CN106784711A - A kind of lithium ion battery negative material Si/TiO2The preparation method of composite - Google Patents
A kind of lithium ion battery negative material Si/TiO2The preparation method of composite Download PDFInfo
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- CN106784711A CN106784711A CN201611236486.4A CN201611236486A CN106784711A CN 106784711 A CN106784711 A CN 106784711A CN 201611236486 A CN201611236486 A CN 201611236486A CN 106784711 A CN106784711 A CN 106784711A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of lithium ion battery negative material Si/TiO2The preparation method of composite, by rice husk Resource Access SiO2Raw material, then using magnesium reduction process by SiO2Raw material is reduced to Si, finally by Si and TiO2It is combined, you can prepare Si/TiO2Composite；The advantage of the invention is that：The present invention makes full use of the abundant raw material of rice husk resource, and Si is obtained the characteristics of with low cost, by with TiO2The compound obtained Si/TiO of sol gel solution2Negative material, have its technological process it is short, reproducible, it is workable the characteristics of.As lithium ion battery negative material, the multiple performance of lithium ion battery can be improved, while the comprehensive utilization ratio to rice husk resource can be improved, fully improve the economic worth of rice husk resource.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, and in particular to a kind of lithium ion battery negative
Material Si/TiO2The preparation method of composite.
Background technology
China's rice husk aboundresources, variation is also tended to the utilization of rice husk resource, such as make activated carbon, waterglass,
Additive and breeding feed as cement etc., but comprehensive utilization ratio is not high, and product economy value is relatively low.By studying people
It was found that, rice husk contains about 15% -20% SiO2, these SiO2 There is high-purity, active spy after being acted on by rice plants
Property, by the Si being reduced from rice husk, even more remain these features.Additionally, Si lithium ion battery negative material tools the most
There are following features（1）With highest theoretical capacity Si:4200mAh/g C:376mAh/g（2）Abundant raw material, preparation method letter
It is single（3）High mechanical properties, high-cooling property（4）Security is good, it is not easy to form Li dendrite.But Si negative materials are also faced with simultaneously
Huge bulk effect causes the cycle life to reduce, and by the shortcoming of traditional electrolyte corrosion, and can be carried out by with TiO2
It is compound, can not only improve the charge-discharge performance of lithium ion battery, increase its cyclical stability, can also improve and rice husk is provided
The new way that source utilizes, creates economic worth, has broad application prospects.
Nian Liu etc. obtain the silicon of nanoporous by the pretreatment to rice husk resource and magnesium reduction process, and obtain
Excellent specific capacity and preferable cycle performance.
Shan Fang etc. are by synthesizing SiO2Ball, then with TiO2It is combined, finally again by the method for magnesiothermic reduction,
TiO is obtained2The Si balls of cladding, as the negative material of lithium ion battery, obtain excellent cycle performance.
Domestic patent No. CN104037390 A describe a kind of method of electrostatic spinning, have prepared a kind of silicon/carbon nanometer
Linear load titanium dioxide lithium battery anode material, while having played the advantage of silicon/carbon nanocoils and titanium dioxide, acquisition is preferably followed
The performance of ring.Domestic patent No. CN104009235 A use rice husk resource, by using silicon therein, carbon, prepare
A kind of porous silicon/graphene composite material, as lithium ion battery negative material, with high rate performance higher.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, now providing that a kind of method is simple to operate, technological process is short,
Lithium ion battery negative material Si/TiO with low cost2The preparation method of composite.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of lithium ion battery negative material Si/
TiO2The preparation method of composite, its innovative point is：By rice husk Resource Access SiO2Raw material, then using magnesiothermic reduction
Method is by SiO2Raw material is reduced to Si, finally by Si and TiO2It is combined, you can prepare Si/TiO2Composite；Specifically include with
Lower step：
（1）Rice husk is filtered into cleaning repeatedly with running water, is then dried at 100 DEG C -150 DEG C；
（2）By step（1）The rice husk that obtains is added in HCl solution, stirs 3-5h at 90 DEG C -100 DEG C of constant temperature water bath, then
