CN103730645A - Silicon-coated carbon fiber nano composite material and preparation method and application thereof - Google Patents
Silicon-coated carbon fiber nano composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicon-coated carbon fiber nano composite material for a lithium ion battery and a preparation method and application of the material. The preparation method specifically comprises the following steps: with tetramethoxysilane as a precursor and natural cellulose as a template and a carbon source, depositing a nano-silica gel film on the surface of the natural cellulose through a surface sol-gel method; calcining and carbonizing in inert gases to obtain a silica-coated carbon fiber nano composite material; and finally, reducing by adopting a low-temperature magnesiothermic reduction method to obtain the silicon-coated carbon fiber nano composite material. According to the preparation method according to the invention, the natural cellulose is taken as a raw material, serves as the template and carbon source and is wide in source and low in cost; the preparation method is simple, feasible, low in cost and pollution-free; the prepared silicon-coated carbon fiber nano composite material can be directly used for a negative electrode of the lithium ion battery without need of an adhesive or a current collector, the total mass of the lithium ion battery is effectively reduced, and the process is simple.
Description
Technical field
The present invention relates to lithium ion battery field, be specifically related to coated carbon fiber nanometer composite material of a kind of silicon for lithium ion battery and its preparation method and application.
Background technology
Lithium ion battery has the advantages such as high, the environmentally friendly and safety and stability of energy density, has been widely used in the energy storage device of portable type electronic product.The expansion of lithium ion battery from small-sized electronic product to high-power power type field, the development of lithium battery is had higher requirement, and the characteristic of electrode material is the key that affects lithium battery various aspects of performance.In commercial Li-ion battery system, carbon cathode material cycle performance is superior at present, but theoretical specific capacity is only 372mAh/g, can not meet the demand of lithium ion battery in high-power power field application such as electric automobiles.Therefore, the cathode material of Novel high-specific capacity flexible obtains paying close attention to widely and studying.In numerous selectable cathode materials, silicon cathode material causes that because having high theoretical specific capacity (4200mAh/g) people pay close attention to greatly.But silicon materials, in charge and discharge process, have larger change in volume up to 300%, thereby cause active material efflorescence and lose and electrically contact with collector.In addition, the conductivity of silicon is not fine, and this has affected the application of cycle performance and the silica-based anode material lithium ion battery of silicon cathode material greatly.
At present, researcher solves by several different methods the problem that silica-based cathode material exists, comprising nanometer, filming, Composite etc.Material with carbon element has stable chemical property, good conductivity, in addition, material with carbon element itself is exactly a kind of well lithium storage materials, in storage lithium process, change in volume is little, can bear certain mechanical stress, and the volumetric expansion of silicon is played to certain cushioning effect and similar compound rear relatively little to material capacity loss with silicon to the embedding lithium current potential of silicon, therefore, in silicon based composite material, studied widely.In recent years, generally adopt high-energy ball milling method or chemical vapor deposition (CVD) method etc. to prepare silicon/carbon nano-composite material.Although these measures have all improved the performance of silica-based cathode material to some extent, preparation process complexity, needs expensive instrument and equipment, and cost is high, makes silica-based anode material and commercial applications also have certain distance.
Summary of the invention
The invention provides coated carbon fiber nanometer composite material of a kind of silicon for lithium ion battery and its preparation method and application.Described preparation method is simple, low cost, pollution-free; Prepare the coated carbon fiber nanometer composite material of silicon with nucleocapsid structure, can, without binding agent and collector, be directly used in lithium ion battery negative, effectively reduced lithium battery gross mass, and technique is simple.
The invention discloses the coated carbon fiber nanometer composite material of a kind of silicon, the even coated Si of described carbon fiber surface, forms nucleocapsid structure, and described carbon fiber has multi-level network structure, and the coated carbon fiber nanometer composite material of described silicon in the form of sheets.
The invention also discloses the preparation method of the coated carbon fiber nanometer composite material of described silicon, take tetramethoxy-silicane as presoma, native cellulose is template and carbon source, first through surface molten glue – gel method at native cellulose surface deposition nanometer titanium dioxide silicate gel film, in inert gas, calcine again charing and obtain coated with silica carbon fiber nanometer composite material, finally adopt the reduction of low temperature magnesium reduction process to obtain the coated carbon fiber nanometer composite material of described silicon.
