CN108807888B - Three-dimensional porous copper silicon carbon composite integrated electrode and preparation method thereof - Google Patents
Three-dimensional porous copper silicon carbon composite integrated electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional porous copper-silicon-carbon composite integrated electrode and a preparation method thereof. The three-dimensional porous structure can provide sufficient space for the volume expansion of silicon in the circulation process, and the graphene and the carbon nano tube have larger specific surface area, can form a stable SEI film, can prevent the electrode material from being pulverized and broken, finally enables the electrode material to keep stable electrochemical circulation, and has wide practical application significance.
Description
Technical Field
The invention belongs to the technical field of research and development and application of three-dimensional porous electrode materials, and particularly relates to a three-dimensional porous copper-silicon-carbon composite integrated electrode and a method for preparing the electrode.
Background
At the present stage, the lithium ion battery has many advantages, such as high-quality specific capacity and volume specific capacity, compared with other energy storage devices, so that the lithium ion battery is widely applied to various portable electronic devices. The graphite used for the current commercial lithium ion battery is a traditional negative electrode material, has volume expansion of only about 10 percent in the charging and discharging process, but has lower theoretical specific capacity, and only 372mAh g-1Since the demand for energy storage technology is gradually increasing, the development of electrode materials having high specific capacity is urgently needed.
Many new anode materials with higher energy storage capacity have attracted considerable research interest from researchers, such as silicon (3579mAh g)-1) Tin (b), tin (b)944mAh g-1) And the like. Compared with other novel anode materials, silicon has great advantages due to the advantages of high theoretical specific capacity, low voltage platform, no toxicity, low cost, high content and the like. However, silicon undergoes large volume expansion (328%) during charge-discharge, inducing fragmentation and pulverization of the active material and destruction of the electrode structure, eventually leading to rapid deterioration of capacity, so that severe volume expansion limits its practical application. At present, researchers have proposed a series of solutions to silicon volume expansion and electrode pulverization, such as Nanjing silicon source technology development Inc. (publication number: 201610883943), which modify the surface of silicon anode material to make the binder adhere to the surface of silicon particles, thereby maintaining the integrity of the electrode during the cycling process and improving the electrochemical cycling stability of the silicon anode material. The Suzhou Gerui power and power technology company Limited (publication number: 201611174374.0) adopts an organic solvent type binder consisting of a mixture of polyvinylidene fluoride, polytetrafluoroethylene and propylene to replace the traditional polyvinylidene fluoride, uses a silicon nanotube spherical structure as a conductive agent, and uses graphite and silicon dioxide as negative electrode materials, thereby being beneficial to improving the overall conductivity and the cyclic charge and discharge performance of the battery and inhibiting the volume expansion of silicon materials to a certain extent.
In order to overcome the problems in the prior art, a three-dimensional porous copper silicon carbon composite integrated electrode and a preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional porous copper-silicon-carbon composite integrated electrode.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a three-dimensional porous copper silicon carbon composite integrated electrode comprises the following steps: (1) preparing a copper-silicon alloy: weighing the dried copper powder and the silicon powder according to the volume ratio of 2: 1-15: 1, pouring the weighed copper powder and the silicon powder into a ball milling tank, weighing the dried ball milling beads according to the ball-material ratio of 10: 1, pouring alcohol into the ball milling tank to submerge the ball milling beads, and performing ball milling on a ball mill for 20-80 hours to obtain a copper-silicon alloy; (2) preparing a three-dimensional porous copper-silicon film precursor: drying the copper-silicon alloy powder prepared in the step (1), pouring the dried copper-silicon alloy powder and a bonding agent polyacrylonitrile into a mortar for uniform grinding, and then adding a solvent N-methyl-2-pyrrolidone for continuous grinding until a casting solution with uniform viscosity and proper film scraping is formed; pouring the prepared casting solution on a dry glass plate, scraping a flat membrane by using a membrane scraping rod, and then placing the flat membrane in prepared deionized water to perform solvent-solvent exchange to obtain a three-dimensional porous copper-silicon membrane precursor; (3) solid-phase sintering of the three-dimensional porous copper-silicon film: a. the porous copper silicon film precursor is subjected to air firing, the temperature is raised to 500 ℃ in the air at the heating rate of 2 ℃/min, the temperature is kept at the highest temperature for 1-5h, and in the process, the binder polyacrylonitrile is decomposed at high temperature to be removed, so that oxidized porous copper silicon film is obtained; b. reducing the oxidized porous copper-silicon film, heating to 800 ℃ at a heating rate of 10 ℃/min in a hydrogen atmosphere, and keeping the temperature at the highest temperature for 1-5h to obtain a three-dimensional porous copper-silicon film; 4) preparing a three-dimensional porous copper silicon carbon composite integrated electrode: and (3) placing the three-dimensional porous copper-silicon film prepared in the step (3) in a crucible, heating to 600 ℃ at a heating rate of 10 ℃/min under the atmosphere of 200sccm argon, keeping the temperature at the highest temperature for 10-50min, introducing 6sccm acetylene and 100sccm hydrogen, closing the acetylene and the hydrogen after 3-20min, and growing graphene and a carbon nano tube by using a rapid heating and cooling furnace to obtain the three-dimensional porous copper-silicon-carbon composite integrated electrode.
Preferably, the copper powder and the silicon powder in the step (1) are dried in a vacuum drying oven respectively at 50-70 ℃ for 5-24h to remove trace water contained in the copper powder and the silicon powder.
Preferably, the drying mode of the copper-silicon alloy powder in the step (2) is that the copper-silicon alloy powder is dried for 5-24 hours in a vacuum drying oven at 50-70 ℃ to remove trace water contained in the copper-silicon alloy powder.
Preferably, in the step (2), the weight ratio of the copper-silicon alloy powder to the adhesive polyacrylonitrile to the solvent N-methyl-2-pyrrolidone is 1: 0.01-0.1: 01-0.5.
Preferably, the thickness of the film scraping rod in the step (2) is 250 μm.
Another object of the present invention is to provide a three-dimensional porous copper silicon carbon composite integrated electrode prepared according to the above method.
Compared with the prior art, the invention has the beneficial effects that: 1. the thickness of the prepared copper silicon film can be controlled by the film scraping rod, so that the content of active substance silicon in unit area can be controlled, and meanwhile, the three-dimensional porous structure of the copper silicon film can provide a buffer space for the volume expansion of silicon; 2. the copper-silicon film prepared by high-temperature solid-phase sintering has high strength and good toughness, and can meet the use requirements of electrodes; 3. acetylene is used as a carbon source, graphene and carbon nanotubes grow on the carbon source by combining the autocatalysis performance of a three-dimensional continuous porous structure, the carbon nanotubes have large specific surface area, a stable SEI film can be formed, electrode materials can be prevented from being pulverized and broken, the stability in the charge and discharge cycle process is improved, and no catalyst is added, so that impurities are not introduced.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of a three-dimensional porous copper-silicon film prepared in step (3) of example 1 according to the present invention;
FIG. 2 is a scanning electron micrograph of the surface of a Cu-Si-C integrated electrode prepared according to example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of the surface of a Cu-Si-C integrated electrode prepared according to example 2 of the present invention;
FIG. 4 is a scanning electron micrograph of the surface of a Cu-Si-C integrated electrode prepared according to example 3 of the present invention.
Detailed Description
The following describes a preferred embodiment of the present invention with reference to the drawings, and the technical solution in the preferred embodiment of the present invention is clearly and completely described.
