CN111342050A - Coating method for improving ionic conductivity of lithium ion battery anode material and coating modified anode material - Google Patents
Coating method for improving ionic conductivity of lithium ion battery anode material and coating modified anode material Download PDFInfo
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Abstract
The invention provides a coating method for improving the ionic conductivity of a lithium ion battery anode material. The invention adopts an in-situ solid state technology, lithium salt and an initiator are dissolved in an organic monomer solvent, a positive electrode material is uniformly dispersed in the organic solution, and the organic solution is uniformly solidified on the surface of the positive electrode material by adopting modes of ultraviolet polymerization, thermal polymerization, electron beam polymerization and the like to form a compact protective layer. Because the lithium salt is dissolved in the organic solvent, lithium ions can be conducted, so that the coating method can inhibit side reactions between the cathode material and the electrolyte, can improve the lithium ion conductivity of the cathode material body, and further improve the rate capability of the lithium ion battery. Meanwhile, the anode material prepared by the coating method has high lithium ion conductivity, so that the anode material is expected to be applied to all-solid-state batteries.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a coating method for improving the ionic conductivity of a lithium ion battery anode material and a coated and modified anode material.
Background
Compared with the traditional secondary battery, the lithium ion battery has the advantages of large capacity density, good cycle performance and safety performance, environmental friendliness and the like, and is widely applied to the fields of portable electronic products, electric automobiles and energy storage. The positive electrode material is an important component of the lithium ion battery, and is a limiting factor of the performance of the whole lithium ion battery because the energy density is lower compared with that of the negative electrode. At present, the commercialized battery adopts organic solvent composite lithium salt as electrolyte, and side reaction can occur at the contact part of the organic electrolyte and the anode material in the circulation process, so that the dissolution of active substances of the anode material, the structural damage and other influences are caused, and the performance of the lithium ion battery is further deteriorated. The existing method for solving the defects is to coat a protective layer on the surface of the anode material, so that the contact between the anode material and the organic electrolyte is reduced, the anode material is protected from being corroded by the organic electrolyte, and the stability of the performance of the lithium ion battery is further maintained.
The existing coating technology generally adopts methods such as coprecipitation, sol-gel, thermal sintering and the like to coat a layer of inactive oxide such as alumina, magnesia, titanium dioxide, silicon dioxide and the like on the surface of a material, and the coating method is difficult to form a net structure coating on the surface of the material uniformly, and most of the materials are coated in an island structure (see Chinese patent CN102315430A, a lithium ion battery metal oxide coating anode material). In addition, since most of these substances do not have the ability to conduct lithium ions, the ion conductivity of the positive electrode material is affected after coating.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a coating method for improving the ionic conductivity of a positive electrode material of a lithium ion battery and a coated and modified positive electrode material, wherein the coating method provided by the present invention can not only inhibit side reactions between the positive electrode material and an electrolyte, but also improve the lithium ion conductivity of the positive electrode material body, thereby improving the rate capability of the lithium ion battery.
The invention provides a coating method for improving the ionic conductivity of a lithium ion battery anode material, which comprises the following steps:
A) mixing lithium salt, an initiator, a polymer monomer and an alcohol solvent to obtain a dispersion liquid;
B) and uniformly mixing the dispersion liquid and the lithium ion battery anode material, and carrying out polymerization reaction to obtain the coated modified anode material.
Preferably, the lithium salt is selected from one or more of lithium perchlorate, lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium fluoroalkylphosphate, lithium bis (trifluoromethylsulfonyl) methide, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethylsulfonyl imide and lithium bis-fluorosulfonylimide.
Preferably, the initiator is selected from one or more of azobisisobutyronitrile and benzoyl peroxide.
Preferably, the organic monomer is one or more of tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 2-alkyl ethyl acrylate, isobornyl acrylate.
Preferably, the alcoholic solvent is selected from ethanol or isopropanol.
