CN112072096A - Preparation method of nano silicon lithium ion battery cathode material - Google Patents

Preparation method of nano silicon lithium ion battery cathode material Download PDF

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CN112072096A
CN112072096A CN201910502577.5A CN201910502577A CN112072096A CN 112072096 A CN112072096 A CN 112072096A CN 201910502577 A CN201910502577 A CN 201910502577A CN 112072096 A CN112072096 A CN 112072096A
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silicon
aluminum
alloy
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冯涛
邵建华
王利峰
孙保安
鲁皓辰
岳继礼
夏晖
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Nanjing University of Science and Technology
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention discloses a preparation method of a nano silicon lithium ion battery cathode material. The method adopts a method of rapid solidification of alloy, firstly, pure aluminum and pure silicon are mixed and smelted into an aluminum-silicon alloy spindle, then the aluminum-silicon alloy spindle is subjected to suction casting molding after an oxide layer is removed, then an alloy material is stirred and corroded by acid to remove alloying to obtain silicon nano-particles, then silicon nano-particle powder is stirred and uniformly mixed with a conductive agent and a binder to obtain electrode slurry, and finally the electrode slurry is uniformly coated on a current collector and is dried, rolled and cut into pieces to obtain the electrode piece. The preparation process is simple and easy to repeat, the prepared nano silicon is used as a lithium ion battery cathode material, the first specific discharge capacity can reach 3699mAh/g, the first coulombic efficiency can reach 83.7 percent, and the preparation method is suitable for large-scale industrial production.

Description

Preparation method of nano silicon lithium ion battery cathode material
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a preparation method of a negative electrode material of a nano silicon lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, environmental protection, long cycle life, small self-discharge and the like, and although the energy density is increased at a speed of 7-10% per year, the energy density is still far lower than the energy demand of the electric automobile. At present, the lithium ion battery cathode material in practical application mainly comprises carbon materials such as graphitized carbon, amorphous carbon and the like, but the maximum theoretical specific capacity of the lithium ion battery cathode material is only 372 mAh/g. The silicon-based negative electrode material can form an alloy with high lithium content after lithium intercalation, wherein Li22Si5The theoretical capacity is up to 4200mAh/g, and the reserve of silicon is extremely rich and more environment-friendly, and is one of the most possible negative electrode materials for replacing commercial graphite. However, in the process of lithium intercalation, the expansion (100-300%) of the silicon-based negative electrode material can be caused, the stability of the electrode material is structurally damaged, and the electrode structure collapses and the electrode material peels off; and an unstable Solid Electrolyte Interphase (SEI) may be formed on the silicon surface, affecting lithium trapping in the active silicon material, resulting in rapid decay of irreversible battery capacity and low initial coulombic efficiency. Furthermore, the kinetics of lithium diffusion in silicon are slow (diffusion coefficient 10)-14～10-13cm2S) and low intrinsic conductivity of silicon (10)-5～10-3S/cm) also significantly affects the rate capability and full capacity utilization of the silicon electrode.
The nano-scale form silicon can solve the problem of expansion/contraction stress of silicon in the lithiation/delithiation process. The nanoscale dimensions allow for rapid relaxation of the pressure, so nanosilica is less prone to cracking than bulk particles. The nano silicon-based negative electrode material has the advantages of unique surface effect, size effect and the like, and can greatly improve the cycle performance of the silicon-based negative electrode material. The existing preparation methods of nano silicon particles comprise chemical methods and physical methods. Chemical method mainlyComprises chemical vapor deposition, plasma reaction synthesis, molten salt electrolysis, metal-induced chemical corrosion, magnesiothermic reduction, etc4Or solid SiO2Process for converting silicide precursors to pure silicon (Zhou Zhu. preparation of silicon and boron nanoparticles using cold plasma [ D ]]Hangzhou Zhejiang university 2013; LIU Nian, HUO Kaifu, MCDOWELL M T, et al, Ricerhusks as a supersteable source of nanostructured silicon for high performance Li-ion batteries [ J]Scientific reports,2013,3(5): 1919.). The chemical method can obtain the nano silicon particles with smaller size and more uniform distribution, but the preparation process has a plurality of defects, such as harsh reaction conditions, complex process route, poor controllability, high cost, low yield and the like, and the chemical method is very difficult to prepare the nano silicon particles with different sizes. The physical methods comprise a ball milling method, a laser ablation method, a spark discharge method and the like, and are all based on the top-down preparation means of solid pure silicon raw materials (Zhao Ming Cao Xiang Wei, Sunzhong Kai, and the like]Electrochemical machining and die, 2017(4) 15-19; VONS V A, DESMET LC P M, MUNAO D, et al silicon nanoparticles produced by spark discharge [ J]Journal of Nanoparticle Research, 2011, 13 (10): 4867-4879.). The preparation methods are complex in preparation process, high in equipment requirement, difficult to produce in mass production and high in cost, so that the silicon-based composite material system is difficult to realize industrialization, and the first coulomb efficiency of the prepared pure silicon is mostly lower than 60%.
