CN103618072A - Preparation method for silicon-carbon composite nano tube array - Google Patents
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Abstract
The invention belongs to the field of lithium ion batteries and discloses a preparation method for a silicon-carbon composite nano tube array. The preparation method for the silicon-carbon composite nano tube array is characterized by comprising the following steps: raising the temperature of a porous-anode aluminum oxide template under inert gas; introducing acetylene gas; generating a carbon nano tube array on the surface of the template by high-temperature gas-phase decomposition of acetylene; vacuumizing and introducing the inert gas, hydrogen and silane after the temperature is raised; decomposing silane to obtain a coaxial carbon nano tube and silicon nano tube array in the template; and removing silicon oxide on the surface of the template by using a hydrofluoric acid aqueous solution and drying to obtain the silicon-carbon composite nano tube array. According to the preparation method for the silicon-carbon composite nano tube array, the silicon-carbon composite nano tube array with controllable pipe diameter, pipe length and wall thickness, and uniform size can be obtained by two-step chemical vapor deposition and hydrofluoric acid corrosion; in a whole production process, complicated equipment is not used and process steps are simple, so that large-scale industrial production is facilitated; the stability of the silicon-carbon composite nano tube array is good.
Description
(1) technical field
The invention belongs to lithium ion battery field, particularly a kind of preparation method of silicon-carbon composite nano tube array.
(2) background technology
Lithium ion battery, since invention, has had benefited from its long cycle life and high specific capacity, has brought into play important effect in life; Particularly along with the aggravation of energy shortage phenomenon, people utilize the in-depth of new forms of energy, we more and more need the energy storage device that can discharge and recharge on a large scale, and lithium ion battery is with its ripe technique, and the outstanding performance of each side becomes first-selected energy accumulating device.But as an energy storing device, the specific capacity of lithium ion battery is large not enough, the specific capacity that therefore how effectively to improve lithium ion battery is main scientific research target of present stage.Silicon atom at most can be in conjunction with 4.4 lithium atoms, its theoretical specific capacity can reach 4200 mAh/g, surpass commercial Li-ion battery negative material graphite (theoretical specific capacity is 372 mAh/g) more than 10 times, the current known negative material with first water specific capacity, so silica-base material is one of direction the most popular in current lithium ion battery negative material research.Yet in embedding the process of lithium, the volumetric expansion of silicon surpasses 300%, makes silicon materials breaking and Dusting in cyclic process, lose and contact and cause the specific capacity of whole negative material sharply to decline even almost nil with current collector.
The various contact problems that cause in order to solve the volumetric expansion of silicon, researcher has been used multiple improving one's methods, typical method mainly contains three classes: one, prepare the silicon materials of nanoscale, as nano silicon particles, silicon nano thin-film etc. reduces the stress of silicon in volumetric expansion process; Two, preparation has the silicon materials of gap structure, as porous silicon, silicon nanometer ghost, silicon nanowire array, nano-tube etc. provide certain space to hold the expansion of silicon; Three, adopt that some volumetric expansions in charge and discharge process are less, the negative material with excellent conductive performance is such as graphite, is assembled into compound nano material with silicon materials.
The people such as Cui (M.-H.Park, M.G.Kim, J.Joo, K.Kim, J.Kim, S.Ahn, Y.Cui and J.Cho.Nano Lett.2009,9,3844) use porous anodic alumina template to prepare nano-tube as the negative material of lithium ion battery, circulate and still can keep the specific capacity of 2500mAh/g for 200 times; But it involves great expense, condition is harsh, and poor reproducibility, is difficult to large-scale production.Chinese patent CN102983311A discloses " preparation method of carbon nano-tube-silicon composite cathode material ", first carbon nano-tube is prepared into carbon nano-tube film, and then silane High Temperature Gas phase decomposition, at carbon nano-tube film surface deposition one deck silicon; But its product thinner thickness, needs accurate apparatus measures, and silicon is coated on carbon tube outside, still there is the pulverizing problem that breaks that produces a large amount of solid electrolytes (solid electrolyte interface, SEI) film and silicon.Chinese patent CN102354739A discloses " a kind of silicon-carbon composite anode material for lithium ion battery and preparation method thereof ", adopting Delanium particulate is core material, and pyrolysis silicon precursor and carbon precursor form the core-shell material of carbon silicon-carbon at the coated one deck silicon of Delanium microparticle surfaces and one deck carbon successively; But this material silicon content is lower, the expansion that does not have enough spaces to hold silicon causes its specific capacity lower, and cycle performance is poor.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides a kind of prepare simple, good product performance, is convenient to the preparation method of the silicon-carbon composite nano tube array of suitability for industrialized production.