The material with carbon element adopting in the present invention is obtained by native cellulose calcining charing, native cellulose is a kind of straight chain polysaccharide, carbon containing, hydrogen, three kinds of elements of oxygen, in inert gas, heat, starting stage is by the moisture evaporation in native cellulose, after arriving 275 ℃, start spontaneous charing, the in the situation that of anoxic, only there are carbon and other the composition of fraction to be burnt, when temperature reaches 400～500 ℃, charing completes, obtain carbon fiber, described carbon fiber has retained the original multi-level network structure of native cellulose material on microcosmic.
As preferably, described native cellulose, before use through preliminary treatment, is specially: described native cellulose through ethanol clean, stand-by after suction filtration.
Further preferably, the preliminary treatment of described native cellulose is carried out in suction filtration device, is specially: native cellulose is placed in to suction filtration device, first with ethanol, cleans 2～3 times vacuum filtration.
As preferably, the preparation method of the described coated carbon fiber nanometer composite material of silicon, concrete steps are:
(1) tetramethoxy-silicane/methanol solution that configuration concentration is 100～1000mM, is impregnated into pretreated native cellulose in described tetramethoxy-silicane/methanol solution, after standing deposition, filters; After methyl alcohol, deionized water washing, in deionized water, after standing hydrolysis, filter respectively; Repeat after aforesaid operations, more after filtration, dry, obtain the native cellulose of surface deposition nanometer titanium dioxide silicate gel film;
Described being impregnated into refer to, the liquid level of tetramethoxy-silicane/methanol solution is higher than the upper surface of native cellulose.
The preparation of individual layer nanometer titanium dioxide silicate gel film comprises deposition-washing-hydrolysis-dry run, and the different number of times that circulates can deposit the nanometer titanium dioxide silicate gel film of different-thickness.
(2) native cellulose charing under inert atmosphere of the surface deposition nanometer titanium dioxide silicate gel film that step (1) obtains, obtains coated with silica carbon fiber nanometer composite material;
Described carbonization temperature is 650 ℃～750 ℃, and carbonization time is 5～10h;
(3) coated with silica carbon fibre material step (2) being obtained and magnesium powder mix, and under 650 ℃～750 ℃, inert atmosphere, reduce, and obtain the coated carbon fiber nanometer composite material of described silicon;
The mass ratio of described coated with silica carbon fiber nanometer composite material and magnesium powder is 1:1～5.
As preferably, the deposition process of described nanometer titanium dioxide silicate gel film is carried out in suction filtration device, is specially:
Described tetramethoxy-silicane/methanol solution is added in suction filtration device, and suction filtration, to the upper surface of liquid level higher than native cellulose, makes solution impregnation native cellulose, suction filtration after standing deposition; Again respectively after methyl alcohol, deionized water rinse, suction filtration after standing hydrolysis in deionized water; Repeatedly, suction filtration is dry.
Above-mentioned process is carried out in suction filtration device, can save the transfer through each step native cellulose after treatment, has not only simplified technique, and avoids native cellulose structural damage.
As preferably, described native cellulose is quantitative filter paper, cotton or cotton; More preferably quantitative filter paper.Preferred quantitative filter paper has the porous network structure that unique hierarchical structure from macroscopic view to nano-level and plurality of fibers are cross-linked with each other, take it as template and carbon source for preparing the coated carbon fiber nanometer composite material of silicon, provide an advantageous platform.
As preferably, described tetramethoxy-silicane/concentration of methanol solution is 500mM.
As preferably, described inert gas is high-purity argon gas, and purity is higher than 99.999%.
As preferably, the described coated with silica carbon fibre material of step (3), after low temperature magnesiothermic reduction, then obtains the coated carbon fiber nanometer composite material of described silicon through salt acid soak, washing, after dry.
The invention also discloses the coated carbon fiber nanometer composite material of described silicon in the application of preparing in electrode of lithium cell.
The coated carbon fiber nanometer composite material of described silicon can be directly as lithium ion battery negative;
Or after coated described silicon carbon fiber nanometer composite material is mixed with binding agent and acetylene black, be coated on copper sheet or nickel foam collector, as lithium ion battery negative.
The chemical property that is coated carbon fiber nanometer composite material in order to detect the silicon of preparation, is assembled into button cell and is carried out electrochemical property test.
