CN112421049A - Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material - Google Patents
Method for preparing lithium battery silicon-carbon negative electrode material through ball milling and silicon-carbon negative electrode material Download PDFInfo
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Abstract
The invention relates to the technical field of lithium battery cathode materials, in particular to a method for preparing a lithium battery silicon-carbon cathode material by ball milling, which comprises the following steps: putting silicon tetrachloride, aluminum trichloride and magnesium powder into a ball mill, heating to 150-250 ℃, and then carrying out ball milling to obtain a ball milling product; adding carbon fibers, a 1, 3-butadiene solution, isoprene, an ionic liquid and a lithium-based initiator into the ball-milled product, ball-milling at 0-10 ℃, and drying the ball-milled slurry in vacuum to obtain the silicon-carbon negative electrode material. The problems that high temperature is needed and the production efficiency is low in the production process of the silicon-based negative electrode material of the lithium battery in the prior art are solved. The preparation method realizes the polymerization of the binder and the adsorption of the ionic conductor in the ball milling process, improves the compounding capability of the silicon-carbon material and effectively improves the lithium ion conduction capability at the same time.
Description
Technical Field
The invention relates to the technical field of lithium battery cathode materials and preparation methods thereof, in particular to a method for preparing a lithium battery silicon-carbon cathode material by ball milling and the silicon-carbon cathode material.
Background
As a new type of high-energy battery, lithium ion batteries have been widely used in people's daily life. The negative electrode material is used as a main component of the lithium battery, and the performance of the negative electrode material directly influences the performance of the lithium battery. The negative electrode refers to the end of the power supply with the lower potential. In galvanic cells, which refer to the electrode that functions as the oxidizing electrode, the cell reaction is written to the left. From a physical point of view, it is the one pole of the electron flow in the circuit. The cathode material refers to a raw material for forming a cathode in a battery, and currently common cathode materials include a carbon cathode material, a tin-based cathode material, a lithium-containing transition metal nitride cathode material, an alloy cathode material and a nano-scale cathode material.
At present, the commercialized negative electrode material mainly takes graphite as a main material, the theoretical capacity of the graphite is low, the theoretical capacity of silicon is high, and the graphite has the advantages of good safety performance, low discharge voltage and the like. However, silicon is accompanied by a large volume change during lithium deintercalation, and a thick SEI film is formed during lithium intercalation, which causes disadvantages of poor cycle performance, low first-pass efficiency, and the like.
The silicon-based negative electrode material has high theoretical capacity (4200 mAh-1) And a more suitable de-intercalation potential (<0.5V) is the most promising high capacity anode material. However, the silicon material has large volume expansion (volume expansion 100% -300%) during lithium extraction/insertion. The structural expansion and contraction change destroys the stability of the electrode structure, leads to the breakage and pulverization of silicon particles, causes the collapse and the peeling of the electrode material structure, leads the electrode material to lose electric contact, finally leads to the rapid attenuation of the specific capacity of the negative electrode, and leads to the deterioration of the cycle performance of the lithium battery.
Carbon has the advantages of high stability, good conductivity, low price, wide sources and the like, but the theoretical lithium storage capacity of the carbon is lower and is only about 1/10 of silicon. In order to solve the problems of silicon materials of lithium ion batteries, a method of compounding silicon and carbon is mainly adopted at present to prepare a silicon-carbon composite negative electrode material with high electric energy storage capacity, good conductivity and excellent cycle performance.
The silicon-carbon cathode is used as a novel lithium ion battery cathode material and is more efficient than the current graphite cathode in the aspect of improving the energy density of the battery. Abroad, mass production of 18650 batteries containing silicon-carbon negative electrode materials has been achieved in panasonic, and tesla has applied silicon-carbon negative electrodes to power batteries for vehicles. The application prospect of the silicon-carbon negative electrode material is more and more bright, and the silicon-carbon negative electrode material is likely to be superior in the negative electrode material in the future.
In the existing industrial production, the silicon-carbon negative electrode material needs a high-temperature sintering process, has relatively high requirements on atmosphere, has low production efficiency and causes great influence on the whole commercialization process. In the non-sintering process, the silicon-carbon cathode powder prepared by a mechanical ball milling method is difficult to reach the nanometer level, so that the capacity and the cycle efficiency are extremely low.
