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CN110627135B - Method for coating carbon by chemical vapor deposition and coating high-voltage ternary material prepared - Google Patents

Method for coating carbon by chemical vapor deposition and coating high-voltage ternary material prepared Download PDF

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CN110627135B
CN110627135B CN201910924082.1A CN201910924082A CN110627135B CN 110627135 B CN110627135 B CN 110627135B CN 201910924082 A CN201910924082 A CN 201910924082A CN 110627135 B CN110627135 B CN 110627135B
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vapor deposition
ternary material
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furnace body
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CN110627135A (en
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宋英杰
徐宁
马倩倩
伏萍萍
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Tianjin B&M Science and Technology Co Ltd
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Abstract

本发明公开了一种化学气相沉积包覆碳的方法及制备的包覆高电压三元材料，首先通过在动态化学气相沉积炉中生成三元材料，然后通过气化液态钛源，利用其在氧气气氛中的氧化分解，在三元材料界面发生化学气相沉积反应，原位生成氧化钛均匀、致密包覆的三元材料；然后在串联的二级气相沉积炉中进行碳包覆；最后通过破碎、过筛、包装即得到最终产品。本发明通过气相包覆氧化钛明显提升了包覆的均匀性和致密性，通过二级气相沉积炉工艺设计，有效解决了在高温条件下碳对三元材料金属元素的还原问题；化学气相沉积炉为动态窑炉，因此一次焙烧产物不会板结，可继续进行包覆，显著简化了工艺流程。

Figure 201910924082

The invention discloses a method for coating carbon by chemical vapor deposition and a prepared coating high-voltage ternary material. First, the ternary material is generated in a dynamic chemical vapor deposition furnace, and then a liquid titanium source is vaporized to utilize the ternary material in a dynamic chemical vapor deposition furnace. Oxidative decomposition in an oxygen atmosphere, chemical vapor deposition reaction occurs at the interface of the ternary material, and a ternary material with uniform and dense coating of titanium oxide is formed in situ; then carbon coating is performed in a series-connected two-stage vapor deposition furnace; The final product is obtained by crushing, sieving and packaging. The invention obviously improves the uniformity and compactness of the coating by coating the titanium oxide in the gas phase, and effectively solves the problem of the reduction of carbon to the metal elements of the ternary material under high temperature conditions through the process design of the two-stage vapor deposition furnace; chemical vapor deposition The furnace is a dynamic kiln, so the first-fired product does not harden and can continue to be clad, which significantly simplifies the process.

Figure 201910924082

Description

Method for coating carbon by chemical vapor deposition and prepared coated high-voltage ternary material
Technical Field
The invention relates to the field of lithium ion secondary battery anode materials, in particular to a method for coating carbon by chemical vapor deposition and a prepared coated high-voltage ternary material.
Background
Popularization and application of new energy automobiles are imperative, wherein a power lithium ion battery is a core part of the new energy automobiles, and a positive electrode material in a lithium ion battery system is a decisive factor. In the existing anode material system, the ternary material has the advantages of high specific energy density, good cycle performance and the like, and is a mainstream material of a new energy automobile. However, divalent nickel and trivalent nickel are oxidized into tetravalent nickel in the charging process of the conventional ternary material, and the tetravalent nickel has strong catalytic and oxidizing effects on the conventional carbonate electrolyte system in a high-voltage environment, so that the electrolyte is continuously consumed, the internal resistance of the battery continuously rises, capacity water jump finally occurs, and swelling occurs to generate potential safety hazards, and the practical application of the ternary material is seriously influenced.
The type and content of the coating also have important influence on the performance of the ternary material, and the coating needs to be chemically inert and cannot react with the active ternary material and the electrolyte; the conductivity is high, otherwise, the discharge specific capacity is influenced; the content is proper, and the insertion and extraction of Li ions are not influenced on the premise of ensuring the stability. In addition, solid phase coating or liquid phase coating is often adopted in industrialization, and the effect of uniform coating is difficult to achieve due to the preparation mechanism.
