CN103280560A - Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery - Google Patents
Preparation method of mesoporous SiOx/C composite negative material of lithium-ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a mesoporous SiOx/C composite negative material of a lithium-ion battery, and belongs to the fields of new materials and electrochemistry. The preparation method comprises the following steps of: taking polyvinylpyrrolidone as an auxiliary template agent, taking an organic surface active agent as a template agent and organic silicon as a silicon source, obtaining mesoporous silica precursor by hydrothermal treatment, adding a carbon source, and preparing SiOx/C composite negative material with a mesoporous structure by carbothermic reduction reaction occurring in the process of high-temperature thermal treatment. The preparation method disclosed by the invention has the advantages that the specific capacity of the material is high, the structure is novel, and simultaneously the cycling stability is good; the yield is high; and the prepared SiOx/C composite material is fine in particle, uniform in particle size and component distribution, high in specific capacity and good in cycling stability, is an ideal composite negative material of the lithium-ion battery, and can be widely applied in the fields such as various portable electronic equipment, electric vehicles and aerospace.
Description
Technical field
The invention belongs to new material and electrochemical field, be specifically related to SiOx/C composite cathode material for lithium ion cell of a kind of high specific discharge capacity and preparation method thereof.
Background technology
The increase of the energy demand of following global population increase, economic development, living standard to improve and arriving, and the crisis of the minimizing of fossil fuel and global warming have forced the mankind to turn to the development and utilization of new forms of energy (as wind energy, solar energy, tidal energy).But these new forms of energy have intermittence; stable energy supply can not be provided; and as storing and the lithium rechargeable battery of stablizing energy supply being provided, might provide an important solution for solving current energy crisis, therefore receive increasing concern.Along with the miniaturization of current portable type electronic product, light-weighted development trend, made the battery of exploitation height ratio capacity become the focus of current research in addition.
At present graphite is because its conductivity height, lithium ion diffusion coefficient are big, little, advantages such as embedding lithium current potential is low, low price of change in volume before and after the embedding lithium, by extensively as lithium ion battery negative material.But because its theoretical specific capacity has only 372 mAh/g, and to the exploitation of its specific capacity near its limiting value, be difficult to adapt to current hybrid vehicle (HEV) and plug-in unit hybrid vehicle (PHEV) for the requirement of height ratio capacity battery.Therefore, the negative material of development height ratio capacity, long-life, high security is extremely urgent.
Silicon is with its specific capacity height (4200 mAh/g), embedding lithium current potential is low, raw material sources have extensively become tool application prospect negative material, but the enormousness in its doff lithium process changes cracking and the efflorescence that easily causes electrode material, cause the cycle performance variation of electrode, this problem never obtains fine solution, has therefore limited its commercial applications.Nano oxidized inferior silicon (SiOx) material can generate active phase nanometer Si and nonactive phase oxidation lithium and lithium metasilicate in embedding lithium process, generated in-situ nanometer Si is dispersed in nonactive phase oxidation lithium and the lithium metasilicate matrix uniformly, both volumetric expansions in the buffer Si doff lithium process to a certain extent, can also prevent the reunion of nanometer Si particle, but the strictness of the inferior silicon preparation condition of the commercial oxidation of extensive use at present makes its price comparison height, and adopts the inferior silicon of nano particle oxidation can make that the high rate performance of material is relatively poor.In addition, the electronic conductance rate variance of the inferior silicon materials of oxidation own also is a big reason that causes its high rate performance difference.
At the above shortcoming of the inferior silicon of silicaization, mainly improve the chemical property of material at present by the following method: 1) nanometer.Reduce particle size by ball milling, high-energy ball milling, reduce the volumetric expansion of material, can shorten the diffusion length of lithium ion simultaneously, thereby improve cycle performance and the high rate performance of material.The Jae-Hun Kim seminar of South Korea Seoul university adopts commercial SiO and PVA to mix to carry out ball milling to carry out high-energy ball milling to prepare the SiO/C composite material, electrode with this material preparation, its first discharge specific capacity and charge ratio capacity are respectively 1050 and 800 mAh/g(J. H. Kim, and et al. Journal of Power Sources 170 (2007): 456-459) 100 reversible capacities still have 710 mAh/g.The Wu of chemical engineering institute of Univ Nat Taiwan is that upright seminar carries out high-energy ball milling to commercialization SiO powder and chemical vapor deposition process prepares the SiO/C composite material, material is made electrode, it discharges first and charging capacity is respectively 1056 and 675 mAh/g, still keep 620 mAh/g(W. Liu, et al. Journal of Applied Electrochemistry 39 (2009) after 50 circulations: 1643-1649) 2) compound with material with carbon element.Mainly by material bag carbon being handled or is mixed to improve with Graphene the electronic conductivity of material, the volumetric expansion that the method also can padded coaming simultaneously.Chil-Hoon Doh seminar of Korea S electrician research institute carries out high-energy ball milling Processing of Preparation SiO/C composite material to commercialization silica powder and graphite mixing, electrode with this material preparation, its first discharge specific capacity and charge ratio capacity are respectively 1556 and 693 mAh/g(C.H. Doh, et al. Journal of Power Sources 179 (2008): 367-370), 30 times circulation back reversible capacity still has 688 mAh/g.Employing silicon dioxide and the compound SiO that prepare of carbon such as Yu Yao
2/ C composite material, the electrode first discharge specific capacity of preparing is 536 mAh/g, 50 times circulation back reversible specific capacity still has 500 mAh/g(Y. Yao, et al. Journal of Power Source 196 (2011): 10240-10243).3) preparation nanometer special appearance.As the many hollow structures of nanometer.The volumetric expansion of buffer Si to a certain extent of this nanometer special appearance material, the cycle performance of raising material; The material that has the porous nano special appearance has in addition shortened the transmission range of lithium ion in material, thereby has also improved the high rate performance of material.The porous SiO/C composite material of height ratio capacity is prepared in the auxiliary corrosion of employing metals such as Jung-In Lee, this material list reveals good cycle performance (the following 50 times capability retention of 0.1C current density be initial capacity 98%) and high rate performance (capability retention under the 5C current density is 62.6% under the 0.1C) (J. I. Lee, et al. Nano Energy 2 (2013): 146-152).Method for preparation method or complex process or productive rate are low, are not suitable for scale preparation.