Cleaning 3-5 times is filtered on the screen cloth of 250 mesh with deionized water, is finally dried at 100 DEG C -150 DEG C；
（3）By step（2）The rice husk for obtaining, 2-3h is calcined at 600 DEG C, and the product that will be obtained sieves in the screen cloth of 250 mesh；
（4）By step（3）The product and 100-200 mesh Mg powder for obtaining proportionally carry out ball milling, then in the hand full of Ar gas
Compound is loaded into stainless steel tube in casing, and is sealed against；
（5）Under an ar atmosphere, by step（4）Sample be heated to 650 DEG C, and 3-5h is incubated, then by product in HCl solution
Immersion 5-10h, centrifugal filtration is subsequently adding the HF solution of 1-2ml, centrifugal filtration after immersion 3-5min, finally by product in 40-
Vacuum drying at 60 DEG C；
（6）Solution A is prepared with butyl titanate, absolute ethyl alcohol, glacial acetic acid, PVP raw materials, with absolute ethyl alcohol, deionized water as former
Material prepares B solution, and then B solution is slowly dropped in solution A, obtains TiO2Sol gel solution；
（7）Si is added to TiO2In sol gel solution, 30min-1h is stirred at room temperature, then in 40 DEG C of -60 DEG C of drying；
（8）N2Under atmosphere, by step（7）Sample be heated to 700 DEG C, and be incubated 2-3h, be cooled to room temperature taking-up；
（9）By step（8）Sample, sodium alginate, Super P be well mixed, add little water, be sufficiently stirred for into starchiness painting
On Copper Foil, 10-15h is vacuum dried at 40 DEG C -60 DEG C, is then cut using 13mm piercers and obtain battery pole piece, activity
The density of material is 0.5-1 mg/cm2, in glove box, button cell being assembled into full of Ar gas, battery size is
2032, electrolyte is 1M LiPF6, then encapsulated with button cell packaging machine, it is 100mA/g that current density is tested first, afterwards
It is 200mA/g.
Further, the step（2）HCl mass fractions be 10%, the volume of the rice husk quality and HCl solution it
Than being 1:15-20.
Further, the step（4）In product Mg powder mol ratio be 1:2.2, the ball, abrasive material, the matter of solvent
Amount is than being 3:1:2, the solvent is absolute ethyl alcohol, and the milling atmosphere is Ar gas, and rotating speed is 300/rmin, and the time is 10-
15h, seal is stainless steel pipe.
Further, the step（3）、（8）Heating rate be 5 DEG C/min, step（5）Heating rate for 1 DEG C/
min。
Further, the step（6）、（7）Middle solution A butyl titanate, absolute ethyl alcohol, the volume ratio of glacial acetic acid are 1:
10:1, the volume ratio 10 of absolute ethyl alcohol, deionized water in B solution:1, the PVP are 1 with the mass ratio of addition Si:2.
Further, the step（5）In centrifugation rate be 8000r/min-10000r/min, centrifugation time is 3-
5min, HCl concentration are 2mol/L, and HF mass fractions are 5%.
Further, the step（8）In step（7）Sample and sodium alginate, SuperP mass ratio be 60%:
20%:20%。
Beneficial effects of the present invention are as follows：The present invention makes full use of the abundant raw material of rice husk resource, the characteristics of with low cost
Obtain Si, by with TiO2The compound obtained Si/TiO of sol gel solution2Negative material, has that its technological process is short, repeatability
Good, workable the characteristics of.As lithium ion battery negative material, the multiple performance of lithium ion battery can be improved,
The comprehensive utilization ratio to rice husk resource can be improved simultaneously, fully improve the economic worth of rice husk resource.
Brief description of the drawings
Fig. 1 is the SiO that the embodiment of the present invention 1 is prepared2XRD diffracting spectrums；
Fig. 2 is the Si/TiO that the embodiment of the present invention 1 is prepared2XRD diffracting spectrum；
Fig. 3 is circulation-specific capacity curve that the embodiment of the present invention 1 is prepared；
Fig. 4 is autonomous dress stainless steel seal schematic diagram of the invention.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages of the invention and effect easily.
A kind of lithium ion battery negative material Si/TiO2The preparation method of composite, by rice husk Resource Access SiO2It is former
Material, then using magnesium reduction process by SiO2Raw material is reduced to Si, finally by Si and TiO2It is combined, you can prepare Si/TiO2
Composite；Specifically include following steps：
（1）Rice husk is filtered into cleaning repeatedly with running water, is then dried at 100 DEG C -150 DEG C；
（2）By step（1）The rice husk that obtains is added in HCl solution, stirs 3-5h at 90 DEG C -100 DEG C of constant temperature water bath, then
Cleaning 3-5 times is filtered on the screen cloth of 250 mesh with deionized water, is finally dried at 100 DEG C -150 DEG C；HCl mass fractions are
10%, the ratio between volume of rice husk quality and HCl solution is 1:15-20.
