, so that the conductivity and the cycle performance of the battery material are improved; the lithium ion battery prepared by the anode material has higher service voltage, high capacity and good long cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of a single crystal positive electrode material of a modified lithium ion battery prepared in example 1 of the present invention;
FIG. 2 is a first charge-discharge curve diagram of a half cell of the modified single-crystal ternary positive electrode material for a lithium ion battery prepared in example 1 of the present invention at 3.0-4.35V and 0.1C;
FIG. 3 is a graph of the cycle capacity retention rate at 45 ℃ of 3.0-4.35V, 0.5C of a half cell of the modified single crystal ternary cathode material of the lithium ion battery prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a coating modified single crystal ternary cathode material:
primary sintering: lithium carbonate, single crystal precursor and Zr-doped substance are mixed according to the molecular formula LicNiaCobMn1-a- bMfO2Mixing materials according to a medium proportion, wherein c is 1.07, a is 0.70, b is 0.10, f is 0.01, the sintering temperature is controlled to be 895 ℃, the sintering time is 10 hours, the sintering atmosphere is oxygen, cooling, crushing, sieving and deironing the sintered materials to obtain primary sintered materials;
coating and sintering: mixing ethanol solution containing phenolic resin and F127 at weight ratio of 70% under 35W power for 15min, and using as coating agent; adding 1kg of primary sintering material into a stirring kettle containing 50 wt% ethanol water solution (3kg), stirring and mixing uniformly, then carrying out suction filtration and drying to obtain an anode material core; adding the coating agent into the positive electrode material core according to the weight ratio of 0.8%, and fully stirring and dispersing to obtain mixed slurry; then, carrying out a solvent evaporation induced self-assembly process on the obtained mixed slurry at the temperature of 70 ℃ under a vacuum condition to obtain a carbon-coated primary positive electrode material microcapsule product; finally, sintering the obtained primary positive electrode material microcapsule product, specifically, carrying out pre-oxidation treatment under the condition of dilute oxygen atmosphere, wherein the pre-oxidation temperature is 350 ℃, and the pre-oxidation time is 1 h; then heating to carry out pre-carbonization and carbonization, wherein the atmosphere condition is nitrogen inert gas, the pre-carbonization temperature is 550 ℃, and the pre-carbonization time is 2 hours; the carbonization temperature is 800 ℃, the carbonization time is 2.5h, and the final coating modified single crystal ternary cathode material is obtained. The results of the performance tests of the batteries made with this material are shown in table 1.
Example 2
Preparing a coating modified single crystal ternary cathode material:
primary sintering: lithium hydroxide, a single crystal precursor and a Zr element-doped substance are mixed according to the formulaFormula LicNiaBobMn1-a- bMfO2Mixing materials according to a medium proportion, wherein c is 1.05, a is 0.60, b is 0.10, f is 0.01, the sintering temperature is controlled to be 910 ℃, the sintering time is 11h, the sintering atmosphere is an air atmosphere with the oxygen volume ratio of 40%, cooling, crushing, sieving and deironing the sintered materials to obtain a primary sintering material;
coating and sintering: ultrasonically mixing ethanol solution containing phenolic resin and P123 according to the weight ratio of 55% for 15min under the power of 35W, and using the mixture as a coating agent; taking 1kg of primary sintering material, stirring and mixing uniformly in a stirring kettle (3kg) containing 20 wt% ethanol water solution, then carrying out suction filtration and drying to obtain an anode material core; adding the coating agent into the positive electrode material core according to the weight ratio of 0.55%, and fully stirring and dispersing to obtain mixed slurry; then, carrying out a solvent evaporation induced self-assembly process on the obtained mixed slurry at the temperature of 50 ℃ under a vacuum condition to obtain a carbon-coated primary positive electrode material microcapsule product; finally, sintering the obtained primary positive electrode material microcapsule product, specifically, carrying out pre-oxidation treatment under the condition of dilute oxygen atmosphere, wherein the pre-oxidation temperature is 300 ℃, and the pre-oxidation time is 1.5 h; then heating to carry out pre-carbonization and carbonization, wherein the atmosphere condition is nitrogen inert gas, the pre-carbonization temperature is 550 ℃, and the pre-carbonization time is 2 hours; the carbonization temperature is 780 ℃ and the carbonization time is 3h, so that the final coated and modified single crystal ternary cathode material is obtained. The results of the performance tests of the batteries made with this material are shown in table 1.