The present invention is achieved through the following technical solutions:
A preparation method for silicon-carbon composite nano tube array, take porous anodic alumina template as raw material, comprises the steps:
(1) porous anodic alumina template is put into the thermal treatment zone of tube furnace, under inert gas, heated up, pass into acetylene gas, the High Temperature Gas phase decomposition of acetylene is at template surface Formed nano-tube array;
(2) carbon nano pipe array is put into the thermal treatment zone of tube furnace, be evacuated to vacuum, pass into inert gas, hydrogen and silane after intensification, the high-temperature low-pressure gas-phase decomposition of silane under hydrogen shield, obtains being included in coaxial carbon nano-tube and nano-tube array in template;
(3) coaxial carbon nano-tube and nano-tube array are soaked and removed template and surperficial silica with hydrofluoric acid aqueous solution, after being dried, obtain product.
More excellent technical scheme of the present invention is:
The aperture of described porous anodic alumina template is 200nm.Because carbon or silicon preferentially deposit at the mouth of pipe, so the less porous anodic alumina template in aperture is easily stopped up the mouth of pipe by carbon or silicon in chemical vapor deposition processes, cause on the inwall of template duct deposition seldom or hardly deposit carbon or silicon, can not get silicon-carbon composite nano tube; And that the larger porous anodic alumina template in aperture itself is prepared productive rate is lower, and pore-size distribution is poor, and duct bifurcated is more, be also not suitable for using as template, so duct order is better, and the porous anodic alumina template of aperture 200nm is best selection.
In step (1), inert gas is nitrogen or argon gas, flow is 50-100sccm(standard-state cubic centimeter per minute, mark condition milliliter per minute), under inert gas, be warming up to 600-900 ℃, in this temperature range, acetylene is decomposed into carbon atom and hydrogen atom, the formation hydrogen that mutually combines between hydrogen atom, carbon atom deposits and forms carbon nano-tube on the inwall of porous anodic alumina template duct; Temperature is higher, and the degree of graphitization of the carbon nano-tube of formation is better, and conductivity and intensity are better, but excess Temperature can cause acetylene decomposition rate too fast, causes the mouth of pipe to stop up, and therefore suitable temperature is 600-900 ℃, preferably 700-800 ℃; The flow that passes into of acetylene gas is 20-50sccm, and the time of passing into is 20-30min, and with this understanding, the wall thickness of the carbon nano-tube of formation is 5-10nm, has enough intensity and conductivity.
In step (2), be evacuated to and be less than 1 * 10
-2pa, is warming up to 600-700 ℃, in this temperature range, silane is decomposed into silicon atom and hydrogen atom, the formation hydrogen that mutually combines between hydrogen atom, silicon atom deposits and forms coaxial silicon-carbon composite nano tube on carbon nano-tube inwall, has reacted rear maintenance temperature and within 2 hours, has carried out crystallization; Inert gas is nitrogen or the argon gas of 100sccm flow, and the flow of hydrogen is 10sccm, and the flow of silane is 5-20sccm, and the time of passing into is 10-20min, and it is 1.1-1.6KPa that the size of control valve is controlled pressure; With this understanding, the dividing potential drop of silane is 48～246Pa, and the silicon atom of decomposition enters carbon nano-tube duct, on carbon nano-tube inwall, deposits; The existence of hydrogen has guaranteed that whole reaction system is in reducing atmosphere, prevents that highly active silicon atom from generating silicon dioxide.
In step (1) and (2), inert gas is high pure nitrogen or high-purity argon gas.
In step (3), the mass concentration of hydrofluoric acid aqueous solution is 10-40%, and soak time is 30-120min; For silicon-carbon composite nano tube array after preventing removing template breaks, post-depositional template is placed on plastic sheet, plastic sheet is put into hydrofluoric acid aqueous solution together with product, the volume of solution is controlled at 20～40ml; After immersion, the silicon-carbon composite nano tube array of plastic sheet holder to removal template takes out from solution, soaks after 30 minutes and take out in deionized water.
In step (3), baking temperature is 80-100 ℃, and the time is 8-20 hour, and it is in order to prevent that the rapid evaporation of moisture content from causing breaking of silicon-carbon composite nano tube array below that baking temperature is controlled at 100 ℃; Preferably dry in vacuum drying chamber, can reduce the oxidation of silicon.