The aluminum-silicon alloy is widely applied to industrial aluminum alloy, accounts for more than 90 percent when being applied to the aluminum alloy, and can be used in the fields of automobile industry, aviation industry, weaponry and the like. The aluminum-silicon binary alloy has a simple binary eutectic phase diagram, and only has two phases of alpha-Al and p-Si at room temperature, and the two phases are immiscible. The content of Si at the eutectic point was about 12.6% (mass fraction). In the eutectic aluminum-silicon alloy, primary silicon exists in the form of coarse needle-like crystals, and eutectic silicon exists in the form of smaller lamellar layers, but the sizes of both phases are in the order of micrometers. After the modifier is added for refining, the primary crystal silicon phase can be refined, but the refining effect of the eutectic silicon phase is not obvious.
Disclosure of Invention
The invention aims to provide a preparation method of a nano silicon lithium ion battery cathode material for improving the specific capacity and the first coulombic efficiency of a lithium ion battery.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the nano silicon lithium ion battery cathode material comprises the following steps:
step 1, placing pure aluminum and pure silicon into a vacuum smelting furnace, and carrying out mixed smelting to obtain an aluminum-silicon alloy spindle with the Si content of 11.0-16.0 wt%;
step 2, removing an oxide layer from an aluminum-silicon alloy spindle, performing suction casting molding, and controlling the aperture of a suction casting copper mold to be 1.5-5.0 mm to obtain an alloy material;
and 3, stirring and corroding the alloy material with acid, removing alloying, washing with water, centrifuging, and drying to obtain the silicon nano particles.
The invention also provides a preparation method of the nano silicon lithium ion battery cathode material, which comprises the following steps:
step 1, putting pure aluminum and pure silicon into a vacuum smelting furnace, and mixing and smelting the pure aluminum and the pure silicon into an aluminum-silicon alloy spindle with the Si content of 11.0-16.0 wt%;
step 2, removing an oxide layer from an aluminum-silicon alloy spindle, performing suction casting molding, and controlling the aperture of a suction casting copper mold to be 1.5-5.0 mm to obtain an alloy material;
step 3, stirring and corroding the alloy material with acid to remove alloying, washing with water, centrifuging, and drying to obtain silicon nanoparticles;
step 4, uniformly stirring and mixing the silicon nanoparticle powder, a conductive agent and a binder to obtain electrode slurry;
and 5, uniformly coating the electrode slurry on a current collector, drying, rolling and cutting into pieces to obtain the electrode slice.
Preferably, the silicon content in the aluminum-silicon alloy is 12.0-16.0 wt%, and more preferably 13.0-15.0 wt%.
Preferably, the aperture of the suction casting copper mold is 2.0-3.0 mm.
Preferably, the mass ratio of the silicon nanoparticles to the conductive agent (super P) to the binder is 1:1: 1.
Further, the invention provides the nano silicon lithium ion battery cathode material prepared by the preparation method.
