CN110943213B - MOF-derived porous carbon box loaded with Co 3 V 2 O 8 Composite negative electrode material and preparation method and application thereof - Google Patents
MOF-derived porous carbon box loaded with Co 3 V 2 O 8 Composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Porous Carbon Box (PCB) loaded with one-dimensional rod-shaped Co, which is obtained by pyrolyzing Metal-Organic Framework (MOF) containing Co 3 V 2 O 8 The formed composite material, a preparation method thereof and application thereof in a lithium ion battery cathode material. The method comprises the steps of preparing a shape-controllable zeolite imidazole ester framework-67 (Zeolite imidazole Frameworks-67, ZIF-67), carrying out high-temperature pyrolysis on the zeolite imidazole ester framework serving as a template precursor, carrying out acid washing to remove Co, ultrasonically dispersing an obtained porous carbon box in a solution, then carrying out self-assembly on the porous carbon box serving as an internal framework through a hydrothermal process, and carrying out Co self-assembly on the Co 3 V 2 O 8 The porous carbon box is attached to the surface and embedded in the pores to form a composite material. The invention does not generate toxic hazardous substances in the whole experimental process, has simple and easy operation and Co 3 V 2 O 8 The @ PCB has a high specific surface area and a porous structure, effectively improves the multiplying power and the cycle performance of the lithium ion battery through the synergistic effect of the composite material, and is an excellent lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery electrode materials, in particular to a Co-loaded MOF (metal-organic framework) derived porous carbon box 3 V 2 O 8 A composite cathode material and a preparation method and application thereof.
Background
In the face of increasingly severe environmental pollution problems and energy crisis, the development of green, efficient and sustainable clean energy is not slow enough. Since clean energy such as solar energy and wind energy can be put into practical use only by a certain storage system, lithium ion batteries are continuously researched and developed as secondary batteries having high-efficiency energy conversion and storage, and are applied to life and other fields. However, in response to the market demands for high energy storage systems and high capacity, the current electrochemical performance of lithium ion batteries is not well satisfied. Therefore, the development of a new generation of lithium ion battery electrode material with high specific capacity, low price, safety and reliability has become a focus in the field of electrochemical research.
The metal oxide negative electrode material has the advantages of abundant resources, low price, higher charge-discharge specific capacity and better safety performance, but the cycle stability and rate capability of the material are reduced due to the defects of poor conductivity, easy pulverization and the like, so that the negative electrode material with better performance needs to be developed. Bimetallic oxide Co 3 V 2 O 8 The lithium ion battery cathode material has a unique crystal structure, has better cooperative electrochemical performance than single metal oxide, has higher reversible capacity and more excellent stability, is an ideal cathode material, has good application prospect in lithium ion batteries, and needs to improve the cycle and rate capability. MOFs are hybrid organic-inorganic materials with adjustable porosity and large specific surface area. The invention realizes the MOF derived porous carbon box as an internal framework through design, and the one-dimensional rod-shaped Co 3 V 2 O 8 The composite material is attached to the porous carbon box or embedded into the porous carbon box to form a composite material, so that the cycling stability and the rate capability of the battery can be obviously improved, the charge-discharge reversible capacity is also greatly improved, and the composite material is an excellent lithium ion battery cathode material.
Disclosure of Invention
Aiming at the defects of poor conductivity, poor cycle stability, poor rate performance and the like of an oxide material, the invention aims to provide a double-transition metal oxide Co 3 V 2 O 8 The composite material with the porous carbon box is prepared by firstly carrying out pyrolysis on ZIF-67 with a special morphology to obtain the porous carbon box and then carrying out one-dimensional rod-like Co 3 V 2 O 8 The composite material negative electrode is attached to the porous carbon box or embedded into the pores of the porous carbon box, and the electrochemical performance of the material is improved through the ingenious process design and the morphology control.