Preferably, the mass ratio of the lithium salt to the initiator to the polymer monomer is (1-20): (1-10): (2-90);
the mass ratio of the total mass of the lithium salt, the initiator and the polymer monomer to the alcohol solvent is 1 (20-60);
the mass ratio of the total mass of the lithium salt, the initiator and the polymer monomer to the positive electrode material is (0.5-50): 100.
Preferably, the positive electrode material is selected from one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, binary material lithium nickel cobalt oxide, ternary material lithium nickel cobalt oxide and ternary material lithium nickel cobalt aluminate and their modified dopants.
Preferably, the polymerization reaction is selected from uv polymerization, thermal polymerization or electron beam polymerization.
Preferably, the specific methods of the ultraviolet polymerization and the electron beam polymerization are as follows:
uniformly mixing the dispersion liquid with the lithium ion battery anode material, and then stirring or performing ultrasonic treatment under the irradiation of an ultraviolet lamp or an electron beam until the alcohol solvent is completely volatilized to obtain a coated modified anode material;
the specific method of the thermal polymerization is as follows:
and (3) uniformly mixing the dispersion liquid and the lithium ion battery anode material, and heating under the ultrasonic or stirring dispersion condition until the alcohol solvent is completely volatilized to obtain the coated modified anode material.
The invention also provides a coating modified cathode material obtained by the coating method.
Compared with the prior art, the invention provides a coating method for improving the ionic conductivity of a lithium ion battery anode material, which comprises the following steps: A) mixing lithium salt, an initiator, a polymer monomer and an alcohol solvent to obtain a dispersion liquid; B) and uniformly mixing the dispersion liquid and the lithium ion battery anode material, and carrying out polymerization reaction to obtain the coated modified anode material. The invention adopts an in-situ solid state technology, lithium salt and an initiator are dissolved in an organic monomer solvent, a positive electrode material is uniformly dispersed in the organic solution, and the organic solution is uniformly solidified on the surface of the positive electrode material by adopting modes of ultraviolet polymerization, thermal polymerization, electron beam polymerization and the like to form a compact protective layer. Because the lithium salt is dissolved in the organic solvent, lithium ions can be conducted, so that the coating method can inhibit side reactions between the cathode material and the electrolyte, can improve the lithium ion conductivity of the cathode material body, and further improve the rate capability of the lithium ion battery. Meanwhile, the anode material prepared by the coating method has high lithium ion conductivity, so that the anode material is expected to be applied to all-solid-state batteries.
Drawings
Fig. 1 is a TEM image of a coating-modified cathode material prepared in example 1;
fig. 2 is a 0.1C capacity-voltage curve of the coated modified cathode material prepared in example 1;
fig. 3 is a 0.1C capacity-voltage curve of the coating-modified cathode material prepared in comparative example 1.
Detailed Description
The invention provides a coating method for improving the ionic conductivity of a lithium ion battery anode material, which comprises the following steps:
A) mixing lithium salt, an initiator, a polymer monomer and an alcohol solvent to obtain a dispersion liquid;
B) and uniformly mixing the dispersion liquid and the lithium ion battery anode material, and carrying out polymerization reaction to obtain the coated modified anode material.
Firstly, mixing lithium salt, an initiator, a polymer monomer and an alcohol solvent to obtain a dispersion liquid.
Specifically, firstly, a lithium salt, an initiator and a polymer monomer are mixed to obtain a mixed solution.
Wherein the lithium salt is selected from one or more of lithium perchlorate, lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium fluoroalkylphosphate, lithium bis (trifluoromethylsulfonyl) methide, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethylsulfonyl imide and lithium bis-fluorosulfonylimide;
the initiator is selected from one or more of Azobisisobutyronitrile (AIBN) and Benzoyl Peroxide (BPO);
the polymer monomer is selected from one or more of tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETEA), 2-alkyl ethyl acrylate (HEA), isobornyl acrylate (IBOA);
the mass ratio of the lithium salt to the initiator to the polymer monomer is (1-20): (1-10): (2-90); preferably (1-10): (1-5): (85-90), most preferably 10%: 0.5%: 89.5 percent.
