CN111029552A - High-voltage high-rate lithium cobalt oxide cathode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a high-voltage high-rate lithium cobaltate cathode material and a preparation method thereof, wherein a conductive oxide on the surface of the lithium cobaltate material is coated to prevent direct contact between a lithium cobaltate body material and an electrolyte to a certain extent, and a side reaction of oxidation of the electrolyte under high voltage is inhibited, so that the stability of a lithium cobaltate interface under high voltage is improved, and the cycling stability of the material is improved. In addition, the surface of the lithium cobaltate material is coated by the conductive oxide, and a conductive network formed on the surface of the particle is connected with the current collector through the conductive agent, so that the electronic conductivity of the surface of the lithium cobaltate particle is improved, the active area of electrochemical reaction is increased, and the load transfer impedance of the electrochemical reaction is reduced, thereby increasing the electrochemical reaction activity during charging and discharging; more importantly, the composite conductive oxide coating layer obtained according to a specific proportion has a more stable structure due to the chemical bonding force among ions, and the rate capability and the stability of the material are favorably improved.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a high-voltage high-rate lithium cobalt oxide positive electrode material and a preparation method thereof.
Background
With the rapid development of 3C mobile electronic devices represented by smart phones, notebook computers, digital cameras, and the like, extremely high requirements are put forward on the performance of lithium ion battery materials. Lithium cobaltate (LiCoO)2) The lithium ion battery positive electrode material is a mainstream positive electrode material of the current 3C electronic product and still occupies an irreplaceable position in the field of the positive electrode material of the lithium ion battery. LiCoO2Albeit with up to 274mAh g-1But only 140mAh g can be discharged in practical application-1The reason for the discharge capacity is that when the battery is charged to 4.2V or more, the amount of lithium ion deintercalation exceeds 50%, and the reversible capacity rapidly decreases. At present, with the development of electronic products, the requirement on the energy density of a battery is higher, and for lithium cobaltate, although the specific capacity of the lithium cobaltate can be improved by increasing the charge cut-off voltage of a lithium cobaltate material, the cycle and rate performance of the lithium cobaltate are reduced, so that the lithium cobaltate material needs to be modified.
In the modification method of lithium cobaltate, the ion doping of the bulk phase can improve the stability of the bulk phase structure, but can not inhibit the side reaction in the process of charging and discharging the lithium cobaltate; the surface coating modification method can improve the stability of the interface and the bulk phase crystal structure of the lithium cobaltate in the circulation process. At present, most of materials commonly used for coating and modifying the surface of lithium cobaltate are electronic or lithium ion insulator materials, and the lithium cobaltate materials show semiconductor characteristics after certain lithium is removed, so the electron and lithium ion conduction performance of the surface of lithium cobaltate particles is influenced by the insulator coating, and the electrochemical performance of the lithium cobaltate materials is limited. Therefore, a proper coating material needs to be selected to achieve a good comprehensive effect.
