Method for mass production of porous copper fluoride lithium ion battery positive electrode material
By forming a precipitate of copper acetate and polyvinylpyrrolidone under alkaline conditions and then calcining it with ammonium fluoride, the problems of high cost and low discharge efficiency of copper fluoride cathode materials were solved, enabling low-cost mass production and high-efficiency discharge of porous structures.
Patent Information
- Application Number
- CN202511491980.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-20
- Publication Date
- 2025-12-30
AI Technical Summary
Existing copper fluoride cathode materials are expensive, mostly lack porous structures, and have low discharge reaction efficiency. Commercial copper fluoride is also expensive and generates toxic substances.
Copper acetate and polyvinylpyrrolidone are mixed and reacted under alkaline conditions to form a precipitate, which is then freeze-dried and mixed with ammonium fluoride and calcined at high temperature in an inert atmosphere to form a porous copper fluoride material.
This technology enables low-cost, high-volume production of porous copper fluoride lithium-ion battery cathode materials, improving discharge reaction efficiency and specific capacity while avoiding the generation of toxic substances.
Smart Images
Figure CN121225643A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of lithium-ion battery technology, and in particular to a method for mass production of porous copper fluoride lithium-ion battery cathode materials. Background Technology
[0002] Improving the capacity of cathode materials for lithium-ion batteries is the primary research goal of scientists and engineers. The development of high-capacity cathode materials can alleviate the current situation where lithium-ion battery packs are large, heavy, and expensive, making it difficult to meet the needs of high-power and high-energy-consuming devices.
[0003] Copper fluoride cathode materials are widely used in lithium-ion primary batteries due to their high voltage and high specific capacity. However, current technology has limitations. Copper fluoride is expensive, commercially available copper fluoride lacks a porous structure, and most are synthesized using copper salts and hydrogen fluoride, resulting in high raw material costs and the presence of toxic reaction products. Furthermore, existing technologies for preparing copper fluoride cathode materials exhibit low discharge reaction efficiency. Summary of the Invention
[0004] In view of this, the present invention provides a method for mass production of porous copper fluoride lithium-ion battery cathode materials. This method involves reacting a mixture under high-temperature inert gas conditions to generate gas, forming a porous and void-like structure and thus forming copper fluoride material. This significantly improves the material's ability to embed lithium ions; provides homogeneous crystallization nuclei for the electrode material during discharge, reducing the kinetic obstacles to new phase formation; and improves the efficiency of the discharge reaction.
[0005] The method for mass production of porous copper fluoride lithium-ion battery cathode material according to the present invention includes the following steps:
[0006] (1) Mix copper acetate and polyvinylpyrrolidone, add distilled water, heat and stir to obtain a mixed solution;
[0007] (2) Under heating and stirring conditions, sodium hydroxide solution is added dropwise to the mixed solution described in step (1). After the addition is complete, the mixture is stirred and the precipitate is collected.
[0008] (3) Wash the precipitate until the pH is neutral, then freeze-dry it;
[0009] (4) The dried precipitate and ammonium fluoride are mixed and calcined to obtain porous copper fluoride.
[0010] Preferably, the mass ratio of copper acetate, polyvinylpyrrolidone and distilled water in step (1) is 3~5:1:45~50.
[0011] Preferably, the heating and stirring temperature in step (1) is 50~60℃ and the time is 1~3h.
[0012] Preferably, the heating and stirring temperature in step (2) is 55~65℃.
[0013] Preferably, the volume ratio of the sodium hydroxide solution to the mixed solution in step (2) is 1~2:1~2.
[0014] Preferably, the dripping rate in step (2) is 100~110 ml / h.
[0015] Preferably, the stirring time after the complete addition in step (2) is 1 to 2 hours.
[0016] Preferably, the freeze-drying temperature in step (3) is -20~-15℃ and the time is 10~12h.
[0017] Preferably, the mass ratio of the precipitate and ammonium fluoride in step (4) is 1:1.5~2.
[0018] Preferably, the calcination in step (4) is carried out in a nitrogen or argon atmosphere; the calcination method is as follows: first calcining at 150°C for 50-60 min, then heating to 150°C and calcining for 300-350 min, and finally heating to 240°C and calcining for 300-350 min; the heating rate is 3-5°C / min.