The present invention has prepared silicon-carbon composite nano tube array by two step chemical vapour deposition techniques, and silicon-carbon composite nano tube array caliber, pipe range and the wall thickness of preparation are controlled, size homogeneous, and the battery specific capacity of assembling is high, and cycle performance is excellent.
Preparation method of the present invention is simple, only need to just can obtain caliber, pipe range and wall thickness by two step chemical vapour deposition (CVD)s and hydrofluoric acid corrosion controlled, the silicon-carbon composite nano tube array of size homogeneous, whole production process do not have complicated equipment and processing step simple, the stability of being convenient to large-scale industrial production and product is better.The outer field carbon pipe of silicon-carbon composite nano tube array can transmit electronics between silicon and external negative pole, and stop silicon in first charge-discharge process, to produce solid electrolyte (SEI) film, the carbon-coating on surface can replace the effect of negative pole currect collecting device simultaneously, so can directly being used as negative material, sample do not need negative pole currect collecting device, this can improve the whole specific capacity of negative pole effectively, manage inner space and can hold the volumetric expansion of silicon in lithium ion telescopiny, make silicon that fragmentation not occur in cyclic process.Above advantage makes silicon-carbon composite nano tube array have high specific capacity, stable cycle performance, and the battery of preparing by the present invention, first discharge specific capacity has reached 1965 mAh/g, after 50 circulations, still has 1407 mAh/g.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is side scintigram and the elementary analysis figure after the embodiment of the present invention 1 silicon-carbon composite nano tube array embedding lithium.
Fig. 2 is the XRD figure of the embodiment of the present invention 1 silicon-carbon composite nano tube array.
Fig. 3 is the charge-discharge performance resolution chart of the lithium ion battery made of the silicon-carbon composite nano tube array of the embodiment of the present invention 1 preparation.
Fig. 4 is the charge-discharge performance resolution chart of the lithium ion battery made of the silicon-carbon composite nano tube array of the embodiment of the present invention 2 preparation.
Fig. 5 is the charge-discharge performance resolution chart of the lithium ion battery made of the silicon-carbon composite nano tube array of the embodiment of the present invention 3 preparation.
Fig. 6 is the charge-discharge performance resolution chart of the lithium ion battery made of the silicon-carbon composite nano tube array of the embodiment of the present invention 4 preparation.
(5) embodiment
Below by specific embodiments, the present invention is described in further detail, but these embodiment are only to illustrate, scope of the present invention are not limited.
Embodiment 1:
The porous anodic alumina template in 200nm aperture is placed in to corundum Noah's ark, put into the thermal treatment zone of tube furnace, flow velocity with 100sccm passed into high-purity argon gas after 2 hours, with 10 ℃ of temperature programmings to 800 ℃ per minute, pass into flow and be the acetylene gas 30 minutes of 50sccm, be incubated 2 hours after cooling naturally, acetylene High Temperature Gas phase decomposition in this process, carbon atom deposits on the inwall of porous anodic alumina template duct, obtains being included in the carbon nano pipe array in template.
Carbon nano pipe array is placed in to corundum Noah's ark, puts into the thermal treatment zone of tube furnace, with mechanical pump and diffusion pump, be evacuated to 5Pa and 10 successively
-2pa; with 10 ℃ of temperature programmings to 700 ℃ per minute; stop diffusion pump; pass into the high-purity argon gas of 100sccm; the position of regulating butterfly valve; with mechanical pump, maintain system pressure at 1.4kPa; pass into the hydrogen of 10sccm flow; the silane gas of 11sccm 15 minutes; be incubated after 2 hours cooling naturally, the High Temperature Gas phase decomposition of silane under hydrogen shield atmosphere, obtains covering the nano-tube array on carbon-coating surface; through above preparation process, the structure that is included in coaxial nano-tube in AAO template and carbon nano pipe array is obtained.
The product of preparation is placed on plastic sheet, plastic sheet is put into plastic beaker together with product, adding 40ml mass fraction is 20% hydrofluoric acid aqueous solution, soaks 1 hour; After immersion, the silicon-carbon composite nano tube array of plastic sheet holder to removal template takes out from solution, soaks after 30 minutes and takes out, 80 ℃ of dry silicon-carbon composite nano tube arrays that obtain for 12 hours in vacuum drying chamber in deionized water.
The silicon-carbon composite nano tube array of gained is transferred in glove box, directly as electrode, used, take lithium metal as the utmost point being assembled into CR2032 type button cell.