Example 1:
the preparation method of the copper-silicon-carbon integrated electrode specifically provided by the embodiment comprises the following steps of:
1) preparing a copper-silicon alloy: copper powder and silicon powder are dried in a vacuum drying oven in advance and dried for 12 hours at the temperature of 60 ℃. Weighing 23g and 2g of copper and silicon according to the volume ratio of 3: 1, pouring the weighed copper and silicon into a ball milling tank, weighing 250g of ball milling beads according to the material ratio of 10: 1, pouring the ball milling beads into the ball milling tank, pouring a proper amount of alcohol to submerge the ball milling beads, and performing ball milling on the ball milling tank for 50 hours to obtain the copper-silicon alloy.
2) Preparing a three-dimensional porous copper-silicon film precursor: placing the copper-silicon alloy prepared in the step 1) in a vacuum drying oven for drying at 60 ℃ for 12h, weighing 1g of copper-silicon alloy powder and 49.18mg of Polyacrylonitrile (PAN) as a binder, uniformly mixing in a mortar, adding 0.5g of N-methyl-2-pyrrolidone (NMP) as a solvent, and continuously grinding until a casting solution with uniform viscosity and proper film scraping is formed. Pouring a proper amount of the prepared casting solution on a glass plate dried in advance, scraping a flat membrane by using a membrane scraping rod with the thickness of 250 mu m, and then placing the flat membrane in prepared deionized water for solvent-non-solvent exchange to obtain the porous copper-silicon membrane precursor.
3) Solid-phase sintering of the three-dimensional porous copper-silicon film: and (3) carrying out solid-phase sintering on the porous copper silicon film precursor prepared in the step 2) by adopting proper sintering parameters. The sintering process is carried out in two steps, firstly, the porous copper-silicon film precursor is subjected to an air sintering process, the temperature is increased to 500 ℃ at the heating rate of 2 ℃/min in the air, the temperature is kept at the highest temperature for 2 hours, then the temperature is reduced along with a furnace, and in the process, the binder PAN is decomposed and removed at high temperature to obtain a pure copper-silicon oxide film; then reducing the oxidized porous copper-silicon film, heating to 800 ℃ at a heating rate of 10 ℃/min in a hydrogen atmosphere, keeping the temperature at the highest temperature for 1h, and then cooling along with the furnace. The reduced porous copper silicon film has certain mechanical strength and flexibility and is of a three-dimensional porous structure. FIG. 3 is a scanning electron micrograph of the surface of the three-dimensional porous Cu-Si film prepared in this example.
4) Preparing a three-dimensional porous copper silicon carbon composite integrated electrode: and (3) placing the three-dimensional porous copper silicon film prepared in the step 3) in a crucible, heating to 600 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, keeping the temperature at the highest temperature for 30min, introducing 6sccm acetylene and 100sccm hydrogen when the temperature reaches 600 ℃, and removing the hearth after 5min to obtain the three-dimensional porous copper silicon carbon composite integrated electrode. And then, the prepared copper silicon/carbon composite integrated electrode is used as a negative electrode material to assemble a battery for electrochemical performance test.
As shown in fig. 2, which is a scanning electron microscope image of the cu-si-c integrated electrode prepared in this example, the growth of the carbon nanotubes can be controlled by controlling the flow rate of acetylene and the holding time, and it can be seen from the image that a small amount of carbon nanotubes are generated on the surface of the cu-si-c integrated electrode, but the generated carbon nanotubes are shorter in length.
Example 2:
the difference from the embodiment 1 is that in the step 4), the prepared three-dimensional porous copper-silicon film is placed in a crucible, the temperature is raised to 600 ℃ by adopting a heating rate of 10 ℃/min under the argon atmosphere, the temperature is kept at the highest temperature for 30min, when the temperature reaches 600 ℃, 6sccm acetylene and 100sccm hydrogen are introduced, and after 10min, the hearth is removed, so that the three-dimensional porous copper-silicon-carbon composite integrated electrode is obtained. Compared with the example 1, the gas flow of acetylene is controlled to be unchanged, and the heat preservation time during gas introduction is increased to control the growth of the carbon nanotubes, as can be seen from the scanning electron microscope image of the copper silicon carbon integrated electrode shown in fig. 3, more carbon nanotubes are generated on the surface of the copper silicon carbon integrated electrode, the length of the copper silicon carbon integrated electrode is uniform, and the copper silicon carbon integrated electrode grows in a bundle shape.