Example 3
Preparing a coating modified single crystal ternary cathode material:
primary sintering: lithium nitrate, monocrystal precursor and Y-doped substance are mixed according to the molecular formula LicNiaCobMn1-a- bMfO2Mixing materials according to a medium proportion, wherein c is 1.05, a is 0.60, b is 0.10, f is 0.01, the sintering temperature is controlled to be 910 ℃, the sintering time is 11h, the sintering atmosphere is air, and after cooling, the sintered materials are subjected to crushing, sieving and iron removal processes to obtain primary sintered materials;
coating and sintering: ultrasonically mixing ethanol solution containing polyacrylonitrile and P123 at a weight ratio of 55% under 35W for 15min to serve as a coating agent; taking 1kg of primary sintering material, stirring and mixing uniformly in a stirring kettle (3kg) containing 30 wt% ethanol water solution, then carrying out suction filtration and drying to obtain an anode material core; adding the coating agent into the positive electrode material core according to the weight ratio of 0.55%, and fully stirring and dispersing to obtain mixed slurry; then, carrying out a solvent evaporation induced self-assembly process on the obtained mixed slurry at the temperature of 50 ℃ under a vacuum condition to obtain a carbon-coated primary positive electrode material microcapsule product; finally, sintering the obtained primary positive electrode material microcapsule product, specifically, carrying out pre-oxidation treatment under the condition of dilute oxygen atmosphere, wherein the pre-oxidation temperature is 300 ℃, and the pre-oxidation time is 1.5 h; then heating to carry out pre-carbonization and carbonization, wherein the atmosphere condition is nitrogen inert gas, the pre-carbonization temperature is 550 ℃, and the pre-carbonization time is 2 hours; the carbonization temperature is 780 ℃ and the carbonization time is 3h, so that the final coated and modified single crystal ternary cathode material is obtained. The results of the performance tests of the batteries made with this material are shown in table 1.
Example 4
Preparing a coating modified single crystal ternary cathode material:
primary sintering: lithium oxalate, single crystal precursor and Mg-doped substance are mixed according to the molecular formula LicNiaCobMn1-a- bMfO2Mixing materials according to a medium proportion, wherein c is 1.10, a is 0.70, b is 0.10, f is 0.03, the sintering temperature is controlled to be 900 ℃, the sintering time is 11h, the sintering atmosphere is oxygen, cooling, crushing, sieving and deironing the sintered materials to obtain primary sintered materials;
coating and sintering: ultrasonically mixing ethanol solution containing polyacrylonitrile and P123/F123 according to the weight ratio of 60% for 15min under the power of 35W, and using the mixture as a coating agent; taking 1kg of material A obtained in the primary sintering stage, uniformly stirring and mixing the material A in a stirring kettle containing 3kg of deionized water, then carrying out suction filtration and drying to obtain an anode material core; adding the coating agent into the positive electrode material core according to the weight ratio of 0.45%, and fully stirring and dispersing to obtain mixed slurry; then, carrying out a solvent evaporation induced self-assembly process on the obtained mixed slurry at the temperature of 60 ℃ under a vacuum condition to obtain a carbon-coated primary positive electrode material microcapsule product; finally, sintering the obtained primary positive electrode material microcapsule product, and carrying out pre-oxidation treatment under the condition of dilute oxygen atmosphere, wherein the pre-oxidation temperature is 320 ℃, and the pre-oxidation time is 1 h; then heating to carry out pre-carbonization and carbonization, wherein the atmosphere condition is nitrogen inert gas, the pre-carbonization temperature is 600 ℃, and the pre-carbonization time is 1.5 h; the carbonization temperature is 750 ℃, the carbonization time is 3.5h, and the final coating modified single crystal ternary cathode material is obtained. The results of the performance tests of the batteries made with this material are shown in table 1.