To achieve the above object, the present invention provides a MOF-derived porous carbon cartridge loaded with Co 3 V 2 O 8 The composite negative electrode material and the preparation method thereof comprise the following steps:
respectively adding a cobalt source and 2-methylimidazole into a proper amount of solvent, stirring for 5-10min for dissolving, then slowly adding a 2-methylimidazole solution into the cobalt source solution, mixing, continuously stirring for 4-6h, separating precipitate, washing with water and methanol for several times, and drying to obtain ZIF-67; and calcining ZIF-67 at high temperature under a protective atmosphere for pyrolysis, cooling to room temperature, washing with acid to leach Co, washing with water and ethanol for several times, and drying to obtain the porous carbon box PCB.
Adding metavanadate into deionized water, heating and stirring for 5-10min, adding hydroxide to adjust pH, adding cobalt source, and continuously stirring for 10-20min; then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, and cooling to room temperature; separating the precipitate, washing and drying to obtain a precursor; calcining the precursor in air atmosphere to obtain rod-like Co 3 V 2 O 8 。
Completely dispersing the prepared porous carbon box PCB in water by ultrasonic for 1-2h, and adding a proper amount of rod-shaped Co according to the proportion of the PCB to the Co 3 V 2 O 8 Stirring for 0.5 to 1h to mix uniformly; then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, and cooling to room temperature; after precipitation separation, washing with water and ethanol for 3 to 4 times, and drying to obtain Co 3 V 2 O 8 @ PCB composite.
The Co 3 V 2 O 8 The @ PCB composite material is a one-dimensional rod-shaped Co with a porous carbon box as an internal framework 3 V 2 O 8 A composite anode material attached to the porous carbon cartridge or embedded in the pores thereof.
The porous carbon cartridge supports Co 3 V 2 O 8 The preparation method of the composite negative electrode material comprises the following steps that the molar ratio of PCB to Co is 1 to 2 to 1; the hydrothermal reaction temperature is 120 to 180 ℃, and the hydrothermal reaction time is 8 to 169h; the precipitation separation mode is one of filtration, suction filtration or centrifugal separation; the drying is one of water bath heating evaporation, drying in a drying box and vacuum drying, and the drying time is 6 to 10h.
According to the preparation method of the porous carbon box PCB, the cobalt source is one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt oxalate or hydrates thereof; the solvent is one or more of water, ethanol and methanol; the precipitation separation mode is one of filtration, suction filtration or centrifugal separation; the protective atmosphere is one of nitrogen, argon and helium; the high-temperature calcination pyrolysis condition is that the heating rate is 1 to 5 ℃/min, and the temperature is kept at 700 to 900 ℃ for 1 to 2h; the cooling to room temperature is one of program controlled slow cooling, natural cooling or quenching in liquid nitrogen; the acid for washing and leaching Co by using acid is one or a mixture of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid and acetic acid; the drying mode is one of water bath heating evaporation, drying in a drying box and vacuum drying, and the drying time is 6-10h.
The rod-like Co 3 V 2 O 8 The preparation method of (1), wherein the metavanadate is one of ammonium metavanadate, sodium metavanadate and potassium metavanadate; the hydroxide is one of sodium hydroxide, lithium hydroxide and potassium hydroxide, and the pH is adjusted to 10 to 11; the cobalt source is one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt oxalate or hydrate thereof; the temperature of the hydrothermal reaction is 160 to 200 ℃, and the time is 12 to 24h; the precipitation separation mode is one of filtration, suction filtration or centrifugal separation; the calcination condition of the precursor in the air atmosphere is that the heating rate is 3 to 5 ℃/min, the temperature is increased to 450 to 550 ℃, the heat preservation is carried out for 5 to 8h, and then the precursor is naturally cooled to the room temperature.
