CN109904429B - Preparation method of silicon-carbon composite material - Google Patents
Preparation method of silicon-carbon composite material Download PDFInfo
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- CN109904429B CN109904429B CN201910167988.3A CN201910167988A CN109904429B CN 109904429 B CN109904429 B CN 109904429B CN 201910167988 A CN201910167988 A CN 201910167988A CN 109904429 B CN109904429 B CN 109904429B
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Abstract
The invention relates to the field of lithium batteries, in particular to a preparation method of a silicon-carbon composite material. The preparation method comprises the following steps: 1) dissolving organic silicon in petroleum ether to prepare an oily solution; 2) adding a polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer into the oily solution, and stirring for reaction to obtain a pre-solution; 3) adding oil-soluble phenolic resin into the pre-solution to obtain a mixed solution, mixing the mixed solution and water according to a certain proportion, and stirring until the mixed solution forms turbid solution; 4) and (3) spinning the turbid solution on the surface of the substrate, pre-drying, and calcining in a protective atmosphere to obtain the powdery silicon-carbon composite material. The raw materials of the invention have wide sources and low cost; the preparation method is simple and efficient, does not need electroplating and heavy metal or noble metal catalysts, and is more environment-friendly; the prepared silicon-carbon composite material has a complete and uniform carbon shell structure, and has good electrochemical performance, cycle performance and mechanical performance; silicon has high stability and strong antibody volume expansion capability.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a preparation method of a silicon-carbon composite material.
Background
With the rapid growth of the world population and the continuous development of the economy, the energy consumption is increasing. The vigorous development and development of new energy sources are necessary for sustainable development. Lithium ion batteries have the advantages of high specific energy, high operating voltage, no memory effect, environmental friendliness and the like, are widely applied to small-sized electrical appliances such as mobile phones, cameras, notebooks and the like, and are also popular in large-sized electric equipment such as electric vehicles, satellites, fighters and the like. The improvement of the performance and the widening of the application range of the lithium ion battery depend on the improvement of the performance of the cathode material and the reduction of the cost to a great extent. At present, the commercial lithium ion battery cathode materials are generally carbon-based materials, such as graphite, mesocarbon microbeads and the like, and have low specific capacity, unstable structure and no large-current charge and discharge. Therefore, although the lithium ion battery in the present stage has been substantially satisfactory for the portable small-sized devices, the materials for the large-sized power lithium ion battery required for the electric vehicle still need to be improved and developed.
In the non-carbon electrode, silicon has extremely high theoretical specific capacitance and a lower lithium storage reaction voltage platform, is a cheap and easily-obtained material, is extremely widely distributed in nature, and has the content in the earth crust second to oxygen, so that the silicon-based negative electrode material is a novel high-energy material with great development prospect. However, the electronic conductivity and ionic conductivity of silicon are low, resulting in poor kinetics of electrochemical reactions; the cycling stability of the common pure silicon is poor, and the phase change and the volume expansion of the silicon in the lithiation process can generate larger stress, so that a series of problems of electrode fracture pulverization, resistance increase, cycle performance sudden drop and the like can occur.
In order to solve the problems, the conventional research aiming at the silicon-based negative electrode material mainly comprises the steps of carrying out ball-milling mixing on silicon powder and a carbon source material and then carrying out pyrolysis on the silicon powder and the carbon source material so as to prepare a silicon-carbon composite material, increasing the stability of silicon and the integral electronic conductivity and ionic conductivity of the negative electrode material in a silicon-in-carbon mode, relieving the volume expansion phenomenon in the charging and discharging process of a battery and improving the cycle performance of the silicon-based material.
In the preparation process of the existing silicon-carbon composite material, the following two methods are generally adopted: firstly, preparing a three-dimensional porous silicon material by adopting a method of inducing chemical corrosion by adopting metal silver as a catalyst, then mixing the three-dimensional porous silicon material with a carbon source by a ball milling method, and sintering to obtain a carbon-coated silicon-carbon material; and secondly, sintering the silicon monoxide under the argon condition, generating silicon and silicon dioxide by utilizing the disproportionation reaction of the silicon monoxide, preparing porous silicon by an etching method, and finally, uniformly mixing the obtained mixture and a carbon source according to a certain mass ratio and then roasting. The methods have a series of defects of high catalyst cost, high raw material cost, complicated operation method steps, difficult control, poor stability in the preparation process, unobvious performance improvement effect and the like. To address such problems, those skilled in the art have made little effort.