Patent CN110723721A proposes a method for preparing silicon carbon negative electrode material of lithium battery, negative electrode material and lithium battery, and the carbon-coated silicon carbon negative electrode material is formed by coating and carbonizing asphalt. The production process is long, the working procedure is complex, and the production cost and large-scale rapid production are extremely unfavorable.
Patent CN107224955A provides a lithium cell silicon carbon negative electrode material carbon cladding device, makes the interior material reaction of staving abundant through double-deck scraper, has improved the cladding effect. However, the raw materials used are nanoscale raw materials, and the pretreatment process of the raw materials is very complicated.
Patent CN109524629A proposes a method for preparing a spherical silicon carbon negative electrode material for lithium ion batteries, in which the coating performance is improved by spheroidizing and granulating graphite powder and nano-silicon powder after hydroxylation treatment, the used raw material is still a nano-grade raw material, and the pretreatment process of the raw material is very complicated.
The solutions are mostly based on nano silicon raw materials, a high-temperature process is inevitably needed, the preparation process is very complicated, and the process control is difficult, so the method has very important practical significance for improving the conventional silicon-carbon cathode synthesis process.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a method for preparing a lithium battery silicon carbon negative electrode material by ball milling, which is used to solve the problems of high temperature and low production efficiency in the production process of a lithium battery silicon base negative electrode material in the prior art, and also to provide a lithium battery silicon carbon negative electrode material. The silicon tetrachloride, the aluminum trichloride and the magnesium powder are reduced at low temperature to form nano-silicon in advance, the nano-silicon and the carbon fibers are ball-milled and compounded, meanwhile, 1, 3-butadiene and isoprene form 1, 2-polybutadiene under the action of a lithium-based initiator, and the 1, 2-polybutadiene colloid has high viscosity, so that the silicon powder and the carbon powder are bonded and compounded better. The preparation method realizes the polymerization of the binder and the adsorption of ionic liquid in the ball milling process, improves the compounding capability of the silicon-carbon material and effectively improves the lithium ion conduction capability at the same time.
In order to achieve the above objects and other related objects, according to a first aspect of the present invention, there is provided a method for preparing a silicon-carbon negative electrode material for a lithium battery by ball milling, comprising the steps of:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing protective gas, sealing, heating the ball mill to 150-250 ℃, and then carrying out ball milling for 2-4 hours to obtain a ball milling product;
and step two, adding the carbon fibers, the 1, 3-butadiene solution, the isoprene, the ionic liquid and the lithium-based initiator into the ball-milled product, carrying out ball milling for 3-4 h at the temperature of 0-10 ℃ to obtain ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon cathode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 25-65 parts, 50-60 parts, 20-30 parts, 50-100 parts, 10-20 parts and 1-5 parts by weight.
Furthermore, the silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 35-50 parts, 50-60 parts, 20-30 parts, 60-80 parts, 10-20 parts and 1-5 parts by weight.
The rotating speed of the ball mill in the first step is 40-80 rpm; in the first step, the heating temperature is 200 ℃, and the ball milling time is 3 hours; and in the second step, the ball milling temperature is 5 ℃.
The lithium-based initiator is a complex of bis-piperidyl ethane and n-butyl lithium.
The ionic liquid is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonimide) salt.
The 1, 3-butadiene solution is a saturated solution of 1, 3-butadiene dissolved in ethanol.
In the preparation method, silicon tetrachloride, aluminum trichloride and magnesium powder are reduced at medium and low temperature (150-250 ℃) to form nano silicon in advance; silicon tetrachloride, aluminum trichloride and magnesium powder react to generate MgAl under the heating state2Cl8、MgCl2And metal Al particles, wherein the metal Al particles have extremely high activity because the surfaces of the metal Al particles are not oxidized, and can reduce silicon tetrachloride into simple substance Si nano particles, thereby forming the nano silicon. The preparation process of the nano silicon is not complicated, the heating temperature belongs to medium and low temperature, and the requirement on equipment is low. When the nano silicon and the carbon fiber are compounded by ball milling, 1, 3-butadiene and isoprene form 1, 2-polybutadiene under the action of a lithium-based initiator, and the 1, 2-polybutadiene colloid has stronger viscosity, so that the silicon powder and carbon powder have better bonding and compounding effects. The preparation method realizes the polymerization of the binder and the adsorption of ionic liquid in the ball milling process, improves the compounding capability of the silicon-carbon material and effectively improves the lithium ion conduction capability at the same time.