Conductive oxides such as tin-doped indium oxide (ITO), aluminum-doped zinc oxide (AZO), and fluorine-doped tin oxide (FTO) have good self-stability under the premise of chemical stability, and are often used as modified coating materials for positive electrode materials. The Chinese patent CN106803586A adopts ITO coated ternary/lithium iron phosphate to prepare the anode material, and the capacity retention rate of the material is obviously improved; the Chinese patent CN104241635A adopts AZO to coat and prepares the AZO-coated complex lithium oxide material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a high-voltage high-rate lithium cobalt oxide positive electrode material and a preparation method thereof, the method is simple, a better coating layer can be obtained through heat conduction treatment in the coating modification process, the exchange of metal ions in the coating layer and ions in the lithium cobalt oxide plays a certain doping role, the structure of the material is improved, and the stability of an interface and a bulk crystal structure of the lithium cobalt oxide in the circulation process is improved, so that better electrochemical performance is obtained.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a high-voltage high-rate lithium cobalt oxide positive electrode material comprises the following steps:
1) preparation of lithium cobaltate material
Mixing Li in a molar ratio of Li/Co of 1.03-1.072CO3And Co3O4Uniformly mixing, carrying out high-temperature reaction in a bell-type furnace, presintering at 950 ℃ for 4-6 h, then increasing the temperature, continuously calcining at 1000-1100 ℃ for 6-14 h, cooling to room temperature along with the furnace, and crushing to obtain a pre-product; uniformly mixing the crushed pre-product with an additive in proportion, calcining for 4-7 hours at 900-950 ℃, and crushing to obtain lithium cobaltate powder;
2) preparation of conductive oxide coating solution by sol-gel method
Dissolving a metal salt A in a mixed solution of water and ethanol, adding a metal salt B after the metal salt A is completely dissolved, stirring in a water bath at 50-70 ℃ to fully dissolve the metal salt B to obtain a clear and transparent solution, cooling, adding ethanol to prepare a conductive oxide coating solution with the concentration of 0.1mol/L, and standing the prepared coating solution at room temperature for 24 hours for later use; wherein the molar ratio of the metal salt A to the metal salt B is 2-20: 1, and the volume ratio of a mixed solution of water and ethanol is 1: 10-30;
3) coating of
Weighing 3-8 g of prepared lithium cobaltate powder, adding the prepared coating solution in the step 2), wherein the addition amount of the coating solution is 0.5-4 wt% of the conductive oxide/lithium cobaltate, based on the net content of the conductive oxide in the coating solution, fully stirring at room temperature, and heating until the solvent is completely evaporated; and sintering for 5-8 h at 500-700 ℃ to obtain the coated and modified lithium cobaltate positive electrode material.
The additive is one or more of magnesium oxide, magnesium hydroxide, titanium dioxide, cerium oxide, aluminum oxide and zirconium chloride. Each of said additives being Li2CO3And Co3O40.03-0.2% of the total mass.
The metal salt A is one or more of soluble zinc salt, tin salt and indium salt; the metal salt B is one or more of soluble aluminum salt, fluorine salt, tin salt and antimony salt; when the metal salt A or the metal salt B is multiple, a dispersant is required to be additionally added, the dispersant is an alcohol amine substance, and the ratio of the amount of the metal salt A to the amount of the dispersant is 1: 0.3-1.
The conductive oxide prepared in the step 2) is one or more of tin-doped indium oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide and antimony-doped tin dioxide.
The conductive oxide prepared in the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide.
The conductive oxide prepared In the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide, wherein the molar amount of Zn In the aluminum-doped zinc oxide and the molar amount of In the tin-doped indium oxide is as follows: and (3) tin-doped indium oxide being 5-8: 3.
The lithium cobaltate positive electrode material prepared by the preparation method of the high-voltage high-rate lithium cobaltate positive electrode material.
The invention has the beneficial effects that: the method adopts the traditional two-stage method to synthesize the lithium cobaltate, is simple and easy to implement, and dopes the additive into the structure of the lithium cobaltate in the synthesis process so as to ensure the stability of the structure when the lithium cobaltate is subjected to lithium intercalation and deintercalation under high voltage. The conductive oxide is selected to carry out coating modification on the lithium cobaltate material, and not only can play a role of a coating layer, but also the electronic conductivity of the surface of the lithium cobaltate particle can be improved to a certain extent.
Drawings
Fig. 1 is an XRD pattern of comparative example 1 and example 1.
Fig. 2 is SEM images of comparative example 1 and example 1.
Fig. 3 is a graph of cycle performance for comparative example 1 and example 1.
Fig. 4 is a graph of rate performance in comparative example 1 and example 2.
Detailed Description
The method for improving the cycling performance and rate capability of lithium cobaltate under high voltage according to the present invention will be described in more detail with reference to the following examples, but is not limited thereto.