The method of assembled battery has two kinds, first method is by active material: polytetrafluoroethylene: the mass ratio=75:10:15 of acetylene black, accurately take each material, after adding N-methyl isophthalic acid-pyrrolidones to mix, be coated onto (copper sheet or nickel foam) on collector and prepare electrode slice, in each electrode slice, the quality of active material is within the scope of 1～2mg, then vacuumize at 120 ℃, then dress up button cell with lithium metal matched group in glove box.The second is not adding additives and collector, gets this flaky composite material 1～2mg, directly as lithium ion battery negative and lithium metal matched group, dresses up button cell.
The battery of two kinds of method assemblings is CR2025 type button cell, and electrolyte is 1MLiPF
6/ EC:DMC:EMC(volume ratio is 1:1:1), between two electrodes, with Celgard2300 barrier film, separate, in order to prevent inside battery loose contact, metal lithium sheet one end adds a slice nickel foam and makes pad.
Material prepared by the present invention, for lithium ion battery negative, has higher specific capacity, shows good charge-discharge cycle, after 100 circulations, without obvious, decays.
Compared with prior art, the present invention has the following advantages:
1. the native cellulose material that the present invention selects is the conventional quantitative filter paper in laboratory, cotton, cotton etc., and source is abundant, cheap.
2. when the present invention prepares material, select low temperature magnesium reduction process, on the basis that keeps the original unique texture of material and pattern, silicon dioxide is successfully reduced to silicon.
3. in the coated carbon fiber nanometer composite material of silicon that prepared by the present invention, silicon is wrapped in the surface of carbon fiber uniformly, and plurality of fibers is cross-linked with each other and reticulates structure, can bear certain mechanical stress, carbon fiber not only plays certain cushioning effect to the volumetric expansion of silicon, increase the conductivity of material simultaneously, effectively improved the specific capacity of material.
4. the coated carbon fiber nanometer composite material of silicon that prepared by the present invention can, without binding agent and collector, be directly used in lithium ion battery negative, effectively reduced lithium battery gross mass, and technique is simple.
Accompanying drawing explanation
Fig. 1 is the carbon fiber nanometer composite material of coated with silica and the morphology characterization of the coated carbon fiber nanometer composite material of silicon of preparing in embodiment:
Fig. 1 (a), 1(b) be ESEM and the transmission electron microscope picture of the carbon fiber nanometer composite material of the coated with silica prepared in embodiment;
Fig. 1 (c), 1(d) be ESEM and the transmission electron microscope picture of the coated carbon fiber nanometer composite material of silicon;
Fig. 2 is the cyclic voltammetry curve figure of battery 1;
Fig. 3 is the cycle performance curve of battery 1 and 2;
Fig. 4 is the charging and discharging curve of battery 1 under different current densities;
Fig. 5 is the cycle performance curve of battery 3 and 4.
Embodiment
Embodiment
1) the tetramethoxy-silicane solution that is 500mM with methyl alcohol compound concentration, stirs under room temperature 2 hours, standby.
2) quantitative filter paper is placed in to suction filtration device, with ethanol rinse 2 to 3 times, vacuum is drained.
3) get about 20mL tetramethoxy-silicane solution and join in suction filtration device, standing 15min, making is that methoxy silane is adsorbed be deposited on filter paper fibre completely, this is deposition process.
4) low vacuum slowly pumps remaining tetramethoxy-silicane solution to approaching filter paper fibre surface, adds methyl alcohol rinse 2 to 3 times, standing 1min.
5) low vacuum pumps remaining methyl alcohol, then adds deionized water rinse 2 to 3 times, standing 10min, and this is hydrolytic process, finally drains, and completes a deposition/hydrolysis circulation, has deposited layer of silicon dioxide film.Repeat 3)～5) step 20 time obtains 20 layers of silica dioxide gel film.If repeat different number of times and can obtain the silicon carbon coated fibrous composite of Different Silicon content.
6) by having deposited the quantitative filter paper of 20 layers of silica dioxide gel film, be placed in tube furnace, pass into argon gas, temperature programming to 750 ℃, calcined after 6 hours, naturally cooled to room temperature, prepared the carbon fiber nanometer composite material of Silica-coated.
Fig. 1 (a) is the scanning electron microscope (SEM) photograph of the carbon fiber nanometer composite material of the Silica-coated prepared of the present embodiment, the plurality of fibers that can see the clearly thickness inequality porous network structure together forming that is interweaved, illustration is the photo of this material, with calcining before filter paper compared with to some extent shrink.
