CN109546090B - Preparation process for synthesizing silicon electrode by taking foam conductive net as carrier - Google Patents
Preparation process for synthesizing silicon electrode by taking foam conductive net as carrier Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation process for synthesizing a silicon electrode by taking a foam conductive net as a carrier, wherein the foam conductive net is taken as the carrier, organic silicon is hydrolyzed to deposit silicon dioxide, and ethanol mixed solution of carbon material and polyvinylidene fluoride is mixed with aluminum chloride, thermally reduced and sprayed to obtain a foam conductive net/SiOx/C electrode; the foam conductive net is composed of framework metal and sacrificial metal; the skeleton metal is one or more of nickel, iron, copper, tin and silver; the sacrificial metal is one or more of magnesium, aluminum and lithium; the molar ratio of the framework metal to the sacrificial metal is 0.1-5; the molar ratio of the sacrificial metal to the silicon is 1-4; the molar ratio of the sacrificial metal to the aluminum chloride is 0.8-1.2; the mixed solution of the carbon material and the polyvinylidene fluoride ethanol is one or more of graphene oxide, a multi-wall carbon nanotube, a single-wall carbon nanotube, carbon black, graphene, acetylene black, activated carbon, graphite, carbon microspheres, polyaniline and polypyrrole; the cathode material has good electrochemical performance and good application prospect in the field of lithium ion batteries.
Description
Technical Field
The invention relates to a preparation process of a silicon electrode, in particular to a preparation process for synthesizing the silicon electrode by taking a foam conductive net as a carrier.
Background
Silicon is a new generation of lithium ion battery cathode material and has the advantages of high electrochemical capacity, rich reserves, low price and the like; however, silicon has poor conductivity and large volume change in the charge and discharge processes, which leads to low electrochemical capacity and poor cycle life of silicon, and limits its commercial application. At present, researchers mainly adopt the following methods to improve the electrochemical performance of silicon; 1) silicon nanoparticles, thin films, nanowires. Compared with micron-sized silicon particles, the nano silicon material has large specific surface area under the same condition, and is beneficial to the full contact of the material with a current collector and electrolyte; the electron transfer rate is high, and the multiplying power performance is good; stress and strain during lithium ion insertion/removal in the charging and discharging process are reduced, and the yield strength and the anti-pulverization capability of the material are strong, so that the electrode can bear larger stress and deformation without pulverization, and higher reversible capacity and better cycling stability are obtained. 2) A silicon-based composite material; the matrix material has high mechanical strength and electrical conductivity; in the process of charging and discharging, the matrix material buffers and regulates the volume change of the silicon active material, and prevents the electrode material from being pulverized and falling off; promote the movement of electrons and ions, reduce the contact area of the active electrode material and the electrolyte, and form a stable SEI film at the interface of the electrode/the electrolyte, thereby improving the cycling stability of the material and reducing the first irreversible capacity. 3) A porous silicon-based composite material; the porous material with the three-dimensional structure can improve the reversible capacity and the circulation stability of the silicon material, a certain buffer space is provided in the volume expansion process of the porous structure, the stress change is relieved, the contact area of the material and electrolyte is increased, the transmission of ions/electrons is improved, and the electrochemical performance of the silicon material is improved.
At present, the preparation of the negative electrode of the lithium ion battery also needs to mix an active substance, conductive carbon and a binder, and then the active substance is coated on a copper sheet to prepare an electrode sheet; the addition of the conductive carbon, the binder and the copper sheet not only increases the preparation cost, but also reduces the mass content of active material silicon particles on the electrode sheet and reduces the electrochemical capacity of the lithium ion negative electrode sheet. Therefore, the silicon material and the electrode plate are effectively combined together, and the method is a method for improving the electrochemical capacity of the negative electrode of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation process for synthesizing a silicon electrode by taking a foam conductive net as a carrier, which overcomes the defects of the prior preparation technology, reduces the preparation cost of the silicon electrode and improves the electrochemical capacity of a negative electrode of a lithium ion battery. In order to achieve the purpose, the technical scheme of the invention is as follows: taking the foam conductive net as a carrier, hydrolyzing organic silicon to deposit silicon dioxide, drying, mixing with aluminum chloride, carrying out thermal reduction, acid washing, spraying ethanol mixed solution of carbon material and polyvinylidene fluoride, and drying to obtain a foam conductive net/SiOx/C electrode; the thickness of the foam conductive net is 0.5-5 mm, the specific surface area is 0.7-10 square meters/gram, the pore diameter is 1-200 micrometers, and the porosity is more than 95%; the foam conductive net is composed of framework metal and sacrificial metal; the skeleton metal is one or more of nickel, iron, copper, tin and silver; the sacrificial metal is one or more of magnesium, aluminum and lithium; the molar ratio of the framework metal to the sacrificial metal is 0.1-5; the molar ratio of the sacrificial metal to the silicon is 1-4; the molar ratio of the sacrificial metal to the aluminum chloride is 0.8-1.2; the carbon material is one or more of graphene oxide, a multi-wall carbon nanotube, a single-wall carbon nanotube, carbon black, graphene, acetylene black, activated carbon, graphite, carbon microspheres, polyaniline and polypyrrole; the mass ratio of the silicon to the carbon material is 20-1, and the mass ratio of the carbon material to the polyvinylidene fluoride is 10-0.05; a preparation process for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following steps:
1) cutting a foam conductive net with a certain area, and immersing the foam conductive net into an ethanol solution of silicate and a surfactant, wherein the temperature is controlled to be 40-70 ℃; spraying hot water, and vibrating the conductive net for 1-40 h;
2) separating and drying the product obtained in the step 1), putting the product and aluminum chloride into a container, vacuumizing, sealing, and standing for 2-40 h at 200-500 ℃;
3) putting the product obtained in the step 2) into a hydrochloric acid solution, and soaking for 5-60 hours; separating, washing with deionized water, and drying;
4) preparing a mixed solution of a carbon material and polyvinylidene fluoride ethanol, spraying the mixed solution of the carbon material and the polyvinylidene fluoride ethanol on the surface of the product obtained in the step 3), drying and tabletting to obtain the foam conductive mesh/SiOx/C electrode.