The preparation method of the high-voltage high-rate lithium cobalt oxide positive electrode material comprises the following steps of:
1) preparation of lithium cobaltate material
Mixing Li in a molar ratio of Li/Co of 1.03-1.072CO3And Co3O4Uniformly mixing, carrying out high-temperature reaction in a bell-type furnace, presintering at 950 ℃ for 4-6 h, then increasing the temperature, continuously calcining at 1000-1100 ℃ for 6-14 h, cooling to room temperature along with the furnace, and crushing to obtain a pre-product; uniformly mixing the crushed pre-product with an additive in proportion, calcining for 4-7 hours at 900-950 ℃, and crushing to obtain lithium cobaltate powder;
2) preparation of conductive oxide coating solution by sol-gel method
Dissolving a metal salt A in a mixed solution of water and ethanol, adding a metal salt B after the metal salt A is completely dissolved, stirring in a water bath at 50-70 ℃ to fully dissolve the metal salt B to obtain a clear and transparent solution, cooling, adding ethanol to prepare a conductive oxide coating solution with the concentration of 0.1mol/L, and standing the prepared coating solution at room temperature for 24 hours for later use; wherein the molar ratio of the metal salt A to the metal salt B is 2-20: 1, and the volume ratio of a mixed solution of water and ethanol is 1: 10-30;
3) coating of
Weighing 3-8 g of prepared lithium cobaltate powder, adding the prepared coating solution in the step 2), wherein the addition amount of the coating solution is 0.5-4 wt% of the conductive oxide/lithium cobaltate, based on the net content of the conductive oxide in the coating solution, fully stirring at room temperature, and heating until the solvent is completely evaporated; and sintering for 5-8 h at 500-700 ℃ to obtain the coated and modified lithium cobaltate positive electrode material.
The additive is one or more of magnesium oxide, magnesium hydroxide, titanium dioxide, cerium oxide, aluminum oxide and zirconium chloride. Each of said additives being Li2CO3And Co3O40.03-0.2% of the total mass.
The metal salt A is one or more of soluble zinc salt, tin salt and indium salt; the metal salt B is one or more of soluble aluminum salt, fluorine salt, tin salt and antimony salt; when the metal salt A or the metal salt B is multiple, a dispersant is required to be additionally added, the dispersant is an alcohol amine substance, and the ratio of the amount of the metal salt A to the amount of the dispersant is 1: 0.3-1.
The conductive oxide prepared in the step 2) is one or more of tin-doped indium oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide and antimony-doped tin dioxide.
The conductive oxide prepared in the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide.
The conductive oxide prepared In the step 2) consists of aluminum-doped zinc oxide and tin-doped indium oxide, wherein the molar amount of Zn In the aluminum-doped zinc oxide and the molar amount of In the tin-doped indium oxide is as follows: and (3) tin-doped indium oxide being 5-8: 3.
The lithium cobaltate positive electrode material prepared by the preparation method of the high-voltage high-rate lithium cobaltate positive electrode material.
The coating of the conductive oxide on the surface of the lithium cobaltate material prevents direct contact between the lithium cobaltate body material and the electrolyte to a certain extent, and inhibits the side reaction of oxidation of the electrolyte under high voltage, so that the stability of a lithium cobaltate interface under high voltage is improved, and the cycling stability of the material is improved. In addition, the surface of the lithium cobaltate material is coated by the conductive oxide, and a conductive network formed on the surface of the particle is connected with the current collector through the conductive agent, so that the electronic conductivity of the surface of the lithium cobaltate particle is improved, the active area of electrochemical reaction is increased, and the load transfer impedance of the electrochemical reaction is reduced, thereby increasing the electrochemical reaction activity during charging and discharging; more importantly, the composite conductive oxide coating layer obtained according to a specific proportion has a more stable structure due to the chemical bonding force among ions, and the rate capability of the material is favorably improved.
The stability of a lithium cobaltate interface under high voltage is improved through the coating of the conductive oxide, and the cycling stability of the material is improved; in addition, the coating of the conductive oxide also improves the conductivity of the surface of the lithium cobaltate particles, thereby increasing the electrochemical reaction activity during charging and discharging and being beneficial to improving the rate capability of the material; in addition, because strong chemical bonding force exists between ions, the structural stability of the material can be obviously improved, and therefore, the composite conductive oxide coating layer obtained by compounding two or more than two conductive oxides according to a proper proportion is beneficial to improving the cycle stability and high rate performance of a lithium cobaltate product.