Example 5
Preparing a coating modified single crystal ternary cathode material:
primary sintering: mixing a mixture of lithium carbonate and lithium nitrate, a single crystal precursor and an Al element-doped substance according to a molecular formula LicNiaCobMn1-a-bMfO2Mixing materials according to a medium proportion, wherein c is 1.12, a is 0.70, b is 0.10, f is 0.05, M is a doping element, the sintering temperature is controlled to be 905 ℃, the sintering time is 10.5h, the sintering atmosphere is oxygen, and after cooling, the sintered material is subjected to the working procedures of crushing, sieving, iron removal and the like to obtain a primary sintered material;
coating and sintering: ultrasonically mixing ethanol solution containing phenolic resin and polyacrylonitrile and a polystyrene colloidal crystal template according to the weight ratio of 50 percent, and using the mixture as a coating agent; taking 1kg of material A obtained in the primary sintering stage, uniformly stirring and mixing the material A in a stirring kettle containing 3kg of deionized water, then carrying out suction filtration and drying to obtain an anode material core; adding the coating agent into the positive electrode material core according to the weight ratio of 0.55%, and fully stirring and dispersing to obtain mixed slurry; then, carrying out a solvent evaporation induced self-assembly process on the obtained mixed slurry at the temperature of 65 ℃ under a vacuum condition to obtain a carbon-coated primary positive electrode material microcapsule product; finally, sintering the obtained primary positive electrode material microcapsule product, and carrying out pre-oxidation treatment under the condition of dilute oxygen atmosphere, wherein the pre-oxidation temperature is 380 ℃, and the pre-oxidation time is 1 h; then heating to carry out pre-carbonization and carbonization, wherein the atmosphere condition is nitrogen inert gas, the pre-carbonization temperature is 600 ℃, and the pre-carbonization time is 1.5 h; the carbonization temperature is 700 ℃, the carbonization time is 3h, and the final coating modified single crystal ternary cathode material is obtained. The results of the performance tests of the batteries made with this material are shown in table 1.
Comparative example 1
Lithium hydroxide and nickel cobalt manganese hydroxide precursor Ni0.6Co0.1Mn0.3(OH)2Uniformly ball-milling and mixing according to the metal molar ratio Li/(Ni + Co + Mn) ═ 1.05 to obtain a mixed material, controlling the sintering temperature at 910 ℃ and the sintering time at 11h in the air atmosphere, cooling, and then crushing, sieving and deironing the sintered material to obtain the single crystal ternary cathode material. The results of the performance tests of the batteries made with this material are shown in table 1.
Comparative example 2
Lithium hydroxide and nickel cobalt manganese hydroxide precursor Ni0.7Co0.1Mn0.2(OH)2Uniformly ball-milling and mixing according to the metal molar ratio Li/(Ni + Co + Mn) ═ 1.07 to obtain a mixed material, controlling the sintering temperature at 895 ℃ and the sintering time at 10h in an oxygen atmosphere, cooling, and then crushing, sieving and deironing the sintered material to obtain the single crystal ternary cathode material. The results of the performance tests of the batteries made with this material are shown in table 1.