Compared with other preparation methods of silicon cathode materials, the preparation process of the foam conductive mesh/SiOx/C electrode provided by the invention has the following advantages:
1) according to the invention, the preparation of the silicon material and the preparation of the electrode plate are combined, so that the preparation process steps are reduced.
2) The invention has simple process and convenient operation, and is beneficial to industrial production.
3) According to the invention, the mixed solution of the carbon material and the polyvinylidene fluoride ethanol is sprayed on the surface of the foam conductive net/SiOx, so that the use of the carbon material and the polyvinylidene fluoride is reduced, the mass content of silicon in the electrode plate is improved, and the electrochemical capacity of the lithium ion negative electrode is improved.
4) The invention takes the foam alloy as a carrier, deposits silicon dioxide, then reacts at high temperature, and then is washed by acid and water to form the foam conductive net/SiOx with a porous structure, thereby not only improving the conductivity of the silicon active material, but also effectively accommodating the volume expansion and contraction of silicon in the charging and discharging processes; the surface of the foam conductive net is coated with carbon material and polyvinylidene fluoride to prevent silicon particles from falling off. Therefore, the invention improves the cycle life of the lithium ion cathode; the discharge capacity is more than 1000mAh/g after 0.1C circulation for 200 times. Therefore, the silicon cathode prepared by the method has good application prospect in the field of lithium ion batteries.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following embodiments are illustrated and described in detail as follows:
example 1
A composition design for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following components:
1) 0.05mol of foamed nickel-magnesium alloy, wherein the molar ratio of nickel to magnesium is 0.5; 0.02mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of graphite; polyvinylidene fluoride, 0.05g
2) 0.05mol of foamed nickel-aluminum alloy, wherein the molar ratio of nickel to magnesium is 0.5; 0.02mol of tetraethoxysilane; 0.05mol of aluminum chloride; acetylene black, 0.1 g; polyvinylidene fluoride, 0.05g
A preparation process for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following steps:
1) cutting a foam conductive net with a certain area, and immersing the foam conductive net into an ethanol solution of silicate and a surfactant, wherein the temperature is controlled at 40 ℃; spraying hot water, and vibrating the foam conductive net for 5 hours;
2) separating and drying the product obtained in the step 1), putting the product and aluminum chloride into a container, vacuumizing, sealing, and standing at 300 ℃ for 5 hours;
3) putting the product obtained in the step 2) into a hydrochloric acid solution, and soaking for 10 hours; separating, washing with deionized water, and drying;
4) preparing a mixed solution of a carbon material and polyvinylidene fluoride ethanol, spraying the mixed solution of the carbon material and the polyvinylidene fluoride ethanol on the surface of the product obtained in the step 3), drying and tabletting to obtain the foam conductive mesh/SiOx/C electrode.
The lithium ion battery cathode has good electrochemical performance; after 0.1C and 200 times of circulation, the discharge capacity is more than 1000mAh/g.
Example 2
A composition design for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following components:
3) 0.05mol of foamed copper-magnesium alloy, wherein the molar ratio of copper to magnesium is 0.3; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of graphene; polyvinylidene fluoride, 0.05g
4) 0.05mol of foamed copper-aluminum alloy, wherein the molar ratio of copper to magnesium is 0.3; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of carbon nano tubes; polyvinylidene fluoride, 0.05g
A preparation process for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following steps:
1) cutting a certain area of the foam conductive net, and immersing the foam conductive net into an ethanol solution of silicate and a surfactant, wherein the temperature is controlled at 60 ℃; spraying hot water, and vibrating the conductive net for 4 h;
2) separating and drying the product obtained in the step 1), putting the product and aluminum chloride into a container, vacuumizing, sealing, and standing at 270 ℃ for 10 hours;
3) putting the product obtained in the step 2) into a hydrochloric acid solution, and soaking for 10 hours; separating, washing with deionized water, and drying;
4) preparing a mixed solution of a carbon material and polyvinylidene fluoride ethanol, spraying the mixed solution of the carbon material and the polyvinylidene fluoride ethanol on the surface of the product obtained in the step 3), drying and tabletting to obtain the foam conductive mesh/SiOx/C electrode.