Furthermore, the electrolyte of the lithium ion battery assembled by the nano silicon lithium ion battery cathode material prepared by the preparation method is 1M LiPF6/EC:DMC:DEC＝1:1:1(V/V/V)。
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts a method of smelting suction casting and then dealloying for the first time, utilizes the rapid solidification technology of alloy melt to refine the size of a silicon phase in an aluminum-silicon alloy eutectic structure, so that the size of the silicon phase can reach the nanometer level, and further adopts the dealloying technology to prepare a silicon cathode material, wherein the size of the prepared silicon material can reach the nanometer level and the particles are more uniform;
(2) the invention regulates and controls the size of the prepared nano silicon particles by regulating and controlling the alloy component ratio and the aperture size of the suction casting forming die;
(3) the nano silicon prepared by the invention is used as a lithium ion battery cathode material, the first-cycle discharge specific capacity can reach 3699mAh/g, the first coulombic efficiency can reach 83.7%, the preparation process is simple, the repetition is easy, and the preparation method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of Al-Si alloy round rods with different Si contents and diameters of 2.5mm prepared by the invention, (a)2.0 wt% Si; (b)11.7 wt% Si; (c)12.6 wt% Si; (d)15.0 wt% Si; (e)16.0 wt% Si; (f)20.0 wt% Si; (g)50.0 wt% Si.
FIG. 2 is a scanning electron microscope image of Al-Si alloy round rods with different diameters and a component of 14.0 wt% Si prepared by the invention, wherein (a) D is 1.5 mm; (b) d is 2.0 mm; (c) d is 2.5 mm; (d) d is 3.0 mm; (e) d is 5.0 mm.
FIG. 3 is a scanning electron micrograph and a silicon particle size distribution of unground nanosilicon (a, c) in comparative example 2 and the nanosilicon (b, d) after grinding in example 1.
Fig. 4 is an X-ray diffraction pattern (XRD) of the nano-silicon prepared in example.
Fig. 5 is a graph showing the charge-discharge curve, specific cyclic discharge capacity and coulombic efficiency of lithium ion batteries assembled by using nano silicon prepared in comparative example 1(a, b), example 2(c, d) and example 1(e, f) as a negative electrode material.
Fig. 6 is a charge-discharge curve, specific cyclic discharge capacity and coulombic efficiency chart of the lithium ion battery assembled by using the nano-silicon prepared in the comparative example 2 as the negative electrode material.
Detailed Description
The invention is further illustrated by the following examples and figures.
The preparation method of the nano silicon lithium ion battery cathode material specifically comprises the following steps:
step 1, smelting:
proportionally mixing pure Al-Si ingot with Ti ingot at a temperature lower than 2X 10-3And introducing argon gas under the Pa vacuum degree, smelting a pure titanium ingot for 2-5 times to remove oxygen, controlling the arc current to be 60-200A, smelting the aluminum-silicon alloy for 3-5 times until the alloy is uniform, and controlling the arc current to be 60-200A to obtain the aluminum-silicon alloy.
Step 2, suction casting:
the aluminum-silicon alloy and the titanium ingot after being polished are lower than 2 multiplied by 10-3And introducing argon gas under the Pa vacuum degree, smelting a pure titanium ingot for 2-5 times to remove oxygen, controlling the arc current to be 60-200A, smelting the aluminum-silicon alloy, controlling the arc current to be 60-200A, keeping the complete melting state for 2-10 s, and performing suction casting to obtain the rod-shaped aluminum-silicon alloy.
Step 3, dealloying:
cutting the obtained aluminum-silicon alloy into a plurality of parts, placing the parts into 0.5-5.0 mol/L HCl solution, stirring and corroding for 6-24 h, and cleaning with water for 3-5 times after centrifuging to remove residual acid solution; putting the solution into HF ethanol solution with the concentration of 0.5-5.0 mol/L, stirring and corroding for 2-24 h, and removing redundant SiO2After centrifugation, washing with water for 3-5 times to remove residual acid solution; and (3) placing the solution in a drying oven at the temperature of 60-80 ℃, and drying until completely dry silicon nanoparticle powder is obtained.
Step 4, preparing electrode slurry:
mixing nano silicon powder and a conductive agent (super P), and grinding for 15-35 min in a mortar; and placing the powder and the binder in a glass bottle, adding water, and stirring for 6-24 h to obtain the electrode slurry.
Step 5, preparing an electrode slice:
coating the slurry on a copper foil, placing the copper foil in a vacuum drying oven for 12-24 hours at the temperature of 60-80 ℃, drying, rolling, and cutting into round electrode plates.