Subsequently, the mixed solution is mixed with an alcohol solvent to obtain a dispersion liquid. Wherein the mixing mode is preferably ultrasonic dispersion. The alcohol solvent is selected from ethanol or isopropanol.
The mass ratio of the total mass of the lithium salt, the initiator and the polymer monomer to the alcohol solvent is 1 (20-60), and preferably 1 (30-50).
And then, uniformly mixing the dispersion liquid and the lithium ion battery positive electrode material, and carrying out polymerization reaction to obtain the coated modified positive electrode material.
Specifically, the dispersion liquid is mixed with a lithium ion battery anode material to obtain mixed slurry;
the lithium ion battery positive electrode material is selected from one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, binary material lithium nickel cobalt oxide, ternary material lithium nickel cobalt aluminate and modified adulterants of the materials.
The mass ratio of the total mass of the lithium salt, the initiator and the polymer monomer to the positive electrode material is (0.5-50): 100, preferably (1-40): 100.
and then, carrying out polymerization reaction on the mixed slurry to obtain the coating modified cathode material.
The polymerization reaction is selected from ultraviolet polymerization, thermal polymerization or electron beam polymerization.
The specific method of the ultraviolet polymerization and the electron beam polymerization comprises the following steps:
uniformly mixing the dispersion liquid with the lithium ion battery anode material, and then stirring or performing ultrasonic treatment under the irradiation of an ultraviolet lamp or an electron beam until the alcohol solvent is completely volatilized to obtain a coated modified anode material;
the specific method of the thermal polymerization is as follows:
and (3) uniformly mixing the dispersion liquid and the lithium ion battery anode material, and heating under the ultrasonic or stirring dispersion condition until the alcohol solvent is completely volatilized to obtain the coated modified anode material.
The heating temperature is 25-100 ℃, preferably 60-80 ℃, and the heating time is 1-24 hours, preferably 3-12 hours.
The invention also provides a coating modified cathode material obtained by the coating method.
The coated and modified cathode material can be prepared into a lithium ion battery cathode and assembled into a lithium ion battery.
According to the invention, a compact protective layer is uniformly formed on the surface of the anode material by an in-situ solid-state technology, so that on one hand, the protective layer can avoid direct contact between the anode material and the electrolyte, reduce side reaction between the anode material and the electrolyte, reduce dissolution of active substances of the anode material, maintain the structural stability of the anode material and further improve the electrochemical performance of the lithium ion battery; on the other hand, the protective layer is formed by curing an organic monomer in which a lithium salt is dissolved, and thus can conduct lithium ions. Compared with the conventional passive oxide coating technology, the method can improve the ionic conductivity of the anode material body, and further improve the rate capability of the lithium ion battery. Meanwhile, the all-solid-state battery with high safety and high specific energy is considered as a necessary product of the next generation of lithium ion battery by industry, and the solid electrolyte cannot be soaked among the particles of the anode material like liquid electrolyte, because the anode material with high ionic conductivity prepared by the invention is expected to be applied to the all-solid-state battery, the problem that the bulk of the anode material is low in ionic conductivity is solved.
Compared with the prior art, the invention has the advantages that:
(1) the existing coating modification method of the cathode material is generally passive oxide coating, and because the passive oxide does not have the capability of conducting lithium ions, the ionic conductivity of the cathode material after coating modification is reduced to a certain extent. According to the invention, a compact protective layer is formed on the surface of the anode material by an organic monomer in-situ curing technology dissolved with lithium salt, and the lithium salt can be dissociated in the organic monomer to conduct lithium ions, so that the ionic conductivity of the modified anode material body obtained by the invention cannot be reduced, but is increased to a certain extent;
(2) the existing coating method of the anode material is difficult to uniformly form a net structure coating on the surface of the material, and most of the material is coated by an island structure. In the invention, the organic monomer solution dissolved with lithium salt can be uniformly dispersed on the surface of the anode material, and under the conditions of the existence of an initiator, ultraviolet polymerization, thermal polymerization, electron beam polymerization and the like, the organic monomer solution uniformly polymerizes the surface of the anode material from a liquid state to a solid state to form a compact reticular coating layer, and the coating layer is more uniform than the coating modification method in the prior art.