Fig. 1 (b) is the transmission electron microscope picture of the carbon fiber nanometer composite material of the Silica-coated prepared of the present embodiment, from scheming, can see that silicon dioxide is coated on carbon fiber surface equably, the thickness of silicon dioxide layer is approximately 40nm, and in illustration, selected area electron diffraction image shows that silicon dioxide and carbon that carbonization obtains are all unbodied.
7) by the carbon fiber nanometer composite material of Silica-coated and magnesium powder in molar ratio 1:2.5 add in stainless steel cauldron, pass into argon gas, temperature programming to 750 ℃ also keeps 3 hours, utilize low temperature magnesium reduction process that silicon dioxide is reduced to silicon, the material obtaining soaks 12 hours in 2M HCl solution, and MgO, Mg are removed in washing
2the impurity such as Si, dry, obtain the coated carbon fiber nanometer composite material (being designated as C/Si) of silicon.
The silicon that Fig. 1 (c) is prepared for the present embodiment is coated the scanning electron microscope (SEM) photograph of carbon fiber nanometer composite material, compared with the stereoscan photograph (Fig. 1 (a)) of coated with silica carbon fiber nanometer composite material, after low temperature magnesiothermic reduction, there is not great variation in material microcosmic surface form, still there is the porous network structure that the unique hierarchical structure of natural fiber cellulosic material from macroscopic view to nano-level and plurality of fibers are cross-linked with each other, illustration is the photo of this material, is flaky material in macroscopic view.
The silicon that Fig. 1 (d) is prepared for the present embodiment is coated the transmission electron microscope picture of carbon fiber nanometer composite material, can see that silicon covers carbon fiber surface uniformly from scheming, and still keeps original structure.What in figure, insert is selected area electron diffraction image, and it is the silicon of crystal formation that electronic diffraction collection of illustrative plates shows, respectively (200), (400) and (422) crystal face of corresponding silicon.Proof is after low temperature magnesiothermic reduction, and silicon dioxide is successfully reduced to crystalline silicon.
Comparative example
Quantitative filter paper is directly calcined to 6h at 750 ℃ in argon gas, obtain carbon fiber nanometer material (being designated as C).
Application examples 1
Materials A is assembled into button cell as active component, press active material: polytetrafluoroethylene: acetylene black mass ratio=75:10:15, accurately take each material, after adding 1-METHYLPYRROLIDONE to mix, be coated onto (copper sheet or nickel foam) on collector and prepare electrode slice, in each electrode slice, the quality of active material is within the scope of 1～2mg, then vacuumize at 120 ℃, then dress up CR2025 type button cell with lithium metal matched group in glove box.Electrolyte is that 1MLiPF6/EC:DMC:EMC(volume ratio is 1:1:1), between two electrodes, with Celgard2300 barrier film, separate, in order to prevent inside battery loose contact, metal lithium sheet one end adds a slice nickel foam and makes pad.
When materials A is the coated carbon fiber nanometer composite material of the silicon for preparing of embodiment, the button cell being assembled into is designated as battery 1;
When materials A be comparative example prepare carbon fiber nanometer material time, the button cell being assembled into is designated as battery 2;
The button cell being assembled into is carried out to electrochemical property test:
One, cyclic voltammetry
Fig. 2 is the cyclic voltammetry curve of battery 1, in figure, curve 1～4 represents the circulation number of turns, and the coated carbon fiber nanometer composite material of silicon, in embedding lithium process first, has occurred a wider reduction peak when 0.7V, the formation of corresponding SEI film (solid electrolyte interface film), when current potential is reduced to 0.2V left and right, reduction current increases rapidly, and approaches peak value approaching 0V part, show this interval interior lithium of embedding first reaction that silicon occurs, generated Li
xsi alloy.In discharge process first, at 0.34V place, there is the corresponding Li of very wide oxidation peak
+from Li
xthe process of deviating from Si alloy, the 2nd, 3,4 whens scanning, the reduction peak of going back 0.7V place on virgin curve no longer occurs, shows that SEI film is mainly forming in embedding lithium process first, and more stable.The following electric current of 0.25V increases rapidly, and in the new reduction peak of 0.15V place appearance, show that embedding lithium reaction is herein with also different first, this is because irreversible crystal transfer has occurred the silicon of embedding lithium reaction first, from crystal, become unformed shape, and amorphous silicon reacts and has obvious difference with the embedding lithium of crystal formation silicon.2nd, on 3,4 oxidation curves, retained the oxidation peak occurring first, and current value successively increases.