Example 1
According to the silicon weight percentage of 11.7 percent, 1.38g of pure silicon and 10.40g of pure aluminum are taken and placed in a vacuum melting furnace, the vacuum degree in the furnace is controlled to be lower than 10-3And Pa, overturning and smelting the titanium ingot for 3 times, overturning and smelting the alloy for 5 times to form an aluminum-silicon alloy spindle, cooling and taking out, wherein the arc current is 110A.
Polishing to remove surface oxide skin, placing in a vacuum smelting furnace, and controlling the vacuum degree in the furnace to be lower than 10-3Pa, melting aluminum-silicon alloy after turning over and melting a titanium ingot for 3 times, keeping the titanium ingot in a complete melting state for 5s, pressing a suction casting switch, immediately extinguishing the arc, suction casting the titanium ingot into a round rod with the diameter of 2.5mm, cooling, and taking out the alloy material, wherein the arc current is 110A.
Cutting a round bar wire into a plurality of sections, carrying out ultrasonic cleaning, then placing the round bar wire into a 2.5mol/L HCl (AR) solution, carrying out magnetic stirring corrosion for 8h at normal temperature, carrying out centrifugation, then washing the round bar wire for 3 times by using deionized water, then placing the round bar wire into a 1.0mol/L HF (hydrofluoric acid) alcohol solution, carrying out magnetic stirring corrosion for 2h at normal temperature, carrying out centrifugation, then washing the round bar wire for 3 times by using deionized water, then placing the round bar wire into an oven, and drying the round bar wire for 24 h.
And (3) putting the obtained silicon powder and a conductive agent (super P carbon black) into a mortar, grinding for 20min, pouring into a glass bottle, adding a binder (SBR: CMC 1:1) and a proper amount of deionized water, and magnetically stirring for 10h at normal temperature to obtain electrode slurry, wherein the rotating speed is 2000 r/min.
And uniformly coating the slurry on a copper foil with the thickness of 20 micrometers, wherein the coating thickness is 50 micrometers, then placing the copper foil in a vacuum oven at 80 ℃ for 24 hours, and rolling and punching the copper foil into a circular electrode plate with the diameter of 12 mm.
Wherein the active material (i.e. the silicon nanopowder prepared by the present invention), and the conductive agent (super P)Carbon black), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to the mass ratio of 2:2:1: 1. The button cell is made by using a lithium sheet as a counter electrode, and the electrolyte is a commonly used lithium ion battery electrolyte: 1M LiPF6/EC:DMC:DEC＝1:1:1(V/V/V)。
The lithium ion battery prepared in the example was subjected to a charge-discharge test at 200mAg-1Constant current charging and discharging under current density, and cut-off potential is 0.01V and 1.5V respectively. The first cycle discharge specific capacity is 3699mAh/g, the first cycle efficiency is 83.72%, and the charge-discharge curve is shown in figure 5.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of Al-Si alloy round rods with different Si contents and diameters of 2.5mm prepared by the invention, (a)2.0 wt% Si; (b)11.7 wt% Si; (c)12.6 wt% Si; (d)15.0 wt% Si; (e)16.0 wt% Si; (f)20.0 wt% Si; (g)50.0 wt% Si. Fig. 1(b) is a scanning electron microscope image of the sample prepared in this embodiment, and it can be seen from the image that the sample is composed of an aluminum phase precipitated first and an aluminum-silicon eutectic structure, silicon in the eutectic structure is in a uniform elongated shape, and the particle size of the silicon particle powder after grinding in fig. 3(b, d) is 70-100nm, and is relatively uniform. From fig. 5(e, f), it can be seen that the prepared nano-silicon powder has higher first-week coulombic efficiency.
Example 2
This example is essentially the same as example 1, except that the electrolyte is a commonly used lithium ion battery electrolyte: 1M LiPF6/EC:DMC＝1:1(V/V)。
The lithium ion battery prepared in the example was subjected to a charge-discharge test at 200mAg-1Constant current charging and discharging under current density, and cut-off potential is 0.01V and 1.5V respectively. The first cycle discharge specific capacity is 2977.5mAh/g, the first cycle efficiency is 82.57%, and the charge-discharge curve is shown in figure 5(c, d).