The lithium ion battery cathode has good electrochemical performance; after 0.1C and 200 times of circulation, the discharge capacity is more than 1000mAh/g.
Example 3
Same procedure as in example 1
A composition design for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following components:
5) 0.05mol of foamed copper-magnesium alloy, wherein the molar ratio of copper to magnesium is 0.1; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of activated carbon; polyvinylidene fluoride, 0.05g
6) 0.05mol of foamed copper-aluminum alloy, wherein the molar ratio of nickel to magnesium is 1; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of carbon black; polyvinylidene fluoride, 0.05g
The lithium ion battery cathode has good electrochemical performance; after 0.1C and 200 times of circulation, the discharge capacity is more than 1000mAh/g.
Example 4
Same as example 2
A composition design for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following components:
7) 0.05mol of foam iron-magnesium alloy, wherein the molar ratio of iron to magnesium is 0.2; 0.02mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of carbon black; polyvinylidene fluoride, 0.08g
8) 0.05mol of foamed tin-aluminum alloy, wherein the molar ratio of tin to aluminum is 0.6; 0.02mol of tetraethoxysilane; 0.06mol of aluminum chloride; 0.1g of activated carbon; polyvinylidene fluoride, 0.05g
9) 0.05mol of foamed silver-aluminum alloy, wherein the molar ratio of silver to aluminum is 0.3; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; acetylene black, 0.1 g; polyvinylidene fluoride, 0.05g
10) 0.05mol of foam tin-magnesium alloy, wherein the molar ratio of tin to magnesium is 1; 0.02mol of tetraethoxysilane; 0.06mol of aluminum chloride; 0.1g of graphene; polyvinylidene fluoride, 0.05g
11) 0.05mol of foamed tin-lithium alloy, wherein the molar ratio of tin to lithium is 0.5; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; acetylene black, 0.1 g; polyvinylidene fluoride, 0.05g
12) 0.05mol of foamed copper-lithium alloy, wherein the molar ratio of copper to lithium is 0.3; 0.03mol of tetraethoxysilane; 0.05mol of aluminum chloride; 0.1g of multi-wall carbon nano-tube; polyvinylidene fluoride, 0.05g
The lithium ion battery cathode has good electrochemical performance; after 0.1C and 200 times of circulation, the discharge capacity is more than 1000mAh/g.
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 (1)
1. A preparation process for synthesizing a silicon electrode by taking a foam conductive net as a carrier comprises the following steps:
1) cutting a certain area of the foam conductive net, immersing the foam conductive net into an ethanol solution of silicate and a surfactant, and controlling the temperature to be 40-70 DEG0C; spraying hot water, and vibrating the conductive net for 1-40 h; the thickness of the foam conductive net is 0.5-5 mm, the specific surface area is 0.7-10 square meters/gram, the pore diameter is 1-200 micrometers, and the porosity is more than 95%; the foam conductive net is composed of framework metal and metal lithium; the skeleton metal is one or more of nickel, iron, copper, tin and silver; the molar ratio of the framework metal to the lithium metal is 0.1-5; the molar ratio of the lithium metal to the silicon is 1-4;
2) separating and drying the product obtained in the step 1), putting the product and aluminum chloride into a container, vacuumizing, sealing and keeping the temperature at 200-500 DEG C0C, standing for 2-40 h; the molar ratio of the lithium metal to the aluminum chloride is 0.8-1.2;
3) putting the product obtained in the step 2) into a hydrochloric acid solution, and soaking for 5-60 hours; separating, washing with deionized water, and drying;
4) preparing a mixed solution of a carbon material and polyvinylidene fluoride ethanol, spraying the mixed solution of the carbon material and the polyvinylidene fluoride ethanol on the surface of the product obtained in the step 3), drying and tabletting to obtain a foam conductive mesh/SiOx/C electrode; the carbon material is one or more of graphene oxide, a multi-wall carbon nanotube, a single-wall carbon nanotube, carbon black, graphene, acetylene black, activated carbon, graphite, carbon microspheres, polyaniline and polypyrrole; the mass ratio of the silicon to the carbon material is 20-1, and the mass ratio of the carbon material to the polyvinylidene fluoride is 10-0.05.
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| CN101465416A (en) * | 2008-12-31 | 2009-06-24 | 大连海事大学 | High specific capacity composite electrode pole piece for lithium ion battery |
| CN102694156A (en) * | 2012-06-15 | 2012-09-26 | 东莞市迈科新能源有限公司 | Silicon-carbon composite negative pole material, preparation method thereof and lithium ion battery using foamed metal as negative pole current collector |
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Effective date of registration: 20230221 Address after: 225600 No.88 Bosideng Avenue, Gaoyou Economic Development Zone, Yangzhou City, Jiangsu Province Patentee after: JIANGSU OLITER ENERGY TECHNOLOGY Co.,Ltd. Address before: 310018 Hangzhou, Zhejiang, Jianggan District province Xiasha Higher Education Park, No. 258 source street Patentee before: China Jiliang University |