The invention has the advantages that: the invention mixes Co 3 V 2 O 8 Mixing and stirring the mixture with PCB according to a certain proportion, and self-assembling the mixture through a hydrothermal process to obtain one-dimensional rod-like Co 3 V 2 O 8 The loading on the surface of the porous carbon box or in the holes of the porous carbon box has the advantages of simple experimental operation, low price, obvious effect and no toxic and harmful substances in the whole experimental process. After ZIF-67 is pyrolyzed and carbonized, acid washing is carried out, so that not only is the surface roughness and a large number of active sites increased, but also cavities and vacancies left after Co is dissolved out by acid washing are more favorable for Co-containing oxide in the space size and bonding inclination 3 V 2 O 8 The surface is closely attached or embedded in the interior of the porous carbon box structure through physical/chemical action. On the one hand, such Co 3 V 2 O 8 The nano-rod particles are firmly attached/embedded on the surface and in the holes of the porous carbon box, and the porous carbon box is used as an internally-communicated conductive framework and is added with Co 3 V 2 O 8 The one-dimensional shape characteristic of the nanorod is beneficial to rapid transmission of ions and charges among particles and in the particles, so that excellent rate characteristic is realized; on the other hand, the tight combination is beneficial to maintaining the appearance and limiting the volume expansion and pulverization phenomena of the active substance in the charging and discharging cycle process; thereby realizing better cycle performance; in addition, the composite material has a large specific surface area and a porous structure, has more active sites, is favorable for the infiltration of electrolyte, is favorable for increasing the reaction activity of the material, and reduces the internal resistance of the battery, thereby obtaining higher reversible capacity. In conclusion, the composite material has excellent comprehensive electrochemical performance when being applied to a lithium ion battery cathode material due to the synergistic effect.
Drawings
FIG. 1 shows Co obtained in example 1 3 V 2 O 8 X-ray diffraction pattern of @ PCB composite.
FIG. 2 shows a rod-like Co obtained in example 1 3 V 2 O 8 Scanning electron micrographs of the particles.
FIG. 3 is a scanning electron micrograph of ZIF-67 obtained in example 1.
FIG. 4 shows the results of example 1Get Co 3 V 2 O 8 The scanning electron microscope picture of @ PCB combined material.
FIG. 5 shows Co obtained in example 2 3 V 2 O 8 @ PCB composite first charge-discharge curve.
FIG. 6 shows Co obtained in example 2 3 V 2 O 8 @ PCB composite cycle performance curve.
FIG. 7 shows Co obtained in example 2 3 V 2 O 8 The rate performance graph of the @ PCB composite material under different current densities.
Detailed Description
In order to facilitate an understanding of the invention, the invention is described in further detail below with reference to specific embodiments and the accompanying drawings. It is to be understood that the embodiments described are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a MOF-derived porous carbon cartridge loaded with Co 3 V 2 O 8 The composite cathode material and the preparation method thereof comprise the following steps:
(1) Respectively adding cobalt nitrate hexahydrate and 2-methylimidazole into methanol, stirring for 10min for dissolving, slowly adding the 2-methylimidazole solution into the cobalt nitrate hexahydrate solution, mixing, continuously stirring for 6h, centrifugally separating precipitate, washing with deionized water and methanol for several times, and drying in a drying oven at 60 ℃ for 6h to obtain ZIF-67. Placing ZIF-67 in N 2 Heating to 800 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, washing and leaching Co with hydrochloric acid, washing with deionized water and ethanol for several times, and drying in a drying oven at 60 ℃ for 6h to obtain the porous carbon box PCB;
(2) Adding ammonium metavanadate into 50ml of deionized water, heating and stirring for 10min, adding sodium hydroxide to adjust the pH value to 11, then adding cobalt chloride hexahydrate, and continuously stirring for 20min; then the mixed solution is transferred into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and the hydrothermal reaction is carried out for 12 hours at 200 DEG, and then the reaction is carried outThen cooling to room temperature; filtering, separating and washing the precipitate with deionized water, drying the precipitate in a drying oven at 60 ℃ for 8h to obtain a precursor, heating the precursor to 550 ℃ at a speed of 5 ℃/min in an air atmosphere, and preserving heat for 5h to obtain rod-shaped Co 3 V 2 O 8 ；
(3) And (3) ultrasonically dispersing the porous carbon box PCB obtained in the step (1) in water for 1h, and adding the Co obtained in the step (2) according to the ratio of the PCB to the Co of 1 3 V 2 O 8 Stirring for 0.5h to mix uniformly, then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 160 ℃ for 12h, and naturally cooling to room temperature; centrifugally separating the precipitate, washing the precipitate with deionized water and ethanol for a plurality of times, and drying the precipitate in a drying oven at 60 ℃ for 6 hours to obtain Co 3 V 2 O 8 @ PCB composite.