[0019] Compared with existing technologies, this invention has the following advantages: This invention provides a method for mass production of porous copper fluoride lithium-ion battery cathode materials. First, copper acetate and polyvinylpyrrolidone are used as raw materials, mixed, stirred, and heated, and precipitated under alkaline conditions. The precipitate is then washed until the pH is neutral, freeze-dried, and finally mixed with ammonium fluoride and calcined to obtain porous copper fluoride. The method of this invention is low-cost and environmentally friendly, generates no toxic substances, can achieve mass production, and the obtained copper fluoride has a porous structure, a higher discharge plateau, and a higher discharge specific capacity. Attached Figure Description
[0020] Figure 1 Here is a scanning electron microscope image of the copper fluoride synthesized in Example 1;
[0021] Figure 2 Discharge diagrams of commercial copper fluoride at different rates;
[0022] Figure 3 The figures show the discharge rates of the copper fluoride synthesized in Example 1 at different rates.
[0023] Figure 4 XRD image of copper fluoride synthesized in Example 1;
[0024] Figure 5 The pore size distribution diagram is shown for the copper fluoride synthesized in Example 1.
[0025] Figure 6The image shows the discharge data of the porous copper fluoride lithium-ion battery cathode material synthesized in Comparative Example 1. Detailed Implementation
[0026] This invention provides a method for mass production of porous copper fluoride lithium-ion battery cathode materials, the steps of which are as follows:
[0027] (1) After mixing copper acetate and polyvinylpyrrolidone, distilled water is added and heated and stirred at 50°C for 1 hour to obtain a mixed solution; the mass ratio of copper acetate, polyvinylpyrrolidone and distilled water is 3.5:1:50.
[0028] (2) Under the condition of heating and stirring at 55°C, sodium hydroxide solution is added dropwise to the mixed solution described in step (1) at a rate of 100 ml / h. After the addition is complete, the mixture is stirred for 1-2 h and the precipitate is collected. The volume ratio of the sodium hydroxide solution to the mixed solution is 1:1.
[0029] (3) Wash the precipitate with distilled water until the pH is neutral, and freeze dry at -20℃ for 12h;
[0030] (4) The dried precipitate and ammonium fluoride are mixed at a mass ratio of 1:1.5~2 and calcined in a nitrogen or argon atmosphere to obtain porous copper fluoride. The calcination method is as follows: first calcined at 80℃ for 50~60min, then heated to 150℃ and calcined for 300~350min, and finally heated to 240℃ and calcined for 300~350min. The heating rate for both heating cycles is 5℃ / min.
[0031] The present invention will be further described below with reference to specific embodiments and comparative examples.
[0032] Example 1
[0033] A method for mass production of porous copper fluoride lithium-ion battery cathode material, comprising the following steps:
[0034] (1) After mixing copper acetate and polyvinylpyrrolidone, distilled water is added and heated and stirred at 50°C for 1 hour to obtain a mixed solution; the mass ratio of copper acetate, polyvinylpyrrolidone and distilled water is 3.5:1:50.
[0035] (2) Under the condition of heating and stirring at 55°C, sodium hydroxide solution is added dropwise to the mixed solution described in step (1) at a rate of 100 ml / h. After the addition is complete, the mixture is stirred for 1 h and the precipitate is collected. The volume ratio of the sodium hydroxide solution to the mixed solution is 1:1.
[0036] (3) Wash the precipitate with distilled water until the pH is neutral, and freeze dry at -20℃ for 12h;
[0037] (4) The dried precipitate and ammonium fluoride are mixed at a mass ratio of 1:1.7 and calcined in an argon atmosphere to obtain porous copper fluoride. The calcination method is as follows: first calcined at 80℃ for 60 min, then heated to 150℃ and calcined for 300 min, and finally heated to 240℃ and calcined for 300 min. The heating rate for both heating cycles is 5℃ / 1 min.