Comparative example 1
This comparative example is essentially the same as example 1, except that the electrolyte is a commonly used lithium ion battery electrolyte: 1M LiPF6/EC:DEC＝1:1(V/V)。
The lithium ion battery prepared by the comparative example is subjected to charge and discharge tests at 200mAg-1Constant current charging and discharging under current density and cut-offBits are 0.01V and 1.5V, respectively. The first cycle discharge specific capacity is 1103.5mAh/g, the first cycle efficiency is 52.27%, and the charge-discharge curve is shown in figure 5(a, b). The first week of the method is low in coulombic efficiency, which indicates that the prepared nano-silicon powder is not suitable for 1M LiPF6DEC ═ 1:1(V/V) electrolyte.
Comparative example 2
This comparative example is essentially the same as example 1, except that the silicon weight fraction is 20.0%, and the electrolyte is a commonly used lithium ion battery electrolyte: 1M LiPF6/EC:DEC＝1:1(V/V)。
FIG. 1(f) is a scanning electron microscope image of the prepared sample of this example, which is a hypereutectic structure, and it can be seen that micron-sized coarse-grained silicon has appeared, and the scanning electron microscope image of the powder of the sample of FIG. 3(a, c) shows that the size of the silicon particle in the eutectic structure is about 100-200 nm.
The lithium ion battery prepared by the comparative example is subjected to charge and discharge tests at 200mAg-1Constant current charging and discharging under current density, and cut-off potential is 0.01V and 1.5V respectively. The first cycle discharge specific capacity is 3938.3mAh/g, the first cycle efficiency is 55.22%, and the charge-discharge curve is shown in figure 6. The morphology of the silicon film is combined to obtain micron-sized coarse-crystal silicon and unsuitable electrolyte (1M LiPF)6DEC ═ 1:1(V/V)) is responsible for its low coulombic efficiency in the first week.
Comparative example 3
This comparative example is essentially the same as example 1 except that the silicon weight fraction was 2.0 wt%. The SEM image of the obtained aluminum-silicon alloy is shown in fig. 1(a), and it can be seen from the figure that the number of nano-silicon particles is too small, which is not suitable for practical use.
Comparative example 4
This comparative example is essentially the same as example 1 except that the silicon weight fraction was 50.0 wt%. The SEM image of the obtained al-si alloy is shown in fig. 1(g), from which it can be seen that a large number of micron-sized coarse-grained silicon particles, having a size greater than 10 μm, appear, so that the electrochemical performance thereof as a negative electrode material is seriously affected.

Claims (10)

1. The preparation method of the nano silicon lithium ion battery cathode material is characterized by comprising the following steps of:
step 1, putting pure aluminum and pure silicon into a vacuum smelting furnace, and mixing and smelting the pure aluminum and the pure silicon into an aluminum-silicon alloy spindle with the Si content of 11.0-16.0 wt%;
step 2, removing an oxide layer from an aluminum-silicon alloy spindle, performing suction casting molding, and controlling the aperture of a suction casting copper mold to be 1.5-5.0 mm to obtain an alloy material;
and 3, stirring and corroding the alloy material with acid, removing alloying, washing with water, centrifuging, and drying to obtain the silicon nano particles.
2. The preparation method of the nano silicon lithium ion battery cathode material is characterized by comprising the following steps of:
step 1, putting pure aluminum and pure silicon into a vacuum smelting furnace, and mixing and smelting the pure aluminum and the pure silicon into an aluminum-silicon alloy spindle with the Si content of 11.0-16.0 wt%;
step 2, removing an oxide layer from an aluminum-silicon alloy spindle, performing suction casting molding, and controlling the aperture of a suction casting copper mold to be 1.5-5.0 mm to obtain an alloy material;
step 3, stirring and corroding the alloy material with acid to remove alloying, washing with water, centrifuging, and drying to obtain silicon nanoparticles;
step 4, uniformly stirring and mixing the silicon nanoparticle powder, a conductive agent and a binder to obtain electrode slurry;
and 5, uniformly coating the electrode slurry on a current collector, drying, rolling and cutting into pieces to obtain the electrode slice.
3. The production method according to claim 1 or 2, wherein the aluminum-silicon alloy contains silicon in an amount of 12.0 to 16.0 wt%.