Example 2
This example provides a MOF-derived porous carbon cartridge loaded with Co 3 V 2 O 8 The composite negative electrode material and the preparation method and the application thereof comprise the following steps:
(1) Respectively adding cobalt acetate tetrahydrate and 2-methylimidazole into a solution formed by mixing deionized water and methanol according to a ratio of 1. Heating ZIF-67 to 900 ℃ at a heating rate of 2 ℃/min under Ar, then preserving heat for 1h, slowly cooling to room temperature under program control, washing and leaching Co with nitric acid, washing with water and ethanol for several times, and drying in a drying oven at 80 ℃ for 6h to obtain the porous carbon box PCB;
(2) Adding sodium metavanadate into 50ml of deionized water, heating and stirring for 10min, adding sodium hydroxide to adjust the pH value to 10, then adding cobalt tetraacetate, continuously stirring for 10min, then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 180 ℃ for 14h, then naturally cooling to room temperature, carrying out suction filtration, separation and precipitation, washing with deionized water and ethanol for several times, drying in a drying oven at 60 ℃ for 8h to obtain a precursor, and then placing the precursor in an air atmosphereHeating to 500 ℃ at the speed of 5 ℃/min and preserving heat for 6 hours to obtain rod-shaped Co 3 V 2 O 8 ；
(3) Ultrasonically dispersing the PCB obtained in the step (1) in water for 1h, and adding the Co obtained in the step (2) according to the ratio of the PCB to the Co of 1 3 V 2 O 8 Stirring for 0.5h to mix uniformly, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 180 ℃ for 12h, cooling to room temperature, performing centrifugal separation on the precipitate, washing with deionized water and ethanol for several times, and drying in a drying oven at 60 ℃ for 6h to obtain Co 3 V 2 O 8 @ PCB composite;
(4) Mixing the above Co 3 V 2 O 8 The @ PCB composite material, the acetylene black and the PVDF are completely mixed in the N-methyl pyrrolidone according to the mass ratio of 7. Coating the stirred slurry on a copper foil current collector with the surface density of 2 mg/cm 2 Punching the sheet by a punching machine with the diameter of 16mm, and then putting the sheet into a vacuum drying oven for drying for 12 hours. And then assembling the battery in a glove box, wherein the battery case adopts a model of 2032, the electrolyte is 1M LiPF6, and the solvent is a mixed solution of EC and DMC in a volume ratio of 1. And (3) standing the battery for more than 12 hours after the assembly is finished, then testing the performance of the battery by adopting a Xinwei battery testing system, and testing the cycle performance and the multiplying power performance under different current densities in a voltage range of 0.02 to 3V.