Among them, carbon materials and Ti-containing materials are commonly used as coating materials because of their good chemical inertness and high electrical conductivity. In the prior art, CN 108963239A adopts a vapor deposition method to prepare a titanium dioxide-coated nickel cobalt lithium manganate positive electrode material, but titanium dioxide is used as a semiconductor, and the specific capacity of the material can be influenced by the single coating; in the prior art, CN106058220B also adopts a vapor deposition method to prepare a titanium nitride and carbon double-coated cathode material, but the method adopts a conventional method of baking a solid-phase carbon source into a carbon layer, carbon source precursors are prone to aggregation at high temperature, the baked product has the problem of uneven coating, and carbon can undergo a reduction reaction with metal ions in the cathode material at high temperature, so that partial metal segregation in the material is caused, and the performance of the cathode material is affected.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for coating carbon by chemical vapor deposition and a prepared high-voltage ternary coating material, namely two uniform and compact coating layers are coated on the surface of the ternary coating material by a chemical vapor deposition method, so that the contact with an electrolyte is completely isolated, and the aims of improving the cycle performance and inhibiting the battery from swelling are fulfilled.
The technical scheme of the invention is as follows: a method of chemical vapor deposition of coated carbon comprising the steps of:
1) putting a material I to be coated into a second-stage furnace body of the chemical vapor deposition furnaces connected in series;
2) introducing organic gas into the first-stage furnace body, and performing carbon deposition on carbon decomposed by the organic gas in the second-stage furnace body to obtain a carbon-coated material II;
the chemical vapor deposition furnaces connected in series comprise a first-stage furnace body and a second-stage furnace body, wherein the furnace temperature of the first-stage furnace body is higher than 500 ℃; the furnace temperature of the second-stage furnace body is lower than 500 ℃, and the furnace body atmosphere of the vapor deposition furnace is inert gas.
The furnace temperature of the first-stage furnace body is 750-850 ℃, and the furnace temperature of the second-stage furnace body is 300-400 ℃.
The carbon-coated substance prepared by the chemical vapor deposition carbon-coating method.
A preparation method of a high-voltage ternary material coated by a chemical vapor deposition method comprises the following steps:
1) according to the formula LiaNixCoyA(1-x-y)O2Weighing lithium source and NixCoyA(1-x-y)(OH)2Adding the precursor into a high-speed mixer, and uniformly mixing to obtain a mixture I, wherein A is any one or two elements of Al or Mn, a is 1.03-1.06, x is 0.5-0.9, and y is 0.05-0.40;
2) adding the mixture I into a vapor deposition furnace for high-temperature roasting, wherein the rotating speed of the furnace body is 1-3 circles/minute, the roasting temperature is 880-960 ℃, the roasting time is 8-12 hours, and the roasting atmosphere is oxygen to obtain a ternary material II;
3) heating a liquid titanium source in a glass container at the temperature of 300-350 ℃, carrying out chemical deposition by using flowing inert gas to bring the volatilized titanium source into the vapor deposition furnace at the deposition temperature of 600-700 ℃ for 4-6 h to obtain a titanium-coated ternary material III;
4) airflow crushing the titanium-coated ternary material III to obtain a material IV with the particle size distribution of D50＝2.5～5.5μm；
5) Putting the material IV into a second-stage furnace body of a chemical vapor deposition furnace connected in series, wherein the temperature of the first-stage furnace body is 750-850 ℃, the atmosphere of the furnace body is inert gas, the temperature of the second-stage furnace body is 300-400 ℃, and the atmosphere of the furnace body is inert gas;
6) introducing organic gas into the first-stage chemical vapor deposition furnace, decomposing the organic gas in the first-stage furnace body, and finally depositing in the second-stage furnace body to obtain a carbon-coated material V;
7) and (4) demagnetizing and packaging the carbon-coated material V to obtain a final product.
The lithium source in the step 1) is lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide.
And 3) the liquid titanium source is one or a mixture of tetrabutyl titanate and titanium tetrachloride.
