Preparation method of iron-manganese-nickel-copper medium-entropy oxide lithium ion battery negative electrode material
By preparing a medium-entropy oxide lithium-ion battery anode material of iron, manganese, nickel, and copper, the capacity decay problem caused by volume change was solved, and high structural stability and excellent electrochemical performance were achieved, exhibiting an initial capacity of 1372 mAh g⁻¹ and a stable capacity of 1049.48 mAh g⁻¹.
Patent Information
- Application Number
- CN202511652969.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-12
- Publication Date
- 2026-02-10
AI Technical Summary
The capacity decay of lithium-ion battery anode materials due to volume changes during charging and discharging limits their commercial potential.
The preparation method of iron-manganese-nickel-copper entropy oxide materials includes ultrasonic dispersion, precipitation reaction, drying, calcination, and coating with copper foil after mixing with binder and conductive agent to form a material with a high phase purity spinel structure.
The material's structural stability and electrochemical performance were improved, with an initial discharge capacity of up to 1372 mAh g⁻¹, and the capacity remained stable at 1049.48 mAh g⁻¹ after 150 charge-discharge cycles, which is significantly better than traditional materials.
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Figure CN121494084A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional material preparation, and particularly relates to a method for preparing a transition metal middle entropy oxide lithium-ion battery anode material. Background Technology
[0002] In recent years, the growing demand for sustainable energy has driven the continuous development of the lithium-ion battery field. Transition metal oxides, due to their excellent theoretical capacity exhibited by their conversion reaction mechanisms, have great potential as next-generation lithium-ion battery anode materials.
[0003] However, during the migration of lithium ions between electrode materials, the large volume changes that occur inside the active material lead to capacity decay, preventing the material from fully utilizing its high capacity advantage and limiting its commercial potential. Summary of the Invention
[0004] The present invention aims to overcome the shortcomings of the prior art and provide a method for preparing a lithium-ion battery anode material with good cycle stability, structural stability and excellent electrochemical performance.
[0005] To solve the above-mentioned technical problems, the present invention is implemented as follows: A method for preparing a lithium-ion battery anode material of iron-manganese-nickel-copper medium-entropy oxide can be implemented sequentially according to the following steps: (1) Disperse ferric chloride, manganese chloride, nickel chloride and copper chloride in deionized water, and after ultrasonic vibration for 10 to 50 minutes to form a uniform solution, add sodium hydroxide solution to initiate precipitation; (2) Collect the precipitate obtained in step (1), wash it alternately with deionized water and ethanol, and then dry it at 60-100℃ for 12-48 hours; (3) The product obtained in step (2) is calcined in a muffle furnace at 500-800°C for 1-5 hours to obtain iron-manganese-nickel-copper entropy oxide; (4) The entropy oxide of iron, manganese, nickel and copper obtained in step (3) is mixed with binder and conductive agent, and then ground and dispersed in N-methyl-2-pyrrolidone. It is then uniformly coated on copper foil and placed in a vacuum oven for drying, slicing and pressing to obtain the target product, iron, manganese, nickel and copper entropy oxide lithium-ion battery anode material.
[0006] Furthermore, in step (4) of the present invention, the product is dried for 6 to 12 hours under vacuum conditions of -0.1 MPa and temperature of 100 to 130°C.
[0007] Further, in step (1) of the present invention, the molar ratio of ferric chloride, manganese chloride, nickel chloride and copper chloride is 3:1:1:1; the molar ratio of sodium hydroxide to the total molar ratio of the four transition metal salts ferric chloride, manganese chloride, nickel chloride and copper chloride is 15:1.
[0008] Furthermore, in step (4) of the present invention, the entropy oxide of iron, manganese, nickel and copper obtained in step (3) is mixed with the binder and the conductive agent in sequence at a mass ratio of 8:1:1.
[0009] Furthermore, in step (2) of the present invention, the drying temperature is 80°C and the drying time is 24 hours.
[0010] Furthermore, in step (3) of the present invention, the calcination temperature is 700°C and the calcination time is 5 hours.
[0011] Furthermore, in step (4) of the present invention, the adhesive is polyvinylidene fluoride; the conductive agent is acetylene black.
[0012] Furthermore, in step (4) of the present invention, the drying temperature is 120°C and the drying time is 12 hours.