[0038] Using commercial copper fluoride (Beijing Innocare Technology Co., Ltd., model A73891-1G) as a comparison, the following tests were conducted:
[0039] The scanning electron microscope image of the copper fluoride synthesized in Example 1 is shown below. Figure 1 Discharge diagrams of commercial copper fluoride at different rates are shown below. Figure 2 The discharge diagrams of copper fluoride synthesized in Example 1 at different rates are shown below. Figure 3 The XRD image of the copper fluoride synthesized in Example 1 is shown below. Figure 4 The pore size distribution of the copper fluoride synthesized in Example 1 is shown in the figure below. Figure 5 .
[0040] As can be seen from the attached diagram, this product has a lower cost compared to commercial copper fluoride, and also has significant advantages in electrochemical performance.
[0041] Comparative Example 1
[0042] A method for preparing a porous copper fluoride lithium-ion battery cathode material, comprising the following steps:
[0043] (1) After mixing copper nitrate and polyvinylpyrrolidone, distilled water is added and heated and stirred at 50°C for 1 hour to obtain a mixed solution; the mass ratio of copper nitrate, polyvinylpyrrolidone and distilled water is 3.5:1:50.
[0044] (2) Under the condition of heating and stirring at 55°C, 1M ammonium fluoride solution is added dropwise to the mixed solution in step (1) at a dropping rate of 100ml / h. After the addition is complete, the mixture is stirred for 1h and the precipitate is collected. The volume ratio of the ammonium fluoride solution to the mixed solution is 1:1.
[0045] (3) Wash the precipitate with distilled water until the pH is neutral, and freeze dry at -20℃ for 12h;
[0046] (4) The dried precipitate is calcined in an argon atmosphere to obtain copper fluoride; the calcination method is: heating to 240℃ and calcining for 300 min; the heating rate is 5℃ / min.
[0047] After obtaining the product, it is manufactured into a battery, and the discharge data is as follows: Figure 6 The discharge data show that the electrochemical performance of copper fluoride prepared by the method in Comparative Example 1 is not as good as that in Example 1.
[0048] Comparative Example 2
[0049] A method for preparing copper fluoride lithium-ion battery cathode material, the steps are the same as in Example 1, the difference is that in step (2) of Example 2, sodium hydroxide solution is added to the mixed solution in step (1) at a dropping rate of 120 ml / h. This method can only prepare a small amount of copper fluoride. The copper fluoride obtained by large-scale preparation has an uneven structure and cannot achieve mass production.
[0050] Comparative Example 3
[0051] A method for preparing copper fluoride lithium-ion battery cathode material, the steps are the same as in Example 1, the difference is that in step (2) of Example 2, sodium hydroxide solution is added to the mixed solution in step (1) at a dropping rate of 80 ml / h. The copper fluoride prepared by this method in large quantities does not have a porous structure.
[0052] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for mass production of porous copper fluoride lithium-ion battery cathode material, characterized in that, Includes the following steps: (1) Mix copper acetate and polyvinylpyrrolidone, add distilled water, heat and stir to obtain a mixed solution; (2) Under heating and stirring conditions, sodium hydroxide solution is added dropwise to the mixed solution described in step (1). After the addition is complete, the mixture is stirred and the precipitate is collected. (3) Wash the precipitate until the pH is neutral, then freeze-dry it; (4) The dried precipitate and ammonium fluoride are mixed and calcined to obtain porous copper fluoride.
2. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The mass ratio of copper acetate, polyvinylpyrrolidone and distilled water in step (1) is 3~5:1:45~50.
3. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The heating and stirring temperature in step (1) is 50~60℃, and the time is 1~3h.
4. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The heating and stirring temperature in step (2) is 55~65℃.
5. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The volume ratio of the sodium hydroxide solution to the mixed solution in step (2) is 1~2:1~2.
6. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The dripping rate in step (2) is 100~110 ml / h.
7. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The stirring time after the addition in step (2) is complete is 1~2 hours.
8. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The freeze-drying temperature in step (3) is ~20~~15℃, and the time is 10~12h.
9. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The mass ratio of the precipitate and ammonium fluoride in step (4) is 1:1.5~2.
10. The method for mass production of porous copper fluoride lithium-ion battery cathode material according to claim 1, characterized in that, The calcination in step (4) is carried out in a nitrogen or argon atmosphere; the calcination method is as follows: first calcining at 150°C for 50-60 min, then heating to 150°C and calcining for 300-350 min, and finally heating to 240°C and calcining for 300-350 min.