In the second step, 1, 2-polybutadiene is formed by 1, 3-butadiene and isoprene under the action of a lithium-based initiator, and the 1, 2-polybutadiene jelly has stronger viscosity, so that the silicon powder and carbon bonding composite effect is better. In order to avoid polymerization of 1, 3-butadiene and isoprene before mixing of carbon and silicon powder, 1, 3-butadiene and isoprene are mixed and then rapidly added into a ball mill, and polymerization of a binder (1, 2-polybutadiene) and adsorption of ionic liquid are realized in the ball mill process, so that the compounding capacity of the silicon-carbon material is improved, and the lithium ion conductivity is effectively improved.
In a second aspect of the invention, a silicon-carbon negative electrode material of a lithium battery is provided, and the silicon-carbon negative electrode material is prepared by the preparation method.
The silicon-carbon cathode material of the lithium battery realizes effective compounding of a silicon-carbon cathode and improves the compounding performance of the silicon-carbon cathode material.
As described above, the method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling and the silicon-carbon negative electrode material have the following beneficial effects: according to the preparation method, silicon tetrachloride, aluminum trichloride and magnesium powder are reduced at low temperature to form nano-silicon in advance, the nano-silicon and carbon fibers are ball-milled and compounded, and 1, 3-butadiene and isoprene form 1, 2-polybutadiene under the action of a lithium-based initiator, and the 1, 2-polybutadiene colloid has high viscosity, so that the silicon powder and the carbon fibers are bonded and compounded better. The preparation method realizes the polymerization of the binder and the adsorption of ionic liquid in the ball milling process, improves the compounding capability of the silicon-carbon material and effectively improves the lithium ion conduction capability at the same time.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 150 ℃ at the rotating speed of 40rpm, and carrying out ball milling for 2 hours to obtain a ball-milled product;
and secondly, adding carbon fibers, saturated solution of 1, 3-butadiene dissolved in ethanol, isoprene, ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt and a lithium-based initiator (a complex of bispiperidyl ethane and n-butyllithium) into the ball-milled product, carrying out ball milling for 3 hours at 0 ℃ to prepare ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 25 parts, 50 parts, 20 parts, 50 parts, 80 parts, 10 parts and 1 part in parts by weight.
Example 2
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 200 ℃ at the rotating speed of 50rpm, and carrying out ball milling for 2 hours to obtain a ball-milled product;
and secondly, adding carbon fibers, saturated solution of 1, 3-butadiene dissolved in ethanol, isoprene, ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt and a lithium-based initiator (a complex of bispiperidyl ethane and n-butyllithium) into the ball-milled product, carrying out ball milling for 3 hours at the temperature of 5 ℃ to prepare ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 30 parts, 50 parts, 30 parts, 60 parts, 70 parts, 15 parts and 1 part in parts by weight.
Example 3
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 250 ℃ at the rotating speed of 40rpm, and carrying out ball milling for 2 hours to obtain a ball-milled product;
and secondly, adding carbon fibers, saturated solution of 1, 3-butadiene dissolved in ethanol, isoprene, ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt and a lithium-based initiator (a complex of bispiperidyl ethane and n-butyllithium) into the ball-milled product, carrying out ball milling for 4 hours at 0 ℃ to prepare ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 30 parts, 40 parts, 50 parts, 70 parts, 12 parts and 1 part in parts by weight.
Example 4
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 150 ℃ and then carrying out ball milling for 4 hours to obtain a ball-milled product, wherein the rotating speed of the ball mill is 80 rpm;
and secondly, adding carbon fibers, saturated solution of 1, 3-butadiene dissolved in ethanol, isoprene, ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt and a lithium-based initiator (a complex of bispiperidyl ethane and n-butyllithium) into the ball-milled product, carrying out ball milling for 4 hours at 10 ℃ to prepare ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 65 parts, 60 parts, 30 parts, 100 parts, 600 parts, 90 parts, 10 parts and 1 part in parts by weight.