Comparative example 1
Mixing Li2CO3And Co3O4Uniformly mixing, carrying out a first high-temperature reaction in a bell-type furnace, preburning at 950 ℃ for 6h, then raising the temperature to 1030 ℃, continuously calcining for 7h, cooling to room temperature along with the furnace, uniformly mixing with magnesium oxide, titanium dioxide and aluminum oxide according to the mass ratio of 0.15%, 0.05% and 0.1%, pulverizing, calcining at 950 ℃ for 6h, and pulverizing to obtain the uncoated lithium cobaltate material.
Example 1
The product synthesized in comparative example 1 was used as a raw material, and subjected to coating modification treatment.
Preparing a mixed solution according to the volume ratio of 1:20, and then adding a proper amount of stannous chloride dihydrate (SnCl)2·2H2O), adding Sn after fully dissolving2+At a molar ratio of 30%And stirring the ammonium fluoride in a water bath at 60 ℃ until the ammonium fluoride is fully dissolved to obtain a clear and transparent solution, cooling the solution, adding ethanol into a volumetric flask to reach the constant volume of 0.1mol/L to obtain the fluorine-doped tin oxide coating solution, and standing the solution for 24 hours at room temperature for later use.
5g of lithium cobaltate powder are weighed, and the powder is added according to SnO2And calculating the mass of the fluorine-doped tin oxide coating solution to be 2 wt.%, stirring at room temperature to fully mix the fluorine-doped tin oxide coating solution, heating to 100 ℃ to evaporate the water and ethanol solvent, and finally carrying out heat treatment on the dried mixture at 600 ℃ to obtain the fluorine-doped tin oxide coating modified lithium cobaltate cathode material (sample FTO-LCO).
As can be seen from FIG. 1, the FTO-LCO is only coated with a layer of FTO material on the surface layer, and does not affect the bulk structure of the material. It can also be seen from the SEM photograph of fig. 2 that the coating is relatively uniform.
The fluorine-doped tin oxide coated lithium cobaltate material does not significantly affect the exertion of the capacity of the lithium cobaltate material, has the most stable cycle performance and excellent rate performance, and has the capacity retention rate of 92.8 percent at 0.1 ℃ after 100 cycles within the voltage range of 2.75-4.5V, while the comparative sample 1 is only 67.9 percent, as shown in FIG. 3; and the rate capability is obviously improved,
further investigation of the material under high charge-discharge multiplying power of 4C and 8C shows that the capacity retention rate of FTO-LCO can still reach 85.0% and 78.4%, while the comparative sample is only 58.8% and 45.5%.
Example 2
The product synthesized in the comparative example was used as a raw material, and subjected to coating modification treatment.
Weighing a proper amount of zinc acetate dihydrate (Zn (CH) according to the molar ratio of 7:0.4:3:0.333COO)2·2H2O), aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), indium trichloride tetrahydrate (InCl)3·4H2O) and stannous chloride dihydrate (SnCl)2·2H2O) is added into 1000ml ethanol solution in turn, ethanolamine (NH) is selected2CH2CH2OH) as dispersant, and adding the dispersant and zinc acetate dihydrate into the solution after stirringAnd (2) fully stirring the mixture in a water bath at 50 ℃ until a clear and transparent solution is obtained, cooling, adding ethanol into a volumetric flask to reach the constant volume of 0.1mol/L to obtain the AZO/ITO composite coating solution, and standing the prepared solution at room temperature for 24 hours for later use.
Weighing 5g of sample LCO powder, adding a composite coating solution with the mass being 2 wt.% calculated according to ZnO, fully stirring and mixing at room temperature, placing the mixture in a water bath at 80 ℃ for continuous heating and stirring until an ethanol solvent is completely evaporated, and finally carrying out heat treatment on the obtained mixture at 600 ℃ to obtain the coating modified lithium cobaltate cathode material (sample AZO/ITO-LCO).