The titanium content in the titanium-coated ternary material III in the step 3) is 2000-4000 ppm.
And 6) the carbon coating mass of the carbon-coated material V is 1-3%.
And 6) the organic gas is any one of acetylene, acetone, ethanol and benzene or mixed gas mixed in any proportion.
The coated high-voltage ternary material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. the method of innovative two-step vapor deposition is adopted, decomposition is carried out firstly, then carbon deposition is carried out, the deposited carbon layer grows by molecular superposition, compared with the traditional method, the method is more uniform, the two-step vapor deposition overcomes the defect that if the temperature is overhigh in the traditional solid phase synthesis, the carbon and the metal elements in the anode material carry out reduction reaction, and after the gas-phase carbon source is decomposed at high temperature, deposition is carried out at low temperature, the uniform carbon layer can be obtained;
2. the uniformity and compactness of the coating are obviously improved by coating the titanium oxide in a gas phase, compared with the titanium nitride in the prior art, the titanium oxide is more favorable for inhibiting the corrosion of electrolyte, and the titanium oxide can react with residual lithium on the surface layer, so that the content of the residual lithium is reduced, and the processing performance is favorably improved; the lithium-titanium oxide produced by the reaction is a fast lithium ion conductor, and is beneficial to improving the rate capability of the ternary material;
3. the invention adopts the chemical vapor deposition furnace as the dynamic kiln, so that the product of primary roasting can not be hardened, the coating can be continuously carried out, and the process flow is obviously simplified.
Drawings
FIG. 1 is a process flow diagram of the method for preparing a vapor-coated high-voltage ternary material of the present invention.
FIG. 2 is a schematic structural diagram of a vapor-phase coated high-voltage ternary material prepared by the present invention.
In the figure: 1-ternary material; 2-titanium oxide layer; 3-carbon layer.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples.
Example 1
A preparation method of a gas-phase-coated high-voltage ternary material comprises the following steps:
1) according to the formula Li1.03Ni0.5Co0.2Mn0.3O2Weighing lithium carbonate and Ni0.5Co0.2Mn0.3(OH)2Adding the precursor into a high-speed mixer, and uniformly mixing to obtain a mixture I;
2) adding the mixture I into a vapor deposition furnace for high-temperature roasting, wherein the rotating speed of the furnace body is 1 circle/minute, the roasting temperature is 880 ℃, the roasting time is 12 hours, and the roasting atmosphere is oxygen, so as to obtain a ternary material II;
3) placing tetrabutyl titanate into a glass container, heating to 300 ℃, introducing volatilized tetrabutyl titanate into the vapor deposition furnace through flowing nitrogen for chemical deposition, wherein the deposition temperature is 600 ℃, and the deposition time is 6 hours, so as to obtain a vapor-coated ternary material III, wherein the titanium content is 2000 ppm;
4) carrying out airflow crushing on the gas-phase coated ternary material III to obtain a material IV with the particle size distribution of D50＝2.5μm；
5) Putting the material IV into a second-stage furnace body of a chemical vapor deposition furnace connected in series, wherein the temperature of the first-stage furnace body is 750 ℃, the atmosphere of the furnace body is nitrogen, the temperature of the second-stage furnace body is 300 ℃, and the atmosphere of the furnace body is nitrogen;
6) introducing acetylene into the first-stage chemical vapor deposition furnace, and finally depositing decomposed carbon in a second-stage furnace body under the action of gas, wherein the carbon coating mass is 1% to obtain a material V;
7) and (5) demagnetizing and packaging the material V to obtain a final product.
Comparative example 1
There is no step 3), the remaining steps are the same.
Comparative example 2
And 5) step 5) and step 6) are not carried out, the material IV is directly subjected to magnetic removal packaging to obtain a final product, and the rest steps are the same.
Comparative example 3
Modifying the step 5) into the following steps: and (3) putting the material IV into a chemical vapor deposition furnace, wherein the temperature of the furnace body is 750 ℃, the atmosphere of the furnace body is nitrogen, and the rest steps are the same.