Example 5
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 250 ℃ at the rotating speed of 40rpm, and carrying out ball milling for 3 hours to obtain a ball-milled product;
and secondly, adding carbon fibers, saturated solution of 1, 3-butadiene dissolved in ethanol, isoprene, ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt and a lithium-based initiator (a complex of bispiperidyl ethane and n-butyllithium) into the ball-milled product, carrying out ball milling for 4 hours at the temperature of 5 ℃ to prepare ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are 45 parts, 40 parts, 50 parts, 70 parts, 12 parts and 2 parts in sequence.
Comparative example 1
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 150 ℃ at the rotating speed of 40rpm, and carrying out ball milling for 2 hours to obtain a ball-milled product;
and secondly, adding carbon fibers, saturated solution of 1, 3-butadiene dissolved in ethanol, isoprene and a lithium-based initiator (a complex of bi-piperidyl ethane and n-butyl lithium) into the ball-milled product, carrying out ball milling for 3 hours at 0 ℃ to obtain ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution and the lithium-based initiator are sequentially 25 parts, 50 parts, 20 parts, 50 parts, 80 parts and 1 part by weight.
Comparative example 1 as a control for example 1, no ionic liquid was added to comparative example 1.
Comparative example 2
A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling comprises the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing with protective gas, sealing, heating the ball mill to 150 ℃ at the rotating speed of 40rpm, and carrying out ball milling for 2 hours to obtain a ball-milled product;
and secondly, adding carbon fibers, ionic liquid 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and a lithium-based initiator (a complex of bispiperidyl ethane and n-butyllithium) into the ball-milled product, carrying out ball milling for 3 hours at the temperature of 0 ℃ to obtain ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon negative electrode material.
The silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 25 parts, 50 parts, 20 parts, 50 parts, 10 parts and 1 part by weight.
Comparative example 2 as a control for example 1, no isoprene, 1, 3-butadiene, was added to comparative example 2.
The silicon-carbon negative electrode materials prepared in the examples 1-5 and the comparative examples 1-2 are used as active materials, and are mixed with PVDF and Super-P according to the ratio of 8: 1: 1, preparing the mixture into slurry in an NMP solvent, coating the slurry on the surface of copper foil to be used as a positive electrode, taking a lithium sheet as a negative electrode, taking lithium hexafluorophosphate/ethylene carbonate as electrolyte and polypropylene as a diaphragm to assemble a CR2032 button cell, and testing the cycle performance of the cell under the current density of 0.4 mA/g. The cycle performance test results are shown in table 1:
table 1
Through detection, the silicon-carbon negative electrode materials prepared in the embodiments 1 to 5 all have good cycle performance, which shows that the silicon/carbon composite performance of the silicon-carbon negative electrode materials is better and the connection between silicon powder and carbon powder is firmer due to the introduction of the ionic liquid and the organic binder phase in the embodiments 1 to 5, and in the charging and discharging processes, the introduced binder can effectively relieve the volume expansion of silicon particles.
Comparative example 1 as a control example to example 1, no ionic liquid was added to comparative example 1. Since no ionic liquid was added in comparative example 1, the cycling performance of the silicon carbon anode material was poor.
Comparative example 2 as a control for example 1, no isoprene, 1, 3-butadiene was added to comparative example 2. Since the organic binder phase (1, 3-butadiene and isoprene form 1, 2-polybutadiene under the action of the lithium-based initiator) is not added in comparative example 2, the silicon/carbon composite connection of the silicon-carbon negative electrode material is not firm, and the cycle performance is poor.