By the battery of this case making, first discharge specific capacity has reached 1965mAh/g, after 50 circulations, still has 1407 mAh/g.
Embodiment 2:
The porous anodic alumina template in 200nm aperture is placed in to corundum Noah's ark, put into the thermal treatment zone of tube furnace, flow velocity with 100sccm passed into argon gas after 2 hours, with 10 ℃ of temperature programmings to 700 ℃ per minute, pass into flow and be the acetylene gas 20 minutes of 50sccm, be incubated 2 hours after cooling naturally, acetylene High Temperature Gas phase decomposition in this process, carbon atom deposits on the inwall of porous anodic alumina template duct, obtains being included in the carbon nano pipe array in template.
Carbon nano pipe array is placed in to corundum Noah's ark, puts into the thermal treatment zone of tube furnace, with mechanical pump and diffusion pump, be evacuated to 5Pa and 10 successively
-2pa; with 10 ℃ of temperature programmings to 700 ℃ per minute; stop diffusion pump; pass into the argon gas of 100sccm; the position of regulating butterfly valve; with mechanical pump, maintain system pressure at 1.6kPa; pass into the hydrogen of 10sccm flow; the silane gas of 20sccm 10 minutes; be incubated after 2 hours cooling naturally, the High Temperature Gas phase decomposition of silane under hydrogen shield atmosphere, obtains covering the nano-tube array on carbon-coating surface; through above preparation process, the structure that is included in coaxial nano-tube in AAO template and carbon nano pipe array is obtained.
The product of preparation is placed on plastic sheet, plastic sheet is put into plastic beaker together with product, adding 40ml mass fraction is 40% hydrofluoric acid aqueous solution, soaks 2 hours; After immersion, the silicon-carbon composite nano tube array of plastic sheet holder to removal template takes out from solution, soaks after 30 minutes and takes out, 100 ℃ of dry silicon-carbon composite nano tube arrays that obtain for 8 hours in vacuum drying chamber in deionized water.
The silicon-carbon composite nano tube array of gained is transferred in glove box, directly as electrode, used, take lithium metal as the utmost point being assembled into CR2032 type button cell.
By the battery of this case making, first discharge specific capacity has reached 1845 mAh/g, after 50 circulations, still has 1006 mAh/g.
Embodiment 3:
The porous anodic alumina template in 200nm aperture is placed in to corundum Noah's ark, put into the thermal treatment zone of tube furnace, flow velocity with 50sccm passed into nitrogen after 2 hours, with 10 ℃ of temperature programmings to 600 ℃ per minute, pass into flow and be the acetylene gas 30 minutes of 20sccm, be incubated 2 hours after cooling naturally, acetylene High Temperature Gas phase decomposition in this process, carbon atom deposits on the inwall of porous anodic alumina template duct, obtains being included in the carbon nano pipe array in template.
Carbon nano pipe array is placed in to corundum Noah's ark, puts into the thermal treatment zone of tube furnace, with mechanical pump and diffusion pump, be evacuated to 5Pa and 10 successively
-2pa; with 10 ℃ of temperature programmings to 600 ℃ per minute; stop diffusion pump; pass into the nitrogen of 100sccm; the position of regulating butterfly valve; with mechanical pump, maintain system pressure at 1.1kPa; pass into the hydrogen of 10sccm flow; the silane gas of 5sccm 20 minutes; be incubated after 2 hours cooling naturally, the High Temperature Gas phase decomposition of silane under hydrogen shield atmosphere, obtains covering the nano-tube array on carbon-coating surface; through above preparation process, the structure that is included in coaxial nano-tube in AAO template and carbon nano pipe array is obtained.
The product of preparation is placed on plastic sheet, plastic sheet is put into plastic beaker together with product, adding 20ml mass fraction is 10% hydrofluoric acid aqueous solution, soaks 30 minutes; After immersion, the silicon-carbon composite nano tube array of plastic sheet holder to removal template takes out from solution, soaks after 30 minutes and takes out, 80 ℃ of dry silicon-carbon composite nano tube arrays that obtain for 20 hours in drying box in deionized water.
The silicon-carbon composite nano tube array of gained is transferred in glove box, directly as electrode, used, take lithium metal as the utmost point being assembled into CR2032 type button cell.
By the battery of this case making, first discharge specific capacity has reached 1319 mAh/g, after 30 circulations, still has 638 mAh/g.