Comparative example 4
Modifying the step 5) into the following steps: and (3) putting the material IV into a chemical vapor deposition furnace, wherein the temperature of the furnace body is 300 ℃, the atmosphere of the furnace body is nitrogen, and the rest steps are the same.
Example 2
A preparation method of a high-voltage ternary material coated by a chemical vapor deposition method comprises the following steps:
1) according to the formula Li1.05Ni0.5Co0.2Mn0.3O2Weighing lithium source and Ni0.5Co0.2Mn0.3(OH)2Adding the precursor into a high-speed mixer, and uniformly mixing to obtain a mixture I;
2) adding the mixture I into a vapor deposition furnace for high-temperature roasting, wherein the rotating speed of the furnace body is 3 circles per minute, the roasting temperature is 960 ℃, the roasting time is 8 hours, and the roasting atmosphere is oxygen to obtain a ternary material II;
3) putting titanium tetrachloride into a glass container, heating to 350 ℃, carrying volatilized titanium tetrachloride into the vapor deposition furnace through flowing argon gas for chemical deposition, wherein the deposition temperature is 700 ℃, and the deposition time is 4 hours, so as to obtain a vapor-coated ternary material III, wherein the titanium content is 4000 ppm;
4) airflow crushing the coated ternary material to obtain a material IV with the particle size distribution of D50＝4.0μm；
5) Putting the material IV into a second-stage furnace body of a chemical vapor deposition furnace connected in series, wherein the temperature of the first-stage furnace body is 850 ℃, the atmosphere of the furnace body is argon, the temperature of the second-stage furnace body is 400 ℃, and the atmosphere of the furnace body is argon;
6) introducing ethanol into the first-stage chemical vapor deposition furnace, and finally depositing decomposed carbon in a second-stage furnace body under the action of gas, wherein the carbon coating mass is 2% to obtain a material V;
7) and (5) demagnetizing and packaging the material V to obtain a final product.
Comparative example 5
Modifying the step 5) into the following steps: and putting the material IV into a second-stage furnace body of the chemical vapor deposition furnaces connected in series, wherein the temperature of the first-stage furnace body is 600 ℃, the atmosphere of the furnace body is argon, the temperature of the second-stage furnace body is 200 ℃, and the atmosphere of the furnace body is argon.
Comparative example 6
Modifying the step 5) into the following steps: and putting the material IV into a second-stage furnace body of the chemical vapor deposition furnaces connected in series, wherein the temperature of the first-stage furnace body is 900 ℃, the atmosphere of the furnace body is argon, the temperature of the second-stage furnace body is 450 ℃, and the atmosphere of the furnace body is argon.
Example 3
A preparation method of a high-voltage ternary material coated by a chemical vapor deposition method comprises the following steps:
1) according to the formula Li1.05Ni0.6Co0.2Mn0.2O2Weighing lithium source and Ni0.6Co0.2Mn0.2(OH)2Adding the precursor into a high-speed mixer, and uniformly mixing to obtain a mixture I;
2) adding the mixture I into a vapor deposition furnace for high-temperature roasting, wherein the rotating speed of the furnace body is 3 circles per minute, the roasting temperature is 880 ℃, the roasting time is 8 hours, and the roasting atmosphere is oxygen, so as to obtain a ternary material II;
3) putting titanium tetrachloride into a glass container, heating to 350 ℃, carrying volatilized titanium tetrachloride into the vapor deposition furnace through flowing helium gas for chemical deposition, wherein the deposition temperature is 700 ℃, and the deposition time is 4 hours, so as to obtain a vapor-coated ternary material III, wherein the titanium content is 3000 ppm;
4) airflow crushing the coated ternary material to obtain a material IV with the particle size distribution of D50＝4μm；
5) Putting the material IV into a second-stage furnace body of a chemical vapor deposition furnace connected in series, wherein the temperature of the first-stage furnace body is 850 ℃, the atmosphere of the furnace body is helium, the temperature of the second-stage furnace body is 400 ℃, and the atmosphere of the furnace body is helium;
6) introducing acetone into the first-stage chemical vapor deposition furnace, and finally depositing decomposed carbon in a second-stage furnace body under the action of gas, wherein the carbon coating mass is 2% to obtain a material V;
7) and (5) demagnetizing and packaging the material V to obtain a final product.