Example 3
This example provides a MOF-derived porous carbon cartridge loaded with Co 3 V 2 O 8 The composite cathode material and the preparation method thereof comprise the following steps:
(1) Respectively adding cobalt chloride hexahydrate and 2-methylimidazole into ethanol, stirring for 5min for dissolving, slowly adding the 2-methylimidazole solution into the cobalt nitrate hexahydrate solution for mixing, continuously stirring for 5h, centrifugally separating precipitate, washing with deionized water and methanol for several times, heating in a water bath at 60 ℃, and evaporating for 4h to obtain ZIF-67. Heating ZIF-67 to 700 ℃ at a heating rate of 2 ℃/min under Ar, preserving heat for 2h, naturally cooling to room temperature, washing with phosphoric acid to leach Co, washing with deionized water and ethanol for several times, and drying in a drying oven at 60 ℃ for 8h to obtain a PCB;
(2) Adding ammonium metavanadate into 50ml of deionized water, heating and stirring for 15min, adding sodium hydroxide to adjust the pH value to 11, then adding cobalt nitrate hexahydrate, continuously stirring for 20min, then transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 18h at 180 ℃, and then cooling to room temperature; filtering, separating and precipitating, washing with deionized water and ethanol for several times, drying in a drying oven at 60 deg.C for 8h to obtain precursor, heating the precursor to 500 deg.C at 3 deg.C/min in air atmosphere, and maintaining for 6h to obtain rod-like Co 3 V 2 O 8 ；
(3) Completely dispersing the PCB obtained in the step (1) in water by ultrasonic for 1h, and adding the Co obtained in the step (2) according to the proportion of the PCB to the Co of 1 3 V 2 O 8 Stirring for 0.5h to mix uniformly, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 140 ℃ for 12h, cooling to room temperature, performing centrifugal separation on the precipitate, washing with deionized water and ethanol for several times, and drying in a drying oven at 60 ℃ for 6h to obtain Co 3 V 2 O 8 @ PCB composite.
Example 4
This example provides a MOF-derived porous carbon cartridge loaded with Co 3 V 2 O 8 The composite cathode material and the preparation method thereof comprise the following steps:
(1) Respectively adding cobalt sulfate heptahydrate and 2-methylimidazole into a solution formed by mixing methanol and deionized water according to a ratio of 1. Placing ZIF-67 in N 2 Heating to 800 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 1h, slowly cooling to room temperature under program control, washing and leaching Co by oxalic acid, washing for a plurality of times by deionized water and ethanol, and drying in a drying oven at 60 ℃ for 8h to obtain the PCB;
(2) Adding sodium metavanadate into 50ml deionized water, heating and stirring for 10min, adding lithium hydroxide to adjust pH to 10, and then adding cobaltous acetate tetrahydrateStirring for 10min, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 180 ℃ for 14h, naturally cooling to room temperature, performing suction filtration, separating and precipitating, washing with deionized water and ethanol for several times, drying in a drying oven at 60 ℃ for 8h to obtain a precursor, heating the precursor to 500 ℃ at a rate of 5 ℃/min in an air atmosphere, and keeping the temperature for 6h to obtain rod-shaped Co 3 V 2 O 8 ；
(3) And (3) ultrasonically dispersing the PCB obtained in the step (1) in water for 1h, and adding the Co obtained in the step (2) according to the ratio of the PCB to the Co of 1 3 V 2 O 8 Stirring for 0.5h to mix uniformly, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 180 ℃ for 12h, naturally cooling to room temperature, performing centrifugal separation on the precipitate, washing with deionized water and ethanol for several times, and drying in a drying oven at 60 ℃ for 6h to obtain Co 3 V 2 O 8 @ PCB composite.
Claims (3)
1. MOF-derived porous carbon box loaded with Co 3 V 2 O 8 The preparation method of the composite cathode material is characterized in that the prepared Co 3 V 2 O 8 @ PCB is a one-dimensional rod-like Co with porous carbon box as internal skeleton 3 V 2 O 8 A composite anode material attached to or embedded in the pores of a porous carbon cartridge, the composite material being prepared comprising the steps of:
1) Completely dispersing the prepared porous carbon box PCB in water by ultrasonic for 1-2h, and adding a proper amount of rod-shaped Co according to the proportion of the PCB to the Co 3 V 2 O 8 Stirring for 0.5 to 1h to mix uniformly;
2) Transferring the mixed solution obtained in the step 1) to a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, and cooling to room temperature;
3) Separating the precipitate obtained in the step 2), washing with water and ethanol for 3 to 4 times, and drying to obtain Co 3 V 2 O 8 @ PCB composite;