Embodiment 4:
The porous anodic alumina template in 200nm aperture is placed in to corundum Noah's ark, put into the thermal treatment zone of tube furnace, flow velocity with 70sccm passed into high pure nitrogen after 2 hours, with 10 ℃ of temperature programmings to 900 ℃ per minute, pass into flow and be the acetylene gas 25 minutes of 40sccm, be incubated 2 hours after cooling naturally, acetylene High Temperature Gas phase decomposition in this process, carbon atom deposits on the inwall of porous anodic alumina template duct, obtains being included in the carbon nano pipe array in template.
Carbon nano pipe array is placed in to corundum Noah's ark, puts into the thermal treatment zone of tube furnace, with mechanical pump and diffusion pump, be evacuated to 5Pa and 10 successively
-2pa; with 10 ℃ of temperature programmings to 650 ℃ per minute; stop diffusion pump; pass into the high pure nitrogen of 100sccm; the position of regulating butterfly valve; with mechanical pump, maintain system pressure at 1.2kPa; pass into the hydrogen of 10sccm flow; the silane gas of 15sccm 10 minutes; be incubated after 2 hours cooling naturally, the High Temperature Gas phase decomposition of silane under hydrogen shield atmosphere, obtains covering the nano-tube array on carbon-coating surface; through above preparation process, the structure that is included in coaxial nano-tube in AAO template and carbon nano pipe array is obtained.
The product of preparation is placed on plastic sheet, plastic sheet is put into plastic beaker together with product, adding 30ml mass fraction is 20% hydrofluoric acid aqueous solution, soaks 1 hour; After immersion, the silicon-carbon composite nano tube array of plastic sheet holder to removal template takes out from solution, soaks after 30 minutes and takes out, 90 ℃ of dry silicon-carbon composite nano tube arrays that obtain for 12 hours in vacuum drying chamber in deionized water.
The silicon-carbon composite nano tube array of gained is transferred in glove box, directly as electrode, used, take lithium metal as the utmost point being assembled into CR2032 type button cell.
By the battery of this case making, first discharge specific capacity has reached 1562 mAh/g, after 50 circulations, still has 722 mAh/g.
Claims (10)
1. the preparation method of a silicon-carbon composite nano tube array, take porous anodic alumina template as raw material, it is characterized by, comprise the steps: that (1) put into porous anodic alumina template the thermal treatment zone of tube furnace, under inert gas, heat up, pass into acetylene gas, the High Temperature Gas phase decomposition of acetylene is at template surface Formed nano-tube array; (2) carbon nano pipe array is put into the thermal treatment zone of tube furnace, be evacuated to vacuum, pass into inert gas, hydrogen and silane after intensification, the high-temperature low-pressure gas-phase decomposition of silane under hydrogen shield, obtains being included in coaxial carbon nano-tube and nano-tube array in template; (3) coaxial carbon nano-tube and nano-tube array are soaked and removed template and surperficial silica with hydrofluoric acid aqueous solution, after being dried, obtain product.
2. the preparation method of silicon-carbon composite nano tube array according to claim 1, is characterized in that: the aperture of described porous anodic alumina template is 200nm.
3. the preparation method of silicon-carbon composite nano tube array according to claim 1, it is characterized in that: in step (1), inert gas is nitrogen or argon gas, flow is 50-100sccm, inert gas intensification 600-900 ℃, the flow that passes into of acetylene gas is 20-50sccm, and the time of passing into is 20-30min.
4. the preparation method of silicon-carbon composite nano tube array according to claim 1, is characterized in that: in step (2), be evacuated to and be less than 1 * 10
-2pa, is warming up to 600-700 ℃, and inert gas is nitrogen or the argon gas of 100sccm flow, and the flow of hydrogen is 10sccm, and the flow of silane is 5-20sccm, and the time of passing into is 10-20min, and it is 1.1-1.6KPa that the size of control valve is controlled pressure.
5. the preparation method of silicon-carbon composite nano tube array according to claim 1, is characterized in that: in step (3), the mass concentration of hydrofluoric acid aqueous solution is 10-40%, and soak time is 30-120min.
6. the preparation method of silicon-carbon composite nano tube array according to claim 1, is characterized in that: in step (3), baking temperature is 80-100 ℃, and environment is chosen vacuum drying chamber, and the time is 8-20 hour.
7. the preparation method of silicon-carbon composite nano tube array according to claim 3, is characterized in that: in step (1), inert gas is warming up to 700-800 ℃.
8. the preparation method of silicon-carbon composite nano tube array according to claim 4, is characterized in that: in step (2), after silane has decomposed, keep temperature within 2 hours, to carry out crystallization again.