Comparative example 7
The step 3) is changed into the following steps: putting titanium tetrachloride into a glass container, heating to 350 ℃, carrying volatilized titanium tetrachloride into the vapor deposition furnace through flowing helium gas for chemical deposition, wherein the deposition temperature is 700 ℃, and the deposition time is 3 hours, so as to obtain a vapor-coated ternary material III, wherein the titanium content is 1500 ppm;
comparative example 8
The step 3) is changed into the following steps: putting titanium tetrachloride into a glass container, heating to 350 ℃, carrying volatilized titanium tetrachloride into the vapor deposition furnace through flowing helium gas for chemical deposition, wherein the deposition temperature is 700 ℃, and the deposition time is 7 hours, so as to obtain a vapor-coated ternary material III, wherein the titanium content is 5000 ppm;
example 4
A preparation method of a high-voltage ternary material coated by a chemical vapor deposition method comprises the following steps:
1) according to the formula Li1.04Ni0.7Co0.1Mn0.2O2Weighing lithium source and Ni0.7Co0.1Mn0.2Adding the precursor into a high-speed mixer, and uniformly mixing to obtain a mixture I;
2) adding the mixture I into a vapor deposition furnace for high-temperature roasting, wherein the rotating speed of the furnace body is 3 circles per minute, the roasting temperature is 900 ℃, the roasting time is 12 hours, and the roasting atmosphere is oxygen to obtain a ternary material II;
3) putting titanium tetrachloride into a glass container, heating to 350 ℃, carrying volatilized titanium tetrachloride into the vapor deposition furnace through flowing nitrogen gas for chemical deposition, wherein the deposition temperature is 700 ℃, and the deposition time is 4 hours, so as to obtain a vapor-coated ternary material III, wherein the titanium content is 3000 ppm;
4) airflow crushing the coated ternary material to obtain a material IV with the particle size distribution of D50＝3.5μm；
5) Putting the material IV into a second-stage furnace body of a chemical vapor deposition furnace connected in series, wherein the temperature of the first-stage furnace body is 850 ℃, the atmosphere of the furnace body is helium, the temperature of the second-stage furnace body is 350 ℃, and the atmosphere of the furnace body is helium;
6) introducing acetone into the first-stage chemical vapor deposition furnace, and finally depositing decomposed carbon in a second-stage furnace body under the action of gas, wherein the carbon coating mass is 3% to obtain a material V;
7) and (5) demagnetizing and packaging the material V to obtain a final product.
Experimental conditions:
table 1 shows the specific capacity of first cycle discharge and rate capability of button cells made of the lithium ion secondary battery positive electrode materials prepared in examples 1-4 and comparative examples 1-3.
The test conditions of the button cell are LR 2032, 0.1C, 3.0-4.3V, vs. Li+and/Li, the charging and discharging equipment used is a blue-charge charging and discharging instrument.
TABLE 1 comparison table of first charge and discharge performance
Figure BDA0002218474570000071
Figure BDA0002218474570000081
As can be seen from the data of the examples 1-4 in the table, the ternary material prepared by the invention has higher specific capacity and rate capability and stronger application performance.
Comparative example 1 with no TiO addition2Notwithstanding a moderate amount of TiO2The generation of a CEI film on the surface of the primary active material can be inhibited, and the specific capacity of the material is also slightly reduced; the comparative example 2 has no carbon coating, and the conductivity of the ternary material and titanium dioxide is poor, so that the conductivity of the material is directly reduced, and the specific capacity and the first effect are obviously reduced.