(3) The modified cathode material prepared by the invention has higher lithium ion conductivity, is expected to solve the problems of lower ion conductivity of the cathode material body and higher interface impedance between the cathode material and the solid electrolyte in the all-solid-state battery, and is further applied to the next generation of all-solid-state battery with high safety and high specific energy.
For further understanding of the present invention, the following describes a coating method for improving the ionic conductivity of a lithium ion battery positive electrode material and a coating modified positive electrode material provided by the present invention with reference to examples, and the scope of the present invention is not limited by the following examples.
Example 1:
(1) weighing 0.1g of LiTFSI and 0.05g of photoinitiator 184, adding the LiTFSI and the photoinitiator 184 into 0.895g of polyethylene glycol diacrylate PEGDA, and magnetically stirring for 30min to obtain a uniform solution;
(2) adding the solution into a beaker filled with 50g of isopropanol, and carrying out ultrasonic dispersion for 2 hours;
(3) adding 20g of NCM811 into the solution dispersed by the ultrasonic waves, stirring by magnetic force overnight, and irradiating the slurry by using a UV lamp in the stirring process until isopropanol in the slurry is completely volatilized to obtain a coating modified positive electrode material;
TEM observation was performed on the above-described coating-modified cathode material, and the result was shown in fig. 1, and fig. 1 is a TEM image of the coating-modified cathode material prepared in example 1. TEM characterization showed that a uniform coating was observed on the surface of the material.
(4) The lithium ion battery is assembled by the coating modified NCM811 material,
the specific method comprises the following steps: the lithium metal is used as a negative electrode, the PP diaphragm is used as a battery diaphragm, and the lithium metal and the PP diaphragm are mixedThe coating modified anode material, NMP as a solvent and PVDF as a binder are prepared into an anode, and the anode is prepared by using EC: DMC: EMC 1:1:1 LiPF6The concentration of the electrolyte is 1mol/L, and the button cell is assembled.
Testing the electrochemical performance of the alloy at room temperature (25 ℃) and within a voltage range of 2.8-4.3V;
the results are shown in fig. 2, and fig. 2 is a 0.1C capacity-voltage curve of the coating-modified cathode material prepared in example 1. The test result shows that: the comparative sample 0.1C had a discharge capacity of 204.0mAh/g and a first coulombic efficiency of 89.63%, while the example 1 sample 0.1C had a discharge capacity of 206.0mAh/g and a first coulombic efficiency of 91.38%, and the comparative sample had a lithium ion conductivity of 4.97 x 10-5S/cm, while the lithium ion conductivity of the sample of example 1 was 6.85 x 10-5S/cm, which shows that the coating method can improve the electrochemical performance of the cathode material.
Example 2:
(1) 0.16g LiClO was weighed4Adding 0.008g of initiator AIBN into 0.836g of isobornyl acrylate IBOA, and magnetically stirring for 20min to obtain a uniform solution;
(2) adding the solution into a beaker filled with 50g of ethanol, and carrying out ultrasonic dispersion for 2 hours;
(3) adding 18g of NCM811 into the solution dispersed by the ultrasonic waves, magnetically stirring for 24h at 80 ℃ until ethanol in the slurry is completely volatilized, and then, carrying out heat treatment on the slurry at 100 ℃ for 3h to prepare a modified NCM811 material;
(4) assembling a lithium ion battery by using the coated and modified NCM811 material, and testing the electrochemical performance of the lithium ion battery at room temperature (25 ℃) and within a voltage range of 2.8-4.3V;
the test result shows that: the comparative sample 0.1C had a discharge capacity of 204.0mAh/g and a first coulombic efficiency of 89.63%, while the example 2 sample 0.1C had a discharge capacity of 207.2mAh/g and a first coulombic efficiency of 90.95%, and the comparative sample had a lithium ion conductivity of 4.97 x 10-5S/cm, while the lithium ion conductivity of the sample of example 2 was 5.93 x 10-5S/cm, which shows that the coating method can improve the electrochemical performance of the cathode material.