9. according to the preparation method of the silicon-carbon composite nano tube array described in claim 3 or 4, it is characterized in that: in step (1) and (2), inert gas is high pure nitrogen or high-purity argon gas.
10. the preparation method of silicon-carbon composite nano tube array according to claim 1 or 5, is characterized in that: in step (3), after coaxial carbon nano-tube and nano-tube array soak with hydrofluoric acid aqueous solution, through the deionized water of 30min, soak dry again.
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| CN103904335A (en) * | 2014-04-21 | 2014-07-02 | 哈尔滨工业大学 | Lithium ion battery negative material structure and preparation method thereof |
| CN104760943A (en) * | 2015-02-10 | 2015-07-08 | 山东玉皇新能源科技有限公司 | Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition |
| CN104979539A (en) * | 2015-05-14 | 2015-10-14 | 浙江大学 | Silicon-carbon composite nano-tube preparation method |
| CN105070943A (en) * | 2015-08-27 | 2015-11-18 | 深圳市燕峰科技有限公司 | Quick charging lithium battery |
| CN107799751A (en) * | 2017-10-27 | 2018-03-13 | 中国科学院过程工程研究所 | The silicon filling carbon nano-pipe material and preparation method and purposes of a kind of ordered arrangement |
| CN108417794A (en) * | 2018-02-05 | 2018-08-17 | 合肥国轩高科动力能源有限公司 | Silicon nano-layer graphite composite heterojunction material and preparation method and application thereof |
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| CN109326788A (en) * | 2018-11-20 | 2019-02-12 | 青海大学 | Negative electrode material and lithium ion battery and preparation method thereof |
| CN112259740A (en) * | 2020-10-28 | 2021-01-22 | 成都新柯力化工科技有限公司 | Dendritic silicon-carbon composite negative electrode material of lithium battery and preparation method |
| CN112670479A (en) * | 2020-12-24 | 2021-04-16 | 惠州亿纬锂能股份有限公司 | Sulfur and nitrogen co-doped coaxial core-shell silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
| CN112779515A (en) * | 2019-11-08 | 2021-05-11 | 南京理工大学 | Preparation method of carbon-based nano material based on AAO template |
| CN115448294A (en) * | 2022-09-16 | 2022-12-09 | 武汉市碳翁科技有限公司 | Method for preparing carbon nano tube and silicon composite film material by chemical gas phase flow reaction |
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| CN104760943A (en) * | 2015-02-10 | 2015-07-08 | 山东玉皇新能源科技有限公司 | Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition |
| CN104979539A (en) * | 2015-05-14 | 2015-10-14 | 浙江大学 | Silicon-carbon composite nano-tube preparation method |
| CN104979539B (en) * | 2015-05-14 | 2017-05-10 | 浙江大学 | Silicon-carbon composite nano-tube preparation method |
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| CN108417794B (en) * | 2018-02-05 | 2021-02-26 | 合肥国轩高科动力能源有限公司 | Silicon nano-layer graphite composite heterojunction material and preparation method and application thereof |
| CN108417794A (en) * | 2018-02-05 | 2018-08-17 | 合肥国轩高科动力能源有限公司 | Silicon nano-layer graphite composite heterojunction material and preparation method and application thereof |
| CN109326788A (en) * | 2018-11-20 | 2019-02-12 | 青海大学 | Negative electrode material and lithium ion battery and preparation method thereof |
| CN112779515A (en) * | 2019-11-08 | 2021-05-11 | 南京理工大学 | Preparation method of carbon-based nano material based on AAO template |
| CN112259740A (en) * | 2020-10-28 | 2021-01-22 | 成都新柯力化工科技有限公司 | Dendritic silicon-carbon composite negative electrode material of lithium battery and preparation method |
| CN112259740B (en) * | 2020-10-28 | 2021-08-17 | 惠州市竤泰科技有限公司 | Dendritic silicon-carbon composite negative electrode material of lithium battery and preparation method |
| CN112670479A (en) * | 2020-12-24 | 2021-04-16 | 惠州亿纬锂能股份有限公司 | Sulfur and nitrogen co-doped coaxial core-shell silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
| CN112670479B (en) * | 2020-12-24 | 2022-08-09 | 惠州亿纬锂能股份有限公司 | Sulfur and nitrogen co-doped coaxial core-shell silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
| CN115448294A (en) * | 2022-09-16 | 2022-12-09 | 武汉市碳翁科技有限公司 | Method for preparing carbon nano tube and silicon composite film material by chemical gas phase flow reaction |
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