（3）By step（2）The rice husk for obtaining, 2-3h is calcined at 600 DEG C, and the product that will be obtained is in the screen cloth of 250 mesh
Sieving；
（4）By step（3）The product and 100-200 mesh Mg powder for obtaining proportionally carry out ball milling, then in the hand full of Ar gas
Compound is loaded into stainless steel tube in casing, and is sealed against；The mol ratio of product Mg powder is 1:2.2, ball, abrasive material, solvent
Mass ratio is 3:1:2, solvent is absolute ethyl alcohol, and milling atmosphere is Ar gas, and rotating speed is 300/rmin, and the time is 10-15h, sealing
Part is stainless steel pipe.
（5）Under an ar atmosphere, by step（4）Sample be heated to 650 DEG C, heating rate is 1 DEG C/min, and is incubated 3-
5h, then soaks 5-10h, centrifugal filtration by product in HCl solution, and centrifugation rate is 8000r/min-10000r/min, from
The heart time is 3-5min, and HCl concentration is 2mol/L, is subsequently adding the HF solution of 1-2ml, and HF mass fractions are 5%, soak 3-
Centrifugal filtration after 5min, finally by product at 40-60 DEG C vacuum drying；
（6）Solution A is prepared with butyl titanate, absolute ethyl alcohol, glacial acetic acid, PVP raw materials, with absolute ethyl alcohol, deionized water as former
Material prepares B solution, and then B solution is slowly dropped in solution A, obtains TiO2Sol gel solution, the fourth of solution A metatitanic acid four
Ester, absolute ethyl alcohol, the volume ratio of glacial acetic acid are 1:10:1, the volume ratio 10 of absolute ethyl alcohol, deionized water in B solution:1, PVP
It is 1 with the mass ratio of addition Si:2.；
（7）Si is added to TiO2In sol gel solution, 30min-1h is stirred at room temperature, then in 40 DEG C of -60 DEG C of drying；
（8）N2Under atmosphere, by step（7）Sample be heated to 700 DEG C, heating rate is 5 DEG C/min, and is incubated 2-3h, cold
But to taking-up after room temperature, sample and sodium alginate, the mass ratio of Super P are 60%:20%:20%；
（9）By step（8）Sample, sodium alginate, Super P be well mixed, add little water, be sufficiently stirred for into starchiness painting
On Copper Foil, 10-15h is vacuum dried at 40 DEG C -60 DEG C, is then cut using 13mm piercers and obtain battery pole piece, activity
The density of material is 0.5-1 mg/cm2, in glove box, button cell being assembled into full of Ar gas, battery size is
2032, electrolyte is 1M LiPF6, then encapsulated with button cell packaging machine, it is 100mA/g that current density is tested first, afterwards
It is 200mA/g.
Reaction mechanism involved in the present invention includes：
Butyl titanate（Ti(OBu)4）Hydrolysis：
Ti(OBu)4+4H2O → Ti(OH)4+4C4H9OH
There is following reaction under an ar atmosphere：
SiO2(s)+2Mg(s) →Si(s)+2MgO(s) ΔH=—291.62kJ/mol
SiO2(s)+2Mg(g) → Si(s)+2MgO(s)ΔH= —546.42kJ/mol
Add the HF of the HCl and 5% of 2mol/L that following reaction occurs：
MgO+2HCl → MgCl2+H2O
SiO2+4HF → SiF4↑+2H2O
Autonomous dress stainless steel seal schematic diagram of the invention is illustrated in figure 4, stainless steel pipe is by the He of stainless steel pipe body 1
The stainless steel screwed tube cap 2 for being connected to the both ends of stainless steel pipe body 1 by internal and external threads is constituted.
Embodiment 1
Step 1, rice husk is cleaned into filtering and impurity removing with running water after, at 100 DEG C dry.
Step 2, the rice husk of 15g is added 300mL mass fractions be 10% HCl solution.Magneton is then placed in, in water
At 90 DEG C of constant temperature of bath, stir 3 hours.Then cleaning 3-5 times is filtered on the screen cloth of 250 mesh with deionized water, finally at 150 DEG C
Lower drying.
Step 3, the rice husk that will be obtained by step 2, are warming up to 600 DEG C by 5 DEG C/min of heating rate in atmosphere, and
Insulation 2.5h obtains SiO2, and sieved with the screen cloth of 250 mesh.
Step 4, to take product 0.3g, the 100-200 mesh Mg powder that step 3 obtains be 0.264g, according to ball, abrasive material, solvent
Mass ratio is 3:1:2, it is put into ball grinder, and be filled with Ar gas.Rotating speed is 300r/min, and the time is 10h, then by abrasive material in room
Dried under temperature, compound is fitted into stainless steel pipe in the glove box full of Ar gas so, and be sealed against.