The electrical property test shows that the AZO/ITO composite coating modified lithium cobaltate cathode material shows excellent electrochemical property, and under the test conditions that the charge-discharge multiplying power is 0.5C and the test voltage range is 2.75-4.5V, the capacity retention rate of a sample AZO/ITO-LCO is 98.2% after 50 times of circulation, while the comparative sample LCO is only 83.3%.
The capacity retention rate of the material was tested by changing the charge and discharge rate to 0.1C, 0.5C, 1C, 2C, 4C, 8C, respectively. When the charge-discharge multiplying power is 8C, the capacity retention rate of the comparative sample is only 45.4%, and the capacity retention rate of the AZO/ITO-LCO sample can still reach 86.6%, which is shown in FIG. 4. Compared with the single coating material in example 1, the capacity retention rate of the double coating material at high discharge rate is more excellent, which is probably caused by the strong chemical bonding force between ions and the obvious improvement of the structural stability of the material.
Comparative example 2
Compared with the example 2, the raw material molar ratio is changed into that the proper amount of zinc acetate dihydrate (Zn (CH) is weighed according to the molar ratio of 4:0.3:3:0.333COO)2·2H2O), aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), indium trichloride tetrahydrate (InCl)3·4H2O) and stannous chloride dihydrate (SnCl)2·2H2O), and other steps are not changed, so that an AZO/ITO-LCO sample is prepared.
Under the test conditions that the charge-discharge multiplying power is 0.5C and the test voltage range is 2.75-4.5V, after 50 cycles, the capacity retention rate of the AZO/ITO-LCO sample is 71.2%.
Comparative example 3
Compared with the example 2, the raw material molar ratio is changed to that the proper amount of zinc acetate dihydrate (Zn (CH) is weighed according to the molar ratio of 9:0.7:3:0.333COO)2·2H2O), aluminum nitrate nonahydrate (Al (NO)3)3·9H2O), indium trichloride tetrahydrate (InCl)3·4H2O) and stannous chloride dihydrate (SnCl)2·2H2O), and other steps are not changed, so that an AZO/ITO-LCO sample is prepared.
Under the test conditions that the charge-discharge multiplying power is 0.5C and the test voltage range is 2.75-4.5V, after 50 cycles, the capacity retention rate of the AZO/ITO-LCO sample is 75.2%.
Comparative example 2, comparative example 3 and example 2 changed the molar ratio of Zn and In the raw material, and thus the amounts of AZO and ITO In the clad layer, and the capacity retention rate was significantly decreased. The reason for this is that Zn and In may form more crosslinking chemical bonds at an appropriate ratio, and a stable composite clad layer may not be formed even when Zn is too much or too little.
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 (8)
1. A preparation method of a high-voltage high-rate lithium cobalt oxide positive electrode material is characterized by comprising the following steps:
1) preparation of lithium cobaltate material
Mixing Li in a molar ratio of Li/Co of 1.03-1.072CO3And Co3O4Uniformly mixing, carrying out high-temperature reaction in a bell-type furnace, presintering at 950 ℃ for 4-6 h, then increasing the temperature, continuously calcining at 1000-1100 ℃ for 6-14 h, cooling to room temperature along with the furnace, and crushing to obtain a pre-product; uniformly mixing the crushed pre-product and an additive in proportion, calcining for 4-7 h at 900-950 ℃, and pulverizingCrushing to obtain lithium cobaltate powder;
2) preparation of conductive oxide coating solution by sol-gel method
Dissolving a metal salt A in a mixed solution of water and ethanol, adding a metal salt B after the metal salt A is completely dissolved, stirring in a water bath at 50-70 ℃ to fully dissolve the metal salt B to obtain a clear and transparent solution, cooling, adding ethanol to prepare a conductive oxide coating solution with the concentration of 0.1mol/L, and standing the prepared coating solution at room temperature for 24 hours for later use; wherein the molar ratio of the metal salt A to the metal salt B is 2-20: 1, and the volume ratio of a mixed solution of water and ethanol is 1: 10-30;
3) coating of
Weighing 3-8 g of prepared lithium cobaltate powder, adding the prepared coating solution in the step 2), wherein the addition amount of the coating solution is 0.5-4% of the net mass content of the conductive oxide in the coating solution, and heating the mixture until the solvent is completely evaporated after fully stirring the mixture at room temperature; and sintering for 5-8 h at 500-700 ℃ to obtain the coated and modified lithium cobaltate positive electrode material.