the ratio of the PCB to the Co in the step 1) is 1 to 2 to 1 in a molar ratio; the hydrothermal reaction temperature in the step 2) is 120 to 180 ℃, and the hydrothermal reaction time is 8 to 1693 h; the precipitation separation mode in the step 3) is one of filtration, suction filtration or centrifugal separation; the drying is one of water bath heating evaporation, drying in a drying box and vacuum drying, and the drying time is 6 to 10 hours;
the preparation method of the porous carbon box PCB in the step 1) comprises the following steps:
4) Respectively adding a cobalt source and 2-methylimidazole into a proper amount of solvent, stirring for 5-10min for dissolving, then slowly adding a 2-methylimidazole solution into the cobalt source solution, mixing, and continuously stirring for 4-6h;
5) Separating the precipitate separated out from the mixed solution obtained in the step 4), washing the precipitate for several times by using deionized water and methanol, and drying the precipitate to obtain ZIF-67;
6) Calcining the ZIF-67 obtained in the step 5) at high temperature under a protective atmosphere for pyrolysis, cooling to room temperature, washing and leaching Co with acid, washing with deionized water and ethanol for several times, and drying to obtain a PCB;
in the step 4), the cobalt source is one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt oxalate or hydrate thereof; the solvent is one or a mixture of water, ethanol and methanol; the precipitation separation mode in the step 5) is one of filtration, suction filtration or centrifugal separation; the protective atmosphere in the step 6) is one of nitrogen, argon and helium; the high-temperature calcination pyrolysis condition is that the heating rate is 1 to 5 ℃/min, and the temperature is kept at 700 to 900 ℃ for 1 to 2h; the cooling to room temperature is one of program-controlled slow cooling, natural cooling or quenching in liquid nitrogen; the acid for washing and leaching Co by using the acid is one or a mixture of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, oxalic acid and acetic acid; the drying mode is one of water bath heating evaporation, drying in a drying box and vacuum drying, and the drying time is 6 to 10h;
the rod-like Co in step 1) 3 V 2 O 8 The preparation method comprises the following steps:
7) Adding metavanadate into deionized water, heating and stirring for 5 to 10min, adding hydroxide to adjust the pH value, then adding a cobalt source, and continuously stirring for 10 to 20min;
8) Transferring the mixed solution obtained in the step 7) to a stainless steel reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, and cooling to room temperature;
9) Separating the precipitate obtained in the step 8), washing and drying to obtain a precursor, and calcining the obtained precursor in an air atmosphere to obtain the rod-shaped Co 3 V 2 O 8 ；
In the step 7), the metavanadate is one of ammonium metavanadate, sodium metavanadate and potassium metavanadate; the hydroxide is one of sodium hydroxide, lithium hydroxide and potassium hydroxide; adjusting the pH value to 10 to 11; the cobalt source is one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt oxalate or hydrate thereof; the hydrothermal reaction temperature in the step 8) is 160 to 200 ℃, and the time is 12 to 24h; the precipitation separation mode in the step 9) is one of filtration, suction filtration or centrifugal separation; and calcining the precursor in an air atmosphere under the condition that the heating rate is 3-5 ℃/min, heating to 450-550 ℃, preserving the heat for 5-8h, and naturally cooling to the room temperature.
2. Co-loaded MOF (Metal organic framework) derived porous carbon box obtained by using preparation method according to claim 1 3 V 2 O 8 A composite material.
3. The MOF-derived porous carbon cartridge loaded with Co of claim 1 3 V 2 O 8 The application of the composite material as the lithium ion battery cathode material is characterized in that: mixing Co 3 V 2 O 8 Mixing the @ PCB composite material serving as an active substance, a conductive agent and a binder in a certain proportion in an N-methyl pyrrolidone dispersing agent, fully stirring to form slurry, coating the slurry on the surface of a copper foil current collector, drying and cutting into a pole piece in a certain shape; the prepared pole piece is used as a negative electrode and assembled with a positive electrode, electrolyte and a diaphragm into a lithium ion battery, or the pole piece is used as a positive electrode and assembled with counter electrode metal lithium, the electrolyte and the diaphragm into an experimental half battery; the battery is charged and discharged at constant current with the current density of 0.5A/g, and the reversible mass specific capacity based on the active substance can reach more than 1000 mAh/g.
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