Under step 5, Ar atmosphere, the sample of step 4 is warming up to 650 DEG C by 1 DEG C/min of heating rate, and be incubated
5h.Then product soaks 6h in the 4mol/L HCl solutions of 50ml, with deionized water centrifugal filtration 3 times.It is subsequently adding 1ml's
Mass fraction is 5%HF solution, and after immersion 5min, with deionized water centrifugal filtration 3 times, front and rear centrifugation rate is 8000r/
Min, centrifugation time is 1min, finally by product at 60 DEG C vacuum drying
Step 6, with the butyl titanate of 1ml, the absolute ethyl alcohol of 10ml, 1ml glacial acetic acid, 0.1gPVP raw materials prepare solution A,
B solution is prepared as raw material with the deionized water of the absolute ethyl alcohol of 5ml, 0.5ml, then B solution is slowly dropped in solution A,
Obtain TiO2Sol gel solution.
Step 7, the Si and magneton of 0.2g are added in the sol gel solution of step 6,10h are stirred at room temperature, then
Dried at 60 DEG C.
Step 8, in N2Under atmosphere, the sample that step 7 is obtained is had and is warming up to 700 DEG C with the speed of 5 DEG C/min, and be incubated
3h, takes out after being cooled to room temperature.
Step 9, take Si/TiO2Sample 0.03g, sodium alginate 0.01g, Super P 0.01g are well mixed, and add a little
Water is sufficiently stirred for into starchiness and is coated on Copper Foil, and 10h is vacuum dried at 60 DEG C.Then cut using 13mm piercers and obtain electricity
Pond pole piece, the density of active material is 0.5-1 mg/cm2.In glove box, button cell is assembled into full of Ar gas, electricity
Pond model 2032, electrolyte is 1M LiPF6, then encapsulating with button cell packaging machine, current density is tested first is
100mA/g, is 200mA/g afterwards.Such as the SiO that Fig. 1 is prepared for embodiment2XRD diffracting spectrums；If Fig. 2 is this reality
Apply the Si/TiO that example is prepared2XRD diffracting spectrum；The circulation prepared for the present embodiment such as Fig. 3-specific capacity is bent
Line；
Embodiment 2
" Si of 0.2g " in the step 7 of embodiment 1 is changed to " Si of 0.15g ", other are constant.
Embodiment 3
By " and then the N in the step 8 of embodiment 12Under atmosphere, sample is heated to 700 DEG C " be changed to " and then N2Under atmosphere, will
Sample is heated to 800 DEG C ", other are constant.
The present invention makes full use of the abundant raw material of rice husk resource, and Si is obtained the characteristics of with low cost, by with TiO2Colloidal sol
The compound obtained Si/TiO of gel solution2Negative material, have its technological process it is short, reproducible, it is workable the characteristics of.
As lithium ion battery negative material, the multiple performance of lithium ion battery can be improved, while can improve being provided to rice husk
The comprehensive utilization ratio in source, fully improves the economic worth of rice husk resource.
Above-described embodiment is presently preferred embodiments of the present invention, is not the limitation to technical solution of the present invention, as long as
Without the technical scheme that creative work can be realized on the basis of above-described embodiment, it is regarded as falling into patent of the present invention
Rights protection scope in.