2. The method for preparing the high-voltage high-rate lithium cobaltate cathode material according to claim 1, wherein the additive is one or more of magnesium oxide, magnesium hydroxide, titanium dioxide, cerium oxide, aluminum oxide and zirconium chloride.
3. The method for preparing a high-voltage high-rate lithium cobaltate cathode material according to claim 2, wherein each additive comprises Li2CO3And Co3O40.03-0.2% of the total mass.
4. The method for preparing the high-voltage high-rate lithium cobaltate cathode material according to claim 1, wherein the metal salt A is one or more of soluble zinc salt, tin salt and indium salt; the metal salt B is one or more of soluble aluminum salt, fluorine salt, tin salt and antimony salt; when the metal salt A or the metal salt B is multiple, a dispersant is required to be additionally added, the dispersant is an alcohol amine substance, and the ratio of the amount of the metal salt A to the amount of the dispersant is 1: 0.3-1.
5. The method for preparing the high-voltage high-rate lithium cobaltate cathode material according to claim 1, wherein the conductive oxide prepared in the step 2) is one or more of tin-doped indium oxide, aluminum-doped zinc oxide, fluorine-doped tin oxide and antimony-doped tin dioxide.
6. The method for preparing a high-voltage high-rate lithium cobaltate cathode material according to claim 1, wherein the conductive oxide prepared in the step 2) is composed of aluminum-doped zinc oxide and tin-doped indium oxide.
7. The method for preparing a high-voltage high-rate lithium cobaltate cathode material according to claim 1, wherein the conductive oxide prepared In the step 2) is composed of aluminum-doped zinc oxide and tin-doped indium oxide, and the molar amount of In the aluminum-doped zinc oxide is as follows, wherein the molar amount of In the aluminum-doped zinc oxide is as follows: and (3) tin-doped indium oxide being 5-8: 3.
8. The lithium cobaltate positive electrode material prepared by the method for preparing the high-voltage high-rate lithium cobaltate positive electrode material according to any one of claims 1 to 7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111825124A (en) * | 2020-06-10 | 2020-10-27 | 昆明理工大学 | Method for preparing high-voltage anode material by surface modification and regeneration of waste lithium cobaltate material |
| CN114105156A (en) * | 2022-01-27 | 2022-03-01 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-boron precursor material, preparation method thereof and nickel-cobalt-boron positive electrode material |
| CN114142010A (en) * | 2021-11-26 | 2022-03-04 | 天津巴莫科技有限责任公司 | Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof |
| CN115064692A (en) * | 2022-06-13 | 2022-09-16 | 天津巴莫科技有限责任公司 | Composite coated lithium cobaltate positive electrode material and preparation process thereof |
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| CN114142010A (en) * | 2021-11-26 | 2022-03-04 | 天津巴莫科技有限责任公司 | Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof |
| CN114142010B (en) * | 2021-11-26 | 2024-05-14 | 天津巴莫科技有限责任公司 | Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof |
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| CN114105156B (en) * | 2022-01-27 | 2022-05-27 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-boron precursor material, preparation method thereof and nickel-cobalt-boron positive electrode material |
| CN115064692A (en) * | 2022-06-13 | 2022-09-16 | 天津巴莫科技有限责任公司 | Composite coated lithium cobaltate positive electrode material and preparation process thereof |
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