Example 3:
(1) weighing 0.12g LiFSI and 0.006g photoinitiator 184, adding into 0.877g pentaerythritol tetraacrylate PETEEA, and magnetically stirring for 30min to obtain a uniform solution;
(2) adding the solution into a beaker filled with 50g of ethanol, and dispersing for 3 hours by magnetic stirring;
(3) adding 20g of NCM811 into the solution dispersed by the ultrasonic waves, stirring by magnetic force overnight, and irradiating the slurry by using a UV lamp in the stirring process until the ethanol in the slurry is completely volatilized;
(4) assembling a lithium ion battery by using the coated and modified NCM811 material, and testing the electrochemical performance of the lithium ion battery at room temperature (25 ℃) and within a voltage range of 2.8-4.3V;
the test result shows that: the comparative example sample 0.1C had a discharge capacity of 204.0mAh/g and a first coulombic efficiency of 89.63%, while the example 3 sample 0.1C had a discharge capacity of 205.4mAh/g and a first coulombic efficiency of 91.07%, and the comparative example sample had a lithium ion conductivity of 4.97 x 10-5S/cm, while the lithium ion conductivity of the sample of example 3 was 7.13 x 10-5S/cm, which shows that the coating method can improve the electrochemical performance of the cathode material.
Comparative example:
uniformly mixing the nano-particle alumina and the NCM811 material in a mass ratio of 1:100 in a high-speed mixer, and performing heat treatment in a tube furnace at 500 ℃ for 5 hours to obtain the NCM811 material coated by the conventional alumina.
Assembling the lithium ion battery according to the battery assembling method provided in the embodiment 1, only changing the anode material, keeping the other conditions unchanged, and testing the electrochemical performance of the lithium ion battery at room temperature (25 ℃) and within the voltage range of 2.8-4.3V;
the results are shown in fig. 3, and fig. 3 is a 0.1C capacity-voltage curve of the coating-modified cathode material prepared in the comparative example. The test result shows that: comparative sample 0.1C had a discharge capacity of 204.0mAh/g, a first coulombic efficiency of 89.63%, and a lithium ion conductivity of 4.97 x 10-5S/cm。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A coating method for improving the ionic conductivity of a lithium ion battery anode material is characterized by comprising the following steps:
A) mixing lithium salt, an initiator, a polymer monomer and an alcohol solvent to obtain a dispersion liquid;
B) and uniformly mixing the dispersion liquid and the lithium ion battery anode material, and carrying out polymerization reaction to obtain the coated modified anode material.
2. The coating process according to claim 1, wherein the lithium salt is selected from one or more of lithium perchlorate, lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium fluoroalkylphosphate, lithium bis (trifluoromethylsulfonyl) methide, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethylsulfonyl imide and lithium difluorosulfonyl imide.
3. The coating process according to claim 1, wherein the initiator is selected from one or more of azobisisobutyronitrile and benzoyl peroxide.
4. The coating process according to claim 1, wherein the organic monomer is one or more of tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 2-alkyl ethyl acrylate, isobornyl acrylate.
5. The coating process according to claim 1, wherein the alcoholic solvent is selected from ethanol or isopropanol.
6. The coating method according to claim 1, wherein the mass ratio of the lithium salt, the initiator and the polymer monomer is (1-20): (1-10): (2-90);
the mass ratio of the total mass of the lithium salt, the initiator and the polymer monomer to the alcohol solvent is 1 (20-60);
the mass ratio of the total mass of the lithium salt, the initiator and the polymer monomer to the positive electrode material is (0.5-50): 100.
7. The coating method according to claim 1, wherein the positive electrode material is selected from one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, binary material lithium nickel cobalt, binary material lithium nickel manganese, ternary material lithium nickel cobalt aluminate, and modified dopants thereof.
8. The coating process according to claim 1, wherein the polymerization reaction is selected from uv polymerization, thermal polymerization or electron beam polymerization.