Claims (7)
1. a kind of lithium ion battery negative material Si/TiO2The preparation method of composite, it is characterised in that：By rice husk resource
Extract SiO2Raw material, then using magnesium reduction process by SiO2Raw material is reduced to Si, finally by Si and TiO2It is combined, you can
Prepare Si/TiO2Composite；Specifically include following steps：
（1）Rice husk is filtered into cleaning repeatedly with running water, is then dried at 100 DEG C -150 DEG C；
（2）By step（1）The rice husk that obtains is added in HCl solution, stirs 3-5h at 90 DEG C -100 DEG C of constant temperature water bath, then
Cleaning 3-5 times is filtered on the screen cloth of 250 mesh with deionized water, is finally dried at 100 DEG C -150 DEG C；
（3）By step（2）The rice husk for obtaining, 2-3h is calcined at 600 DEG C, and the product that will be obtained sieves in the screen cloth of 250 mesh；
（4）By step（3）The product and 100-200 mesh Mg powder for obtaining proportionally carry out ball milling, then in the hand full of Ar gas
Compound is loaded into stainless steel tube in casing, and is sealed against；
（5）Under an ar atmosphere, by step（4）Sample be heated to 650 DEG C, and 3-5h is incubated, then by product in HCl solution
Immersion 5-10h, centrifugal filtration is subsequently adding the HF solution of 1-2ml, centrifugal filtration after immersion 3-5min, finally by product in 40-
Vacuum drying at 60 DEG C；
（6）Solution A is prepared with butyl titanate, absolute ethyl alcohol, glacial acetic acid, PVP raw materials, with absolute ethyl alcohol, deionized water as former
Material prepares B solution, and then B solution is slowly dropped in solution A, obtains TiO2Sol gel solution；
（7）Si is added to TiO2In sol gel solution, 30min-1h is stirred at room temperature, then in 40 DEG C of -60 DEG C of drying；
（8）N2Under atmosphere, by step（7）Sample be heated to 700 DEG C, and be incubated 2-3h, be cooled to room temperature taking-up；
（9）By step（8）Sample, sodium alginate, Super P be well mixed, add little water, be sufficiently stirred for into starchiness painting
On Copper Foil, 10-15h is vacuum dried at 40 DEG C -60 DEG C, is then cut using 13mm piercers and obtain battery pole piece, activity
The density of material is 0.5-1 mg/cm2, in glove box, button cell being assembled into full of Ar gas, battery size is
2032, electrolyte is 1M LiPF6, then encapsulated with button cell packaging machine, it is 100mA/g that current density is tested first, afterwards
It is 200mA/g.
2. a kind of lithium ion battery negative material Si/TiO according to claim 12The preparation method of composite, it is special
Levy and be：The step（2）HCl mass fractions be 10%, the ratio between volume of the rice husk quality and HCl solution is 1:15-
20。
3. a kind of lithium ion battery negative material Si/TiO according to claim 12The preparation method of composite, it is special
Levy and be：The step（4）In product Mg powder mol ratio be 1:2.2, the ball, abrasive material, the mass ratio of solvent are 3:1:
2, the solvent is absolute ethyl alcohol, and the milling atmosphere is Ar gas, and rotating speed is 300/rmin, and the time is 10-15h, and seal is
Stainless steel pipe.
4. a kind of lithium ion battery negative material Si/TiO according to claim 12The preparation method of composite, it is special
Levy and be：The step（3）、（8）Heating rate be 5 DEG C/min, step（5）Heating rate be 1 DEG C/min.
5. a kind of lithium ion battery negative material Si/TiO according to claim 12The preparation method of composite, it is special
Levy and be：The step（6）Middle solution A butyl titanate, absolute ethyl alcohol, the volume ratio of glacial acetic acid are 1:10:1, in B solution
The volume ratio 10 of absolute ethyl alcohol, deionized water:1, the PVP are 1 with the mass ratio of addition Si:2.
6. a kind of lithium ion battery negative material Si/TiO according to claim 12The preparation method of composite, it is special
Levy and be：The step（5）In centrifugation rate be 8000r/min-10000r/min, centrifugation time is 3-5min, HCl concentration
It is 2mol/L, HF mass fractions are 5%.
7. a kind of lithium ion battery negative material Si/TiO according to claim 12The preparation method of composite, it is special
Levy and be：The step（8）In step（7）Sample and sodium alginate, Super P mass ratio be 60%:20%:20%.
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| CN109192932A (en) * | 2018-07-12 | 2019-01-11 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material |
| CN113178564A (en) * | 2021-04-25 | 2021-07-27 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| CN115784300A (en) * | 2022-12-19 | 2023-03-14 | 攀钢集团研究院有限公司 | Preparation method of titanium dioxide coated silicon composite material |
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| CN108923027A (en) * | 2018-06-26 | 2018-11-30 | 华南师范大学 | A kind of organic acid modified Si/TiO2/ rGO@C lithium ion battery negative material and the preparation method and application thereof |
| CN108711617A (en) * | 2018-07-12 | 2018-10-26 | 苏州思创源博电子科技有限公司 | A kind of preparation method of lithium battery carbon coating titanium black anode material |
| CN109192932A (en) * | 2018-07-12 | 2019-01-11 | 苏州思创源博电子科技有限公司 | A kind of preparation method of carbon titanium composite lithium ion battery negative electrode material |
| CN113178564A (en) * | 2021-04-25 | 2021-07-27 | 陈庆 | Silicon dioxide-carbon composite material and preparation method and application thereof |
| CN115784300A (en) * | 2022-12-19 | 2023-03-14 | 攀钢集团研究院有限公司 | Preparation method of titanium dioxide coated silicon composite material |
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Application publication date: 20170531 |