For example, the preparation method of the silicon-carbon negative electrode material and the patent application of the invention of the porous silicon-carbon microsphere negative electrode material, which are disclosed by the chinese patent office in 2018, 9, 28 and the application publication number is CN108598430A, the preparation method comprises the following steps: and grinding the silicon powder slurry to obtain ground silicon powder slurry. And (3) carrying out graphitization treatment on the carbon micro powder to obtain graphitized carbon micro powder. Stirring the ground silicon powder slurry, continuously adding graphitized carbon micro powder into the ground silicon powder slurry in the stirring process, adding a coating carbon source, performing ultrasonic treatment, stirring simultaneously, and then performing spray drying to obtain the silicon carbon microspheres. And carbonizing the silicon-carbon microspheres to obtain the silicon-carbon microspheres. And etching the silicon carbide carbon microspheres, and then washing and drying the silicon carbide carbon microspheres to obtain the porous silicon carbon microsphere negative electrode material.
Also, for example, the preparation method of the silicon-carbon negative electrode material, the silicon-carbon negative electrode material and the patent application for the invention of the lithium ion battery, which are disclosed by the chinese patent office in 2017, 12, month and 22, the application publication number is CN107507972A, and the preparation method includes the following steps: taking silicon alloy powder as a raw material, and removing other metals except silicon in the silicon alloy powder by acid washing treatment to obtain porous silicon; putting porous silicon into a carbon precursor, and carrying out carbon coating treatment to form a silicon-carbon composite material with a carbon coating layer; and carbonizing the silicon-carbon composite material to obtain the silicon-carbon negative electrode material.
However, the silicon-carbon composite material prepared by the two technical schemes has poor coating uniformity of the outer carbon shell, namely, the outer carbon shell is uneven in thickness, the internal three-dimensional network porous silicon structure has general expression on volume expansion of antibodies, and the problems of silicon structure damage, pulverization and the like are still easy to occur after the volume expansion.
Disclosure of Invention
The invention provides a preparation method of a silicon-carbon composite material, which aims to solve the problems that the existing silicon-carbon composite material is high in preparation cost, complex in process and low in yield, and on the other hand, silicon materials are easy to damage, pulverize and the like due to phase change and volume expansion. The purpose of preparing the silicon-carbon composite material in the carbon-coated silicon structure form at low cost is realized, the prepared silicon-carbon composite material is ensured to have excellent electrochemical performance on the basis, and the environment protection and high efficiency of the preparation process are ensured.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of a silicon-carbon composite material comprises the following preparation steps:
1) dissolving organic silicon in petroleum ether to prepare an oily solution;
2) adding a polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer into the oily solution, and stirring for reaction to obtain a pre-solution;
3) adding oil-soluble phenolic resin into the pre-solution to obtain a mixed solution, mixing the mixed solution and water according to a certain proportion, and stirring until the mixed solution forms turbid solution;
4) and (3) spinning the turbid solution on the surface of the substrate, pre-drying, and calcining in a protective atmosphere to obtain the powdery silicon-carbon composite material.