9. The coating method according to claim 8, wherein the specific methods of ultraviolet polymerization and electron beam polymerization are as follows:
uniformly mixing the dispersion liquid with the lithium ion battery anode material, and then stirring or performing ultrasonic treatment under the irradiation of an ultraviolet lamp or an electron beam until the alcohol solvent is completely volatilized to obtain a coated modified anode material;
the specific method of the thermal polymerization is as follows:
and (3) uniformly mixing the dispersion liquid and the lithium ion battery anode material, and heating under the ultrasonic or stirring dispersion condition until the alcohol solvent is completely volatilized to obtain the coated modified anode material.
10. A coating-modified positive electrode material obtained by the coating method according to claims 1 to 9.
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| CN113285071A (en) * | 2021-05-14 | 2021-08-20 | 合肥国轩高科动力能源有限公司 | Lithium iron phosphate and preparation method and application thereof |
| CN113471408A (en) * | 2021-09-06 | 2021-10-01 | 中航锂电科技有限公司 | Method for manufacturing all-solid-state battery composite positive electrode, composite positive electrode and all-solid-state battery |
| CN113871588A (en) * | 2021-09-13 | 2021-12-31 | 武汉理工大学 | Lithium battery core-shell cathode material, lithium battery containing lithium battery core-shell cathode material and preparation method of lithium battery |
| WO2022052425A1 (en) * | 2020-09-09 | 2022-03-17 | 蜂巢能源科技股份有限公司 | Electrolyte material, preparation method therefor and use thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035943A (en) * | 2012-12-25 | 2013-04-10 | 天津市捷威动力工业有限公司 | Polymer electrolyte additive and gel polymer cell using same |
| CN103682354A (en) * | 2012-09-18 | 2014-03-26 | 华为技术有限公司 | All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery |
| CN108232138A (en) * | 2017-12-20 | 2018-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of solid state lithium battery low internal resistance positive electrode and preparation method thereof |
| CN110148709A (en) * | 2019-05-25 | 2019-08-20 | 珠海冠宇电池有限公司 | A kind of preparation method and lithium ion battery of anode pole piece that leading lithium composite material clad anode material comprising conduction |
-
2020
- 2020-03-06 CN CN202010150700.4A patent/CN111342050A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682354A (en) * | 2012-09-18 | 2014-03-26 | 华为技术有限公司 | All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery |
| CN103035943A (en) * | 2012-12-25 | 2013-04-10 | 天津市捷威动力工业有限公司 | Polymer electrolyte additive and gel polymer cell using same |
| CN108232138A (en) * | 2017-12-20 | 2018-06-29 | 中国科学院青岛生物能源与过程研究所 | A kind of solid state lithium battery low internal resistance positive electrode and preparation method thereof |
| CN110148709A (en) * | 2019-05-25 | 2019-08-20 | 珠海冠宇电池有限公司 | A kind of preparation method and lithium ion battery of anode pole piece that leading lithium composite material clad anode material comprising conduction |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022052425A1 (en) * | 2020-09-09 | 2022-03-17 | 蜂巢能源科技股份有限公司 | Electrolyte material, preparation method therefor and use thereof |
| CN112421037A (en) * | 2020-11-04 | 2021-02-26 | 成都新柯力化工科技有限公司 | Hydrophobic NCA positive electrode material of lithium battery and preparation method |
| CN113285071A (en) * | 2021-05-14 | 2021-08-20 | 合肥国轩高科动力能源有限公司 | Lithium iron phosphate and preparation method and application thereof |
| CN113471408A (en) * | 2021-09-06 | 2021-10-01 | 中航锂电科技有限公司 | Method for manufacturing all-solid-state battery composite positive electrode, composite positive electrode and all-solid-state battery |
| CN113871588A (en) * | 2021-09-13 | 2021-12-31 | 武汉理工大学 | Lithium battery core-shell cathode material, lithium battery containing lithium battery core-shell cathode material and preparation method of lithium battery |
| CN115064672A (en) * | 2022-06-17 | 2022-09-16 | 哈尔滨工业大学 | Star-shaped coating layer battery electrode material and preparation method and application thereof |
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