Example 3:
the difference from the embodiment 1 is that in the step 4), the prepared three-dimensional porous copper-silicon film is placed in a crucible, the temperature is raised to 600 ℃ by adopting a heating rate of 10 ℃/min under the argon atmosphere, the temperature is kept at the highest temperature for 30min, when the temperature reaches 600 ℃, 6sccm acetylene and 100sccm hydrogen are introduced, and after 15min, the hearth is removed, so that the three-dimensional porous copper-silicon-carbon composite integrated electrode is obtained. Compared with the examples 1 and 2, the gas flow of acetylene is kept unchanged, and the heat preservation time during gas introduction is continuously increased to control the growth of the carbon nanotubes, as shown in a scanning electron microscope image of the copper silicon carbon integrated electrode shown in fig. 4, a large amount of carbon nanotubes are generated on the surface of the copper silicon carbon integrated electrode, and the generated carbon nanotubes are wrapped in a copper silicon film in a three-dimensional continuous cage-shaped structure.
Example 4:
the difference from the example 1) is that in the step 1), 30g and 0.5g of copper and silicon are weighed according to the volume ratio of 15: 1, then the weighed copper and silicon are poured into a ball milling tank, 305g of ball milling beads are weighed according to the material ratio of 10: 1, the weighed ball milling beads are also poured into the ball milling tank, a proper amount of alcohol is poured to submerge the ball milling beads, and then the ball milling is carried out on a ball mill for 50 hours, so that the copper-silicon alloy can be obtained.
The method adopts a simple and feasible mode to prepare the three-dimensional porous copper-silicon integrated electrode, uses acetylene as a carbon source, and combines the autocatalysis performance of a three-dimensional continuous porous structure to grow graphene and carbon nano tubes on the three-dimensional porous copper-silicon integrated electrode. The preparation method comprises the steps of forming a copper-silicon alloy by a simple ball milling method of copper-silicon, preparing a precursor by combining a non-solvent induced phase separation (NIPS) method of an organic film, preparing a three-dimensional porous copper-silicon film with certain toughness and mechanical strength by a solid-phase sintering method of powder metallurgy, growing graphene and carbon nanotubes by a Chemical Vapor Deposition (CVD) method, controlling the growth of the graphene and the carbon nanotubes by controlling the temperature, the gas introduction time and the flow of acetylene, and finally preparing the copper-silicon/carbon composite integrated electrode. The three-dimensional porous structure can provide sufficient space for the volume expansion of silicon in the circulation process, and the graphene and the carbon nano tube have larger specific surface area, can form a stable SEI film, can prevent the electrode material from being pulverized and broken, finally enables the electrode material to keep stable electrochemical circulation, and has wide practical application significance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A three-dimensional porous copper silicon carbon composite integrated electrode is characterized in that: the preparation method of the electrode comprises the following steps,
(1) preparing a copper-silicon alloy: weighing the dried copper powder and the silicon powder according to the volume ratio of 2: 1-15: 1, pouring the weighed copper powder and the silicon powder into a ball milling tank, weighing the dried ball milling beads according to the ball-material ratio of 10: 1, pouring alcohol into the ball milling tank to submerge the ball milling beads, and performing ball milling on a ball mill for 20-80 hours to obtain a copper-silicon alloy;