Comparative examples 3 and 4 are both one-step vapor deposition coating methods, with comparative example 3 having a higher deposition temperature and comparative example 4 having a lower deposition temperature. Compared with the two-step deposition coating method, the one-step method has the following defects: when the deposition temperature is too high, carbon can generate reduction reaction with metal elements in the anode material, the crystal structure is damaged, and the electrical property of the product is seriously influenced; when the deposition temperature is too low, the organic gas cannot be decomposed, and the purpose of carbon coating is difficult to achieve. Thus, the specific capacity of comparative example 3 is very low and the rate capability of comparative example 4 is poor.
The overall calcination temperature in comparative example 5 was lower; in the comparative example 6, the integral roasting temperature is higher, and the crystal structure is damaged due to overhigh roasting temperature; and the roasting temperature is too low, the carbon source may not be completely decomposed or the graphitization degree of the carbon is very low, and the conductivity is poor, so that the specific capacity and the rate capability of the carbon source and the carbon source are reduced.
In addition to the effect of the experimental conditions on the material, the deposition time of titanium is also an important factor to consider. The deposition time is too short, a tightly coated titanium dioxide layer cannot be formed, and the electrolyte cannot be effectively isolated; the deposition time is too long, the titanium dioxide layer is too thick, the conductivity of the material is influenced, the content of active substances is reduced, and the exertion of specific capacity is influenced. The deposition time of titanium in the comparative example 7 is shorter, the specific capacity is not changed greatly, and the multiplying power is slightly reduced; in contrast, the deposition time of titanium in comparative example 8 was too long, and the specific capacity was significantly reduced.
Table 2 shows the cycle performance of practical batteries 053048 made from the positive electrode materials of the lithium ion secondary batteries obtained in examples 1 to 4 and comparative examples 1 to 8. The test conditions of the effective battery are 1.0C charging, 1.0C discharging, 3.0-4.2V, the cycle number is 2000 times, and the used charging and discharging equipment is a blue charging and discharging instrument.
TABLE 2 actual cell cycle performance
Sample (I) Ratio of increase in resistance/%) Capacity retention ratio/%)
Example 1 12.1 83.1
Comparative example 1 66.9 67.8
Comparative example 2 51.3 78.5
Comparative example 3 55.5 80.2
Comparative example 4 78.8 60.4
Example 2 16.3 82.2
Comparative example 5 49.4 75.4
Comparative example 6 80.2 59.2
Example 3 17.5 84.8
Comparative example 7 27.9 75.3
Comparative example 8 18.3 83.5
Example 4 17.7 84.5
The data in the table show that the high-voltage ternary material prepared by the invention has good cycle performance, and the capacity retention rate reaches more than 80% after 2000 cycles.
Comparative example 1 with no TiO addition2Of materials directlyThe electrolyte is contacted with the electrolyte, so that the cycle performance is poor; comparative example 2 has no carbon coating, and in the cycle process, the active material loses electric contact due to lattice expansion and contraction, so that the internal resistance is greatly increased, and the cycle performance is poor.
Comparative examples 3 and 4 adopt a one-step coating method, and the coating effect is poor, so that the resistance rise is large, and the cycle performance is poor.
Comparative example 5 is poor in conductivity due to low graphitization degree; comparative example 6 the internal resistance increased greatly and the cycle performance was poor because the crystals of the prepared material were destroyed as a result.
Comparative example 7 has too little T i content and no complete coating layer is formed, thus having poor cycle performance; comparative example 8, although superior in cycle stability, had poor specific discharge capacity as described previously.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.