[0013] The present invention also provides a lithium-ion battery negative electrode, which is prepared by the above method, and a corresponding lithium-ion battery is prepared from the lithium-ion battery negative electrode.
[0014] Iron, manganese, and nickel are the active components contributing to capacity in the conversion reaction. Copper tends to promote the formation of oxygen vacancies, thereby improving the conductivity of the material. These four elements, together with oxygen, form a high-phase-purity spinel structure of medium-entropy oxides, unlike common multi-metal doped materials which are primarily multiphase mixtures. Medium-entropy materials effectively improve the cycling stability of electrode materials due to their entropy stabilizing effect.
[0015] This invention successfully synthesized a novel iron-manganese-nickel-copper medium-entropy oxide material using four transition metal salts. This material exhibits strong structural stability and excellent electrochemical performance. Using FeMnNiCuO as a lithium-ion battery electrode material, 0.1 Ag... -1 At current density, the initial discharge capacity can reach as high as 1372 mAh g. -1 After 150 constant current charge-discharge cycles, the battery capacity stabilized at 1049.48 mAh g. -1 The results were compared with those of FeMnNiO and FeMnCuO materials as lithium-ion electrode materials, respectively, with a yield of 0.1 Ag. -1 The initial cycle capacities under the given conditions were 1473 and 1185 mAhg, respectively. -1However, as the reaction proceeds, the capacity shows a continuous decreasing trend. After 150 charge-discharge cycles, the capacity stabilizes at 436.22 and 750.43 mAh g, respectively. -1 Based on the comparison of the above electrochemical performance, the excellent electrochemical performance of FeMnNiCuO material can be attributed to the entropy stabilization effect.
[0016] This invention successfully synthesized a novel iron-manganese-nickel-copper medium-entropy oxide material. The process is simple, and the material exhibits good reproducibility of its electrochemical performance. Comparative analysis revealed that the electrochemical performance of the iron-manganese-nickel-copper medium-entropy oxide material (FeMnNiCuO) is superior to that of heterogeneous oxide materials. Therefore, this material holds great promise and market value for future development. Attached Figure Description
[0017] The present invention will now be described in detail through specific embodiments. These embodiments are provided to enable a more thorough understanding of the invention and to fully convey the scope of the invention to those skilled in the art. As used throughout the specification and claims, the terms "comprising" or "including" are open-ended and are interpreted as "comprising but not limited to". The following description is a preferred embodiment for carrying out the invention; however, this description is intended to illustrate the general principles of the specification and is not intended to limit the scope of the invention. The scope of protection of the present invention is determined by the appended claims.
[0018] Figure 1 This is a constant current cyclic voltammetry curve of the FeMnNiCuO composite material of the present invention; Figure 2 The cycling curve of the FeMnNiCuO composite material; Figure 3 XRD characterization diagram of FeMnNiCuO composite material; Figure 4 The image shows the SEM characterization of the FeMnNiCuO composite material. Detailed Implementation Example
[0019] The preparation method of iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material is carried out in the following steps: (1) Disperse 4.05g of ferric chloride, 0.99g of manganese chloride, 0.85g of copper chloride and 1.19g of nickel chloride in 400mL of deionized water, and after ultrasonic vibration for 30min, add 3g of sodium hydroxide to initiate precipitation. (2) The precipitate was washed alternately with deionized water and ethanol, transferred to an oven and dried at 60-100°C for 36 hours, and then removed and allowed to stand at room temperature. (3) The obtained precursor was transferred to an alumina crucible and calcined in a muffle furnace at 700°C for 5 hours to obtain an iron-manganese-nickel-copper entropy oxide material. (4) The synthesized iron-manganese-nickel-copper entropy oxide material was ground and dispersed with polyvinylidene fluoride and acetylene black in N-methyl-2-pyrrolidone at a mass ratio of 8:1:1. The mixture was then uniformly coated onto the surface of copper foil that had been wiped with anhydrous ethanol. The electrode was then placed in a vacuum drying oven (-0.1 MPa) at 120°C for 12 hours. After the electrode was dried and allowed to stand at room temperature, it was pressed into a circular electrode with a diameter of 12 mm.