According to the technical scheme, firstly, organic silicon is used as a silicon source, an oily solution prepared after the organic silicon is dissolved is added with a polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer (triblock copolymer for short) and then is stirred for reaction, then oil-soluble phenolic resin is added, the oil-soluble phenolic resin can be connected with a polycaprolactone part of the triblock copolymer to generate an assembly effect, mixed liquid is obtained, and a complete carbon-coated silicon precursor can be generated after the mixed liquid is added with water. In this process, firstly, since the triblock copolymer used in the present invention is an amphiphilic triblock copolymer, the polyethylene glycol end is hydrophilic, the polycaprolactone end is oleophilic, water is not mutually soluble with petroleum ether, thus emulsion is formed after water is added, the triblock copolymer moves to the interface of water drops and petroleum ether in the emulsion, the polycaprolactone is in the petroleum ether, the polyethylene glycol end is inserted into the water drops, further the organosilicon contacts water to hydrolyze, the hydrolysate is coated by the triblock copolymer, thereby forming a special structure assembly particle with oil-soluble phenolic resin at the outermost end, triblock copolymer at the middle layer and organosilicon hydrolysate as the core, after subsequent spin coating, pre-drying and calcining, the oil-soluble phenolic resin and the triblock copolymer are used as a carbon source, and the organosilicon hydrolysate is used as a silicon source, so that spherical particles with a silicon-in-carbon structure, namely the silicon-carbon composite material, are formed. In the silicon-carbon composite material, the carbon shell has uniform thickness, and because the triblock copolymer forms a spiral lamellar structure after being assembled, the formed carbon shell keeps a microstructure to a certain extent, has larger specific surface area and more excellent mechanical property; and the silicon inside is amorphous silicon, and the silicon-carbon particles formed after the hydrolysate of the organic silicon is coated by a carbon source and is further calcined are finer, so that the silicon-carbon composite material also has extremely large specific surface area and electrochemical activity. The monolithic silicon-carbon composite material has excellent electrochemical performance, the volume expansion of the internal silicon is not easy to occur, and the high integrity of the monolithic silicon-carbon composite material can be maintained even if the expansion occurs. The outer carbon shell has good electronic conductivity and ionic conductivity, the stability of silicon is high, and the cycle performance of the whole silicon-carbon composite material is very excellent.
Preferably, the organic silicon in the step 1) is tetraethoxysilane.
When the organic silicon is tetraethoxysilane, the polyethylene glycol end of the triblock copolymer can react with the tetraethoxysilane, so that silicon in the tetraethoxysilane is connected to the polyethylene glycol of the triblock copolymer. Therefore, when tetraethoxysilane is selected as a silicon source, the subsequent reaction and the structure of the product are also changed. The triblock copolymer in the formed assembled particle is connected with a silicon source, a polyethylene glycol end is inserted into water drops, polycaprolactone is in oil, and oil-soluble phenolic resin is located at the outermost end and is connected with the polycaprolactone part. In the final product silicon-carbon composite material obtained by subsequent preparation, silicon is not amorphous silicon any more, but is grown in the carbon shell to form a silicon nanorod array and/or a silicon nanowire on the basis of long-chain polyethylene glycol, compared with amorphous silicon, the silicon-carbon composite material has larger specific surface area and volume expansion resistance, and the carbon shell has larger internal space and higher utilization rate, so that the overall performance of the prepared silicon-carbon composite material is further optimized.
Preferably, the concentration of the organic silicon in the oily solution in the step 1) is 0.1-1.2 mol/L.
The organosilicon is used as a silicon source, if the concentration is too low, the silicon content in the prepared silicon-carbon composite material is too low, the performance is poor, and if the concentration is too high, a large amount of hydrolysis of the organosilicon in water drops and the structure of assembled particles are damaged, so that the preparation cannot be realized. Within the concentration range, the silicon-carbon composite material with good performance can be successfully prepared.
Preferably, the polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer in the step 2) is added in a proportion of 5-60 mmol per liter of oily solution.
The triblock copolymer mainly plays a role similar to a rope, is respectively connected with oil-soluble phenolic resin and an organic silicon hydrolysate or directly reacts with tetraethoxysilane at one end to serve as a silicon source and is inserted into water drops to form a carbon-silicon-coated structure, and also serves as a carbon source in the subsequent calcining process, so that the formed carbon shell has high uniformity, and the spiral lamellar structure during self-assembly is kept to a certain extent. Therefore, the using amount of the silicon-carbon composite material is not required to be excessive, the excessive using amount not only causes resource waste, but also causes uneven silicon components in the prepared silicon-carbon composite material, wherein part of the silicon-carbon composite material has higher silicon content, and the other part of the silicon-carbon composite material has lower silicon content; when the amount is too small, the organosilicon hydrolysate or tetraethoxysilane cannot be completely captured/connected, impurities are formed in the prepared product, and the product yield is reduced.
Preferably, the concentration of the oil-soluble phenolic resin in the mixed solution in the step 3) is 0.3-1.5 mol/L.
The oil-soluble phenolic resin is used as a carbon source, and if the concentration is too low, the carbon shell is too thin, so that the volume expansion performance of the silicon-carbon composite material is reduced, and if the consumption is too large, resource waste is generated, and the electrochemical performance of the silicon-carbon composite material is easily influenced.