Table 1 results of testing of the charging performance of the positive electrode material prepared in the examples and comparative examples
According to the invention, after the surface treatment is carried out on the single crystal anode material, the carbon coating modification of the single crystal ternary anode material is completed by utilizing the solvent evaporation self-assembly process, so that the conductivity and the long-cycle stability of the battery material are improved; the lithium ion battery prepared by the anode material has higher service voltage, high capacity and good long cycle performance.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The coating modified lithium ion ternary cathode material is characterized by comprising a cathode material core and a coating agent coated on the surface of the cathode material core, wherein the coating agent accounts for 0.5-5% of the total weight of the cathode material core;
the chemical general formula of the anode material core is LicNiaCobMn1-a-bMfO2Wherein c is more than or equal to 0.9 and less than or equal to 1.2, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, and a + b<F is more than or equal to 1, 0.01 and less than or equal to 0.10; m is a doping element;
the coating agent is obtained by mixing a solution containing a carbon source and a template agent, wherein the carbon source accounts for 50-70% of the weight of the template agent.
2. The coating-modified lithium ion ternary positive electrode material according to claim 1, wherein the doping element is a complex of any of Zr, Ti, Mg, Zn, La, Y, B, V, Ca or Al with other metal elements or a mixture of one or more of oxides, hydroxides, metallo-organics, phosphates containing the same.
3. The coating-modified lithium ion ternary cathode material according to claim 1, wherein the carbon source is one or more of glucose, polyacrylonitrile, sucrose or phenolic resin.
4. The coating-modified lithium ion ternary cathode material according to claim 1, wherein the solvent in the solution containing the carbon source is one or more of deionized water, alcohols, dimethylformamide and ethylene carbonate.
5. The coating-modified lithium ion ternary positive electrode material as claimed in claim 1, wherein the template agent is one or more of polystyrene colloidal crystal template, P123 or F127.
6. The preparation method of the coating modified lithium ion ternary cathode material according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) primary sintering: a method for producing a lithium ion battery, a single crystal precursor and a dopant element according to the general chemical formula Li in claim 1cNiaCobMn1-a-bMfO2Mixing the materials according to the ratio, then sintering, and crushing, screening and deironing the sintered materials to obtain a primary sintered material;
(2) coating and sintering: ultrasonically mixing a solution containing a carbon source and a template agent to obtain a coating agent, putting a primary sintering material into a stirring kettle containing the solvent, uniformly stirring and mixing, performing suction filtration and drying to obtain an anode material core, adding the coating agent into the anode material core, stirring and dispersing to obtain mixed slurry, then performing a solvent evaporation induced self-assembly process on the mixed slurry at 50-70 ℃ under a vacuum condition to obtain a primary product, and finally sintering the primary product to obtain the coating modified lithium ion ternary anode material.
7. The method as claimed in claim 6, wherein the sintering temperature in step (1) is 800-950 ℃ for 6-15h, and the sintering atmosphere is a mixed atmosphere containing 30-70% by volume of oxygen or air.
8. The preparation method of the coating modified lithium ion ternary cathode material according to claim 6, wherein the lithium source in step (1) is a mixture of one or more of lithium hydroxide, lithium carbonate, lithium nitrate or lithium oxalate.
9. The preparation method of the coating-modified lithium ion ternary cathode material as claimed in claim 6, wherein the solvent in the stirred tank in the step (2) is 20-50 wt% ethanol water solution or deionized water.
10. The method for preparing the coating-modified lithium ion ternary cathode material according to claim 6, wherein the sintering treatment of the primary product in the step (2) comprises: firstly, carrying out pre-oxidation treatment at 90-320 ℃ for 1.5-3.5 h; then carrying out pre-carbonization treatment at the temperature of 400-550 ℃ for 1.5-3.5 h; then carrying out carbonization treatment at the temperature of 550-800 ℃ for 1-3 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114005971A (en) * | 2021-10-22 | 2022-02-01 | 陕西红马科技有限公司 | Positive electrode material with p-type doped conductive polymer coating and preparation method thereof |
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| CN114005971B (en) * | 2021-10-22 | 2024-04-19 | 陕西红马科技有限公司 | Positive electrode material with p-type doped conductive polymer coating and preparation method thereof |
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