In conclusion, in the preparation method, the silicon tetrachloride, the aluminum trichloride and the magnesium powder are reduced at low temperature to form the nano-silicon in advance, the 1, 3-butadiene and the isoprene form the 1, 2-polybutadiene and the 1, 2-polybutadiene jelly with stronger viscosity under the action of the lithium-based initiator while the nano-silicon is ball-milled and compounded with the carbon fibers, so that the silicon powder and the carbon powder have better bonding and compounding effects. The preparation method realizes the polymerization of the binder and the adsorption of the ionic conductor in the ball milling process, improves the compounding capability of the silicon-carbon material and effectively improves the lithium ion conduction capability at the same time. Therefore, the invention effectively overcomes the defect of high-temperature compounding in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. A method for preparing a lithium battery silicon-carbon negative electrode material by ball milling is characterized by comprising the following steps:
putting silicon tetrachloride, aluminum trichloride, magnesium powder and grinding balls into a ball mill, replacing protective gas, sealing, heating the ball mill to 150-250 ℃, and then carrying out ball milling for 2-4 hours to obtain a ball milling product;
and step two, adding the carbon fibers, the 1, 3-butadiene solution, the isoprene, the ionic liquid and the lithium-based initiator into the ball-milled product, carrying out ball milling for 3-4 h at the temperature of 0-10 ℃ to obtain ball-milled slurry, and carrying out vacuum drying on the ball-milled slurry to obtain the silicon-carbon cathode material.
2. The method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling according to claim 1, wherein the method comprises the following steps: the silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 25-65 parts, 50-60 parts, 20-30 parts, 50-100 parts, 10-20 parts and 1-5 parts by weight.
3. The method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling according to claim 2, wherein the method comprises the following steps: the silicon tetrachloride, the aluminum trichloride, the magnesium powder, the isoprene, the carbon fiber, the 1, 3-butadiene solution, the ionic liquid and the lithium-based initiator are sequentially 35-50 parts, 50-60 parts, 20-30 parts, 60-80 parts, 10-20 parts and 1-5 parts by weight.
4. The method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling according to claim 1, wherein the method comprises the following steps: the rotating speed of the ball mill in the first step is 40-80 rpm; in the first step, the heating temperature is 200 ℃, and the ball milling time is 3 hours;
and in the second step, the ball milling temperature is 5 ℃.
5. The method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling according to claim 1, wherein the method comprises the following steps: the lithium-based initiator is a complex of bis-piperidyl ethane and n-butyl lithium.
6. The method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling according to claim 1, wherein the method comprises the following steps: the ionic liquid is 1-butyl-3-methylimidazole bis (trifluoromethanesulfonimide) salt.
7. The method for preparing the silicon-carbon negative electrode material of the lithium battery by ball milling according to claim 1, wherein the method comprises the following steps: the 1, 3-butadiene solution is a saturated solution of 1, 3-butadiene dissolved in ethanol.
8. A lithium battery silicon carbon negative electrode material is characterized in that: the silicon-carbon negative electrode material is prepared by the preparation method of any one of claims 1 to 7.
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| CN114843496A (en) * | 2022-05-26 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN115763822A (en) * | 2023-01-06 | 2023-03-07 | 碳佳(北京)科技有限公司 | Silicon-carbon negative electrode composite material, application and lithium battery |
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| CN107634199A (en) * | 2017-09-05 | 2018-01-26 | 惠州亿纬锂能股份有限公司 | A kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery |
| US20190097222A1 (en) * | 2015-08-14 | 2019-03-28 | Energ2 Technologies, Inc. | Composites of porous nano-featured silicon materials and carbon materials |
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| CN103897405A (en) * | 2014-03-25 | 2014-07-02 | 华东理工大学 | Preparation method of ionic liquid modified graphite micro plate/silicon rubber conductive composite material |
| US20190097222A1 (en) * | 2015-08-14 | 2019-03-28 | Energ2 Technologies, Inc. | Composites of porous nano-featured silicon materials and carbon materials |
| CN107634199A (en) * | 2017-09-05 | 2018-01-26 | 惠州亿纬锂能股份有限公司 | A kind of nano-silicon, preparation method and its application in silicon-carbon composite cathode material and lithium ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114843496A (en) * | 2022-05-26 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN115763822A (en) * | 2023-01-06 | 2023-03-07 | 碳佳(北京)科技有限公司 | Silicon-carbon negative electrode composite material, application and lithium battery |
| CN115763822B (en) * | 2023-01-06 | 2023-08-04 | 碳佳(北京)科技有限公司 | Silicon-carbon negative electrode composite material, application and lithium battery |
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