4. The production method according to claim 1 or 2, wherein the content of silicon in the aluminum-silicon alloy is 13.0 to 15.0 wt%.
5. The preparation method according to claim 1 or 2, wherein the pore diameter of the suction casting copper mold is 2.0-3.0 mm.
6. The preparation method according to claim 1 or 2, characterized in that the specific steps of step 1 are: proportionally mixing pure Al-Si ingot with Ti ingot at a temperature lower than 2X 10-3Introducing argon gas under the Pa vacuum degree, smelting a pure titanium ingot for 2-5 times to remove oxygen, controlling the arc current to be 60-200A, smelting the aluminum-silicon alloy for 3-5 times until the alloy is uniform, and controlling the arc current to be 60-200A to obtain the aluminum-silicon alloy; the specific steps of the step 2 are as follows: the aluminum-silicon alloy and the titanium ingot after being polished are lower than 2 multiplied by 10-3And introducing argon gas under the Pa vacuum degree, smelting a pure titanium ingot for 2-5 times to remove oxygen, controlling the arc current to be 60-200A, smelting the aluminum-silicon alloy, controlling the arc current to be 60-200A, keeping the complete melting state for 2-10 s, and performing suction casting to obtain the rod-shaped aluminum-silicon alloy.
7. The preparation method according to claim 1 or 2, wherein the specific steps of step 3 are: cutting the aluminum-silicon alloy, placing the cut aluminum-silicon alloy in 0.5-5.0 mol/L HCl solution, stirring and corroding for 6-24 h, centrifuging, and cleaning with water for 3-5 times to remove residual acid solution; putting the solution into 0.5-5.0 mol/L HF ethanol solution, stirring and corroding for 2-24 h, and removing redundant SiO2After centrifugation, washing with water for 3-5 times to remove residual acid solution; and drying the solution at 60-80 ℃ to obtain the silicon nanoparticles.
8. The preparation method of claim 2, wherein the mass ratio of the silicon nanoparticles to the conductive agent to the binder is 1:1: 1.
9. The negative electrode material of the nano silicon lithium ion battery prepared by the preparation method of any one of claims 2 to 8.
10. The lithium ion battery assembled by the negative electrode material of the nano-silicon lithium ion battery as claimed in claim 9, wherein the electrolyte is 1M LiPF6/EC:DMC:DEC＝1:1:1(V/V/V)。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115133012A (en) * 2022-07-22 2022-09-30 合肥综合性国家科学中心能源研究院(安徽省能源实验室) Coral-shaped nano silicon powder for lithium ion battery negative electrode, negative electrode material and preparation method
CN115367760A (en) * 2022-08-17 2022-11-22 贵州安达科技能源股份有限公司 Porous silicon material, preparation method and application thereof, carbon-silicon composite material, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103993356A (en) * 2014-05-06 2014-08-20 上海大学 Method for high-pressure optical zone-melting growth of high-orientation crystal of easily volatile material
CN106222585A (en) * 2016-10-12 2016-12-14 湖南理工学院 A kind of siliceous Cu base bulk metallic glass composite and preparation technology thereof
CN106611843A (en) * 2016-12-26 2017-05-03 东北大学 Preparation method for porous silicon/graphene compounded lithium ion battery anode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103993356A (en) * 2014-05-06 2014-08-20 上海大学 Method for high-pressure optical zone-melting growth of high-orientation crystal of easily volatile material
CN106222585A (en) * 2016-10-12 2016-12-14 湖南理工学院 A kind of siliceous Cu base bulk metallic glass composite and preparation technology thereof
CN106611843A (en) * 2016-12-26 2017-05-03 东北大学 Preparation method for porous silicon/graphene compounded lithium ion battery anode material

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CN115133012A (en) * 2022-07-22 2022-09-30 合肥综合性国家科学中心能源研究院(安徽省能源实验室) Coral-shaped nano silicon powder for lithium ion battery negative electrode, negative electrode material and preparation method
CN115367760A (en) * 2022-08-17 2022-11-22 贵州安达科技能源股份有限公司 Porous silicon material, preparation method and application thereof, carbon-silicon composite material, and preparation method and application thereof

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Application publication date: 20201211