Two, cycle life test
Fig. 3 is the cycle performance curve of battery 1 and 2 when current density is 100mA/g, observing Fig. 3 can find, electric discharge for the first time (discharge) specific capacity of battery 1 is 778mAh/g, charging (charge) specific capacity is 321mAh/g, along with charge and discharge cycles is carried out, the reversible specific capacity of material increases gradually, and 100 circulation time reversible specific capacities are 335mAh/g, after 150 circulations, the reversible specific capacity of material does not still decay to 353mAh/g.Compare battery 2, reversible specific capacity has improved 123mAh/g.
Three, the test of the charge and discharge cycles under different charge-discharge velocities
Fig. 4 is the charging and discharging curve of battery 1 under different current densities, is respectively 100mA/g, 200mA/g in current density, 500mA/g, during 1000mA/g, reversible specific capacity is respectively 272mAh/g, 236mAh/g, 184mAh/g, 145mAh/g after high current density discharges and recharges, then discharges and recharges under 100mA/g current density, reversible specific capacity still can keep original value, illustrates that electrode prepared by this material discharges and recharges and has higher invertibity and stability under higher current density.
Application examples 2
The carbon fiber nanometer material of preparing in coated the silicon of preparing in embodiment carbon fiber nanometer composite material and comparative example is assembled into lithium battery according to second method respectively, is specially:
Not adding additives and collector, intercepts respectively two kinds of above-mentioned nano material 1～2mg, directly as lithium ion battery negative and lithium metal matched group, dresses up CR2025 type button cell.The condition of assembled battery and method are as first method, and electrolyte is 1M LiPF
6/ EC:DMC:EMC(volume ratio is 1:1:1), barrier film used is Celgard2300, in order to prevent inside battery loose contact, metal lithium sheet one end adds a slice nickel foam and makes pad.
The button cell being assembled into the coated carbon fiber nanometer composite material of silicon of preparing in embodiment is designated as battery 3;
The button cell being assembled into the carbon fiber nanometer material of preparing in comparative example is designated as battery 3;
Fig. 5 is the cycle performance curve of battery 3 and 4 when current density is 100mA/g, the specific discharge capacity for the first time of battery 3 is 386mAh/g, and charge ratio capacity is 326mAh/g, after 100 circulations, the reversible specific capacity of battery 3 has a small amount of decay, is 286mAh/g.Although battery 4 has higher electric discharge first, charge ratio capacity is respectively 823mAh/g, 323mAh/g, irreversible specific capacity is larger first, and after 100 times discharge and recharge, reversible specific capacity is 210mAh/g.Compare carbon fiber nanometer material, the coated carbon fiber nanometer composite material of silicon shows better chemical property.
Claims (10)
1. the coated carbon fiber nanometer composite material of silicon, is characterized in that, the even coated Si of described carbon fiber surface, forms nucleocapsid structure, and described carbon fiber has multi-level network structure, and the coated carbon fiber nanometer composite material of described silicon in the form of sheets.
2. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 1, it is characterized in that, take tetramethoxy-silicane as precursor, native cellulose is template and carbon source, first through surface molten glue – gel method at native cellulose surface deposition nanometer titanium dioxide silicate gel film, in inert gas, carbonization obtains coated with silica carbon fiber nanometer composite material again, finally adopts the reduction of low temperature magnesium reduction process to obtain the coated carbon fiber nanometer composite material of described silicon.
3. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 2, is characterized in that, described native cellulose, before use through preliminary treatment, is specially: described native cellulose is stand-by after ethanol cleaning, suction filtration.
4. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 3, is characterized in that, concrete steps are:
(1) tetramethoxy-silicane/methanol solution that configuration concentration is 100～1000mM, is impregnated into pretreated native cellulose in described tetramethoxy-silicane/methanol solution, after standing deposition, filters; After methyl alcohol, deionized water washing, in deionized water, after standing hydrolysis, filter respectively; Repeat after aforesaid operations 10～20 times, more after filtration, dry, obtain the native cellulose of surface deposition nanometer titanium dioxide silicate gel film;
(2) native cellulose charing under inert atmosphere of the surface deposition nanometer titanium dioxide silicate gel film that step (1) obtains, obtains coated with silica carbon fiber nanometer composite material;
Described carbonization temperature is 650 ℃～750 ℃, and carbonization time is 5～10h;
(3) coated with silica carbon fiber nanometer composite material step (2) being obtained and magnesium powder mix, and under 650 ℃～750 ℃, inert atmosphere, reduce, and obtain the coated carbon fiber nanometer composite material of described silicon;
The mass ratio of described coated with silica carbon fiber nanometer composite material and magnesium powder is 1:1～5.
5. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 4, it is characterized in that, the preliminary treatment of described native cellulose with in the process of native cellulose surface deposition nanometer titanium dioxide silicate gel film, all in suction filtration device, carry out, be specially:
(1) preliminary treatment of native cellulose: native cellulose is placed in to suction filtration device, with ethanol cleaning 2～3 times, is still placed in suction filtration device after vacuum filtration stand-by;
(2) at native cellulose surface deposition nanometer titanium dioxide silicate gel film: described tetramethoxy-silicane/methanol solution is added in suction filtration device, and suction filtration, to the upper surface of liquid level higher than native cellulose, makes solution impregnation native cellulose, suction filtration after standing deposition; Again respectively after methyl alcohol, deionized water rinse, suction filtration after standing hydrolysis in deionized water; Repeatedly, suction filtration is dry, obtains the native cellulose of surface deposition nanometer titanium dioxide silicate gel film.
6. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 5, is characterized in that, described native cellulose is quantitative filter paper, cotton or cotton.
7. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 6, is characterized in that, described native cellulose is quantitative filter paper.
8. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 7, is characterized in that, described tetramethoxy-silicane/concentration of methanol solution is 500mM.
9. the preparation method of the coated carbon fiber nanometer composite material of silicon as claimed in claim 8, it is characterized in that, the described coated with silica carbon fibre material of step (3), after low temperature magnesiothermic reduction, then obtains the coated carbon fiber nanometer composite material of described silicon through salt acid soak, washing, after dry.
10. the coated carbon fiber nanometer composite material of silicon as claimed in claim 1, in an application of preparing in electrode of lithium cell, is characterized in that, described silicon is coated to carbon fiber nanometer composite material directly as lithium ion battery negative;
Or after coated described silicon carbon fiber nanometer composite material is mixed with binding agent and acetylene black, be coated on copper sheet or nickel foam collector, as lithium ion battery negative.
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| CN104332620A (en) * | 2014-08-26 | 2015-02-04 | 中国科学技术大学先进技术研究院 | Method for synthesizing silicon nano powder through hydrothermal reactions and applications of silicon nano powder |
| CN104766963A (en) * | 2015-04-22 | 2015-07-08 | 安徽理工大学 | Method for preparing metal oxide-carbon fiber nano composite material |
| CN105118961A (en) * | 2015-07-17 | 2015-12-02 | 江苏华盛精化工有限责任公司 | Polypyrrole coated nanotube silicon material preparation method, product, and application of product |
| CN105810889A (en) * | 2016-04-25 | 2016-07-27 | 浙江工业大学 | Binder-free porous silicon/carbon composite electrode and application thereof |
| CN105826519A (en) * | 2016-04-25 | 2016-08-03 | 浙江工业大学 | Porous silicon-based electrode without adhesive and application thereof |
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| CN108346786A (en) * | 2018-01-23 | 2018-07-31 | 浙江大学 | The preparation method and product of nano-silicon/carbon composite and nano silicon dioxide/carbon composite |
| CN109004196A (en) * | 2018-07-24 | 2018-12-14 | 大连理工大学 | A kind of preparation method of cotton cladding lithium titanate anode material |
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| CN110885074A (en) * | 2018-09-07 | 2020-03-17 | 青岛绿锦和环境保护有限公司 | Cellulose nanofiber-assisted nitrogen-doped carbon nanocage flexible film and preparation method thereof |
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| CN113005424A (en) * | 2019-12-19 | 2021-06-22 | 明基材料股份有限公司 | Method for optimizing atomic layer deposition |
| CN113005424B (en) * | 2019-12-19 | 2022-05-06 | 明基材料股份有限公司 | Method for optimizing atomic layer deposition |
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| CN113178562B (en) * | 2021-04-23 | 2022-08-19 | 天津科技大学 | Fabric-like carbon-coated silicon dioxide composite material and application thereof |
| CN114335553A (en) * | 2022-03-15 | 2022-04-12 | 湖南金阳烯碳新材料有限公司 | Silicon-carbon-graphite negative electrode material and preparation method and application thereof |
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