Preferably, the mixed liquid in the step 3) and water are mixed according to the volume ratio of 100: 2-5.
If the water is added too much, obvious layering can be generated, products cannot be prepared, if the water is added too little, the product yield is low, and within the proportion range, the product yield can be ensured to be higher.
Preferably, the substrate in step 4) is a glass substrate.
The glass substrate has good stability, no reaction, good high temperature resistance and convenient subsequent product separation.
Preferably, the temperature in the pre-drying process in the step 4) is controlled to be 60-80 ℃, and the pre-drying time is 0.5-2 hours.
The petroleum ether can be recovered in the pre-drying process, and the recycling of the petroleum ether is realized.
Preferably, in the calcining process in the step 4), the calcining temperature is 550-580 ℃, the heating rate is 1-2 ℃/min, and the calcining time is 3-6 h.
And reducing silicon and carbon in the silicon source and the carbon source in the calcining process to form the silicon-carbon composite material with a good structure. Too high a calcination temperature leads to a loss of microstructure in the product, too low a calcination temperature leads to poor reduction, and the calcination effect is optimal in this temperature range.
The invention has the beneficial effects that:
1) the raw materials are wide in source and low in cost;
2) the preparation method is simple and efficient, does not need electroplating and heavy metal or noble metal catalysts, and is more environment-friendly;
3) the prepared silicon-carbon composite material has a complete and uniform carbon shell structure, and has good electrochemical performance, cycle performance and mechanical performance;
4) silicon has high stability and strong antibody volume expansion capability.
Drawings
FIG. 1 is a schematic diagram of the process for preparing amorphous silicon-carbon composite material according to the present invention;
FIG. 2 is a schematic diagram of a process for preparing a silicon-carbon nano-array composite material.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawing figures. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only examples of a part of the present invention, and not all examples. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
The starting materials used in the present invention are all those which are commercially available or available to those skilled in the art, unless otherwise specified; unless otherwise specified, all methods used in the present invention are known to those skilled in the art.
Examples 1 to 5
A preparation method of a silicon-carbon composite material comprises the following preparation steps:
1) dissolving 1,1,3, 3-tetramethyl disiloxane in petroleum ether to prepare an oily solution;
2) adding a polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer into the oily solution, and stirring for reaction to obtain a pre-solution;
3) adding oil-soluble phenolic resin (2402 phenolic resin is selected) into the pre-solution to obtain a mixed solution, mixing the mixed solution and water according to a certain proportion, and stirring until the mixed solution forms turbid solution;
4) and (3) spin-coating the turbid solution on the surface of the glass substrate, pre-drying the turbid solution to form a film, and then placing the film in a nitrogen atmosphere for calcination to obtain the powdery silicon-carbon composite material.
Specific preparation parameters of examples 1 to 5 are shown in table 1 below.
TABLE 1 specific preparation parameters for examples 1-5
The process for preparing the silicon-carbon composite material in the embodiments 1 to 5 is shown in fig. 1, the prepared silicon-carbon composite material is in a structure that a spherical carbon shell coats amorphous silicon, the silicon-carbon composite material with the structure has excellent electrochemical performance, and the problems of negative electrode material pulverization and the like caused by volume expansion of a silicon material in the charging and discharging processes can be avoided.
Examples 6 to 10
The preparation methods and preparation parameters of examples 6 to 10 correspond to those of examples 1 to 5 in this order, with the only difference that 1,1,3, 3-tetramethyldisiloxane used in step 1) of examples 1 to 5 was replaced by ethyl orthosilicate.
The processes for preparing the silicon-carbon composite materials in the embodiments 6 to 10 are shown in fig. 2, and the prepared silicon-carbon composite materials are in a structure in which a spherical carbon shell coats a nano silicon array, and the structure is further optimized in electrochemical performance and is more excellent in cycle performance compared with the structures of the silicon-carbon composite materials prepared in the embodiments 1 to 5.