Claims (7)

1. A preparation method of a high-voltage ternary material coated by a chemical vapor deposition method is characterized by comprising the following steps:
1) according to the formula LiaNixCoyA(1-x-y)O2Weighing lithium source and NixCoyA(1-x-y)(OH)2Adding the precursor into a high-speed mixer, and uniformly mixing to obtain a mixture I, wherein A is any one or two elements of Al or Mn, a is 1.03-1.06, x is 0.5-0.9, and y is 0.05-0.40;
2) adding the mixture I into a vapor deposition furnace for high-temperature roasting, wherein the rotating speed of the furnace body is 1-3 circles/minute, the roasting temperature is 880-960 ℃, the roasting time is 8-12 hours, and the roasting atmosphere is oxygen to obtain a ternary material II;
3) heating a liquid titanium source in a glass container at the temperature of 300-350 ℃, carrying out chemical deposition by using flowing inert gas to bring the volatilized titanium source into the vapor deposition furnace at the deposition temperature of 600-700 ℃ for 4-6 h to obtain a titanium-coated ternary material III;
4) airflow crushing the titanium-coated ternary material III to obtain a material IV with the particle size distribution of D50＝2.5～5.5μm；
5) Putting the material IV into a second-stage furnace body of a chemical vapor deposition furnace connected in series, wherein the temperature of the first-stage furnace body is 750-850 ℃, the atmosphere of the furnace body is inert gas, the temperature of the second-stage furnace body is 300-400 ℃, and the atmosphere of the furnace body is inert gas;
6) introducing organic gas into the first-stage chemical vapor deposition furnace, decomposing the organic gas in the first-stage furnace body, and finally depositing in the second-stage furnace body to obtain a carbon-coated material V;
7) and (4) demagnetizing and packaging the carbon-coated material V to obtain a final product.
2. The method for preparing a high-voltage ternary material coated by chemical vapor deposition according to claim 1, wherein the lithium source in step 1) is lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide.
3. The method for preparing a high-voltage ternary material coated by chemical vapor deposition according to claim 1, wherein the liquid titanium source in step 3) is one or a mixture of tetrabutyl titanate and titanium tetrachloride.
4. The method for preparing the high-voltage ternary material coated by the chemical vapor deposition method according to claim 1, wherein the titanium content in the titanium-coated ternary material III in the step 3) is 2000-4000 ppm.
5. The method for preparing the high-voltage ternary material coated by the chemical vapor deposition method according to claim 1, wherein the carbon coating mass of the carbon-coated material V in the step 6) is 1-3%.
6. The method for preparing a high-voltage ternary material coated by a chemical vapor deposition method according to claim 1, wherein the organic gas in the step 6) is any one of acetylene, acetone, ethanol and benzene or a mixed gas mixed in any proportion.
7. The coated high-voltage ternary material prepared by the preparation method according to any one of claims 1 to 6.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102186775A (en) * 2008-10-07 2011-09-14 南方化学股份公司 Carbon-coated lithium titanium spinel
CN102394295A (en) * 2011-11-23 2012-03-28 东莞新能源科技有限公司 Lithium ion battery and its positive material
CN106058220A (en) * 2016-08-12 2016-10-26 合肥国轩高科动力能源有限公司 Preparation method of titanium nitride and carbon double-coated lithium manganese iron phosphate composite material
CN108598448A (en) * 2018-06-27 2018-09-28 合肥工业大学 A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application
CN108963239A (en) * 2018-08-14 2018-12-07 上海力信能源科技有限责任公司 Nickel-cobalt lithium manganate cathode material of coated by titanium dioxide and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101282593B1 (en) * 2012-05-08 2013-07-12 한국과학기술연구원 Carbon coating method of lithium titanium oxide nanoparticle and carbon-coated nanoparticle made by using it

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102186775A (en) * 2008-10-07 2011-09-14 南方化学股份公司 Carbon-coated lithium titanium spinel
CN102394295A (en) * 2011-11-23 2012-03-28 东莞新能源科技有限公司 Lithium ion battery and its positive material
CN106058220A (en) * 2016-08-12 2016-10-26 合肥国轩高科动力能源有限公司 Preparation method of titanium nitride and carbon double-coated lithium manganese iron phosphate composite material
CN108598448A (en) * 2018-06-27 2018-09-28 合肥工业大学 A kind of three-dimensional structure carbon coating cobalt acid manganese nano-material and preparation method and application
CN108963239A (en) * 2018-08-14 2018-12-07 上海力信能源科技有限责任公司 Nickel-cobalt lithium manganate cathode material of coated by titanium dioxide and preparation method thereof

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