(2) preparing a three-dimensional porous copper-silicon film precursor: drying the copper-silicon alloy powder prepared in the step (1), pouring the dried copper-silicon alloy powder and a bonding agent polyacrylonitrile into a mortar for uniform grinding, and then adding a solvent N-methyl-2-pyrrolidone for continuous grinding until a casting solution with uniform viscosity and proper film scraping is formed; pouring the prepared casting solution on a dry glass plate, scraping a flat membrane by using a membrane scraping rod, and then placing the flat membrane in prepared deionized water to perform solvent-solvent exchange to obtain a three-dimensional porous copper-silicon membrane precursor;
(3) solid-phase sintering of the three-dimensional porous copper-silicon film: a. the porous copper silicon film precursor is subjected to air firing, the temperature is raised to 500 ℃ in the air at the heating rate of 2 ℃/min, the temperature is kept at the highest temperature for 1-5h, and in the process, the binder polyacrylonitrile is decomposed at high temperature to be removed, so that oxidized porous copper silicon film is obtained; b. reducing the oxidized porous copper-silicon film, heating to 800 ℃ at a heating rate of 10 ℃/min in a hydrogen atmosphere, and keeping the temperature at the highest temperature for 1-5h to obtain a three-dimensional porous copper-silicon film;
(4) preparing a three-dimensional porous copper silicon carbon composite integrated electrode: and (3) placing the three-dimensional porous copper-silicon film prepared in the step (3) in a crucible, heating to 600 ℃ at a heating rate of 10 ℃/min under the atmosphere of 200sccm argon, keeping the temperature at the highest temperature for 10-50min, introducing 6sccm acetylene and 100sccm hydrogen, closing the acetylene and the hydrogen after 3-20min, and growing graphene and a carbon nano tube by using a rapid heating and cooling furnace to obtain the three-dimensional porous copper-silicon-carbon composite integrated electrode.
2. The three-dimensional porous copper silicon carbon composite integrated electrode according to claim 1, characterized in that: and (2) the copper powder and the silicon powder in the step (1) are dried in a vacuum drying box at 50-70 ℃ for 5-24 hours to remove trace water contained in the copper powder and the silicon powder respectively.
3. The three-dimensional porous copper silicon carbon composite integrated electrode according to claim 1, characterized in that: and (3) drying the copper-silicon alloy powder in the step (2) in a manner that the copper-silicon alloy powder is placed in a vacuum drying oven to be dried for 5-24h at the temperature of 50-70 ℃ so as to remove trace water contained in the copper-silicon alloy powder.
4. The three-dimensional porous copper silicon carbon composite integrated electrode according to claim 1, characterized in that: in the step (2), the weight ratio of the copper-silicon alloy powder, the adhesive polyacrylonitrile and the solvent N-methyl-2-pyrrolidone is 1: 0.01-0.1: 01-0.5.
5. The three-dimensional porous copper silicon carbon composite integrated electrode according to claim 1, characterized in that: the thickness of the film scraping rod in the step (2) is 250 mu m.
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| CN109560256A (en) * | 2018-11-29 | 2019-04-02 | 西交利物浦大学 | The preparation method and applications of copper silicon composite cathode piece |
| CN109599534B (en) * | 2018-11-29 | 2021-04-27 | 西交利物浦大学 | Graphene-based nano flower-shaped silicon-copper alloy electrode material and preparation method and application thereof |
| CN109888173B (en) * | 2019-02-26 | 2021-09-17 | 天津工业大学 | Preparation method of three-dimensional continuous porous copper/graphite electrode |
| CN112117441A (en) * | 2019-06-19 | 2020-12-22 | 万向一二三股份公司 | Preparation method of high-strength silicon alloy composite negative electrode material of lithium ion battery |
| CN110416509B (en) * | 2019-07-17 | 2021-05-25 | 肇庆市华师大光电产业研究院 | High-specific-capacity lithium ion battery negative electrode material and preparation method thereof |
| CN113564524B (en) * | 2021-07-13 | 2023-08-01 | 南京邮电大学 | Method for preparing carbon-coated three-dimensional porous copper current collector |
| CN117117154B (en) * | 2023-10-19 | 2024-01-30 | 河南鑫泉能源科技有限公司 | Lithium ion battery silicon anode material and preparation method and application thereof |
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