And (3) detection:
the performance test was performed for examples 1 to 10. Some of the results are shown in Table 2 below. The detection result data are the average values of twenty effective data. The detection is mainly divided into the following two parts: firstly, physical property detection: detecting the particle size, the specific surface area, the compacted density and the like of the silicon-carbon composite material prepared in the embodiment 1-10 according to a method in the national standard GB/T243360-2009 graphite cathode material for lithium ion batteries; secondly, preparing the negative plate from the silicon-carbon composite material prepared in the embodiment 1-10 by a conventional assembly method, and assembling the negative plate into a button battery for detection (the charge-discharge multiplying power is 0.5C/voltage range is 0.01-2V). The specific assembling process comprises the steps of mixing LA132 binder, SP conductive agent, distilled water and silicon-carbon composite material according to the mass ratio of 1:3:200:96, and adopting LiPF6(1mol/L)/EC-EMC-DMC (1:1:1) electrolyte, a metallic lithium counter electrode and a polyethylene film were assembled in a glove box.
TABLE 2 test results
As is apparent from table 2 above, the silicon-carbon composite material prepared by the present invention has excellent physical properties and electrochemical properties, and compared with the conventional silicon negative electrode material, the cycle performance of the silicon-carbon composite material is greatly improved, and after 100 cycles, the silicon-carbon composite material can basically maintain more than 96% of capacity, and some silicon-carbon composite materials can even maintain 97% of capacity. And the electrochemical performance of the catalyst can be kept better under low-temperature conditions. Compared with the conventional silicon-carbon cathode material on the market, the silicon-carbon cathode material has very obvious effect of improving various performances.
Claims (8)
1. The preparation method of the silicon-carbon composite material is characterized by comprising the following preparation steps:
1) dissolving hydrolyzable organic silicon in petroleum ether to prepare an oily solution, wherein the concentration of the hydrolyzable organic silicon in the oily solution is 0.1-1.2 mol/L;
2) adding a polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer into the oily solution, adding the polyethylene glycol/polycaprolactone/polyethylene glycol triblock copolymer into the oily solution at a ratio of 5-60 mmol/L, and stirring to react to obtain a pre-solution;
3) adding oil-soluble phenolic resin into the pre-solution to obtain a mixed solution, wherein the concentration of the oil-soluble phenolic resin in the mixed solution is 0.3-1.5 mol/L, mixing the mixed solution and water according to a volume ratio of 100: 2-5, and stirring until the mixed solution forms turbid solution;
4) and (3) spinning the turbid solution on the surface of the substrate, pre-drying, and calcining in a protective atmosphere to obtain the powdery silicon-carbon composite material.
2. The method for preparing a silicon-carbon composite material according to claim 1, wherein the hydrolyzable organosilicon in step 1) is tetraethoxysilane.
3. The method for preparing a silicon-carbon composite material according to claim 1, wherein the substrate in step 4) is a glass substrate.
4. The method for preparing the silicon-carbon composite material according to claim 1, wherein the pre-drying temperature in the step 4) is 60-80 ℃.
5. The method for preparing the silicon-carbon composite material according to claim 1, wherein the pre-drying time in the step 4) is 0.5-2 hours.
6. The method for preparing the silicon-carbon composite material according to claim 1, wherein the calcination temperature in the calcination in the step 4) is 550-580 ℃.
7. The method for preparing the silicon-carbon composite material according to claim 1, wherein the temperature rise rate of the calcination in the step 4) is 1-2 ℃/min.
8. The preparation method of the silicon-carbon composite material as claimed in claim 1, wherein the calcination time in the step 4) is 3-6 h.
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| CN102123967A (en) * | 2008-08-13 | 2011-07-13 | 康宁股份有限公司 | Synthesis of ordered mesoporous carbon-silicon nanocomposites |
| CN107204445A (en) * | 2017-05-26 | 2017-09-26 | 郑州中科新兴产业技术研究院 | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof |
| CN109346696A (en) * | 2018-10-11 | 2019-02-15 | 桑德集团有限公司 | Silicon-carbon cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102123967A (en) * | 2008-08-13 | 2011-07-13 | 康宁股份有限公司 | Synthesis of ordered mesoporous carbon-silicon nanocomposites |
| CN107204445A (en) * | 2017-05-26 | 2017-09-26 | 郑州中科新兴产业技术研究院 | A kind of lithium ion battery three-dimensional porous silicon-carbon cathode material and preparation method thereof |
| CN109346696A (en) * | 2018-10-11 | 2019-02-15 | 桑德集团有限公司 | Silicon-carbon cathode material and preparation method thereof |
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