[0020] Lithium-ion battery assembly and testing: The half-cell assembly process must be carried out in a glove box filled with argon gas. The water and oxygen levels inside the glove box are both <0.1 ppm. The assembled cells are kept at 0.1 Ag. -1 Testing was conducted at various current densities. First, the battery performance was investigated using FeMnNiCuO composite material as the lithium-ion battery electrode material. The initial discharge capacity reached 1372 mAh g⁻¹. -1 After 150 charge-discharge cycles, the battery capacity stabilizes at 1049.48 mAh / g. -1 Using FeMnNiO as the lithium-ion electrode material, 0.1Ag -1 Under these conditions, the initial cycle capacity can reach 1473 mAh g. -1 However, in contrast, the capacity showed a continuous decreasing trend as the reaction proceeded, stabilizing at 436.22 mAh g after 150 charge-discharge cycles. -1 When FeMnCuO is used as an electrode material for lithium batteries, 0.1 A g -1 The first discharge capacity at the current density is 1185 mAhg. -1 The discharge capacity after 150 cycles is 750.43 mAh g. -1 Based on the comparison of the above electrochemical performance, FeMnNiCuO materials exhibit excellent electrochemical cycling stability, which can be attributed to a good entropy stabilization effect.
[0021] This invention successfully synthesized a novel iron-manganese-nickel-copper medium-entropy oxide material. The process is simple, and the material exhibits good reproducibility of electrochemical performance. Deionized water was used as the solvent during the synthesis. Comparative analysis revealed that the electrochemical performance of this iron-manganese-nickel-copper medium-entropy oxide material surpasses that of other metal oxide materials, avoiding the severe capacity decay caused by volume expansion in traditional metal oxide electrodes. Therefore, this material holds immense promise and market value for future development.
[0022] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a lithium-ion battery anode material of iron-manganese-nickel-copper medium-entropy oxide, characterized in that, Follow these steps in sequence: (1) Disperse ferric chloride, manganese chloride, nickel chloride and copper chloride in deionized water, and after ultrasonic vibration for 10 to 50 minutes to form a uniform solution, add sodium hydroxide solution to initiate precipitation; (2) Collect the precipitate obtained in step (1), wash it alternately with deionized water and ethanol, and then dry it at 60-100℃ for 12-48 hours; (3) The product obtained in step (2) is calcined in a muffle furnace at 500-800°C for 1-5 hours to obtain iron-manganese-nickel-copper entropy oxide; (4) The entropy oxide of iron, manganese, nickel and copper obtained in step (3) is mixed with binder and conductive agent, and then ground and dispersed in N-methyl-2-pyrrolidone. It is then uniformly coated on copper foil and placed in a vacuum oven for drying, slicing and pressing to obtain the target product, iron, manganese, nickel and copper entropy oxide lithium-ion battery anode material.
2. The preparation method of the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 1, characterized in that, In step (4), the product is dried for 6 to 12 hours under vacuum conditions of -0.1 MPa and temperature of 100 to 130°C.
3. The preparation method of the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 2, characterized in that, In step (1), the molar ratio of ferric chloride, manganese chloride, nickel chloride and copper chloride is 3:1:1:1; the molar ratio of sodium hydroxide to the total molar ratio of the four transition metal salts ferric chloride, manganese chloride, nickel chloride and copper chloride is 15:
1.
4. The preparation method of the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 3, characterized in that, In step (4), the entropy oxide of iron, manganese, nickel and copper obtained in step (3) is mixed with the binder and the conductive agent in sequence at a mass ratio of 8:1:
1.
5. The preparation method of the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 4, characterized in that, In step (2), the drying temperature is 80°C and the drying time is 24 hours.
6. The method for preparing the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 5, characterized in that, In step (3), the calcination temperature is 700℃ and the calcination time is 5 hours.
7. The preparation method of the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 6, characterized in that, In step (4), the adhesive is polyvinylidene fluoride; the conductive agent is acetylene black.
8. The method for preparing the iron-manganese-nickel-copper medium-entropy oxide lithium-ion battery anode material according to claim 7, characterized in that, In step (4), the drying temperature is 120°C and the drying time is 12 hours.
9. A lithium-ion battery negative electrode, characterized in that, It is prepared by the method described in any one of claims 1 to 8.
10. A lithium-ion battery, characterized in that, It includes the lithium-ion battery negative electrode as described in claim 9.