Summary of the invention
The object of the present invention is to provide that a kind of particle is tiny, particle diameter is evenly distributed, pattern is regular, have the mesoporous SiOx/C composite cathode material for lithium ion cell of higher relatively specific capacity and good circulation performance.This preparation method's productive rate height, be convenient to scale preparation.
The preparation method of the inferior silicon-carbon composite cathode material of a kind of lithium ion battery oxidation, it is characterized in that: it is to be made of two kinds of components of SiOx, C, and the quality percentage composition of C in the SiOx/C composite negative pole material is 1 ~ 30%.
Its concrete steps are:
(1) with PVP as the auxiliary template agent, be dissolved in a certain amount of sodium hydrate aqueous solution, be stirred to fully dissolving.The addition of NaOH is 2.5-4.0 mg/ml, and the addition of PVP is 5.0-12.0 mg/ml.
(2) agent joins above-mentioned making in the settled solution as template with surfactant, and brute force is stirred to dissolving fully.Wherein, the addition of surfactant is 8.0-12 mmol/L.
(3) organosilicon joins in the above-mentioned solution as the silicon source.Addition is 0.02-0.05 mol/L.
(4) the powerful stirring of above-mentioned solution after 24 hours, is moved on in the band teflon-lined water heating kettle with a constant volume, in insulating box, react 12 ~ 48h under the uniform temperature.
(5) after the repeatedly washing and suction filtration of white powder through ethanol and deionized water that step (4) is made, join in the deionized water, brute force is stirred to even dispersion.
(6) carbon source is joined in the solution that step (5) makes, brute force is stirred to carbon source and fully dissolves, and the carbon source addition is the 0-30% that organosilicon source theoretical water solves the silicon dioxide quality.
(7) aforesaid liquid is rotated dry processing of evaporation bag carbon.Temperature is 80-90
oC, rotating speed are 90-120 rmp.
(8) under the inertia protective atmosphere, with the powder of step (7) gained with 5
oC/min speed is warming up to 800 ~ 1200
oC insulation 1 ~ 5 hour, temperature programmed control cools off or cools to room temperature with the furnace then, can obtain mesoporous SiOx/C composite material.
Surfactant in the step (2) is one or more in DTAB, softex kw (CTAB), octadecyl trimethylammonium bromide, poly(ethylene oxide), the myristyl betaine (TB).
Silicon source in the step (3) is methyl silicate or tetraethoxysilane (TEOS).
The described hydrothermal temperature of step (4) is 50 ~ 150
oC.
The described carbon source of step (6) is sucrose.
The described inertia protective atmosphere of step (8) is one or both in nitrogen, the argon gas.
It is the template agent that the present invention adopts a kind of surfactant, and PVP is that meso pore silicon oxide material is at first prepared in the auxiliary template agent, carries out compoundly with carbon source then, obtains the inferior silicon/carbon composite of oxidation by Technology for Heating Processing.Major advantage of the present invention is that the powder of preparing has meso-hole structure and particle is tiny, and particle diameter, distributed components have good cyclical stability and high rate performance, and simultaneously, preparation technology is simple, productive rate is high, is convenient to scale preparation.Be a kind of preparation method of desirable lithium ion battery negative material, can be widely used in fields such as various portable electric appts, electric automobile and Aero-Space.
Description of drawings
Fig. 1 is the nitrogen adsorption desorption curve that obtains the mesopore silicon oxide presoma of embodiment 1;
Fig. 2 is the transmission electron microscope picture of mesopore silicon oxide/carbon compound cathode materials of embodiment 1;
Fig. 3 is the circulation volume figure of mesopore silicon oxide/carbon compound cathode materials of embodiment 1.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited to protection scope of the present invention:
Embodiment 1:
Take by weighing 0.46 g dissolution of sodium hydroxide in 120 ml deionized waters, be stirred to dissolving fully; Take by weighing 1.0 g polyvinylpyrrolidones (PVP) and 1.40 g softex kws respectively and be dissolved in the above-mentioned solution, be stirred to dissolving fully.Measure 5.80 ml tetraethoxysilanes and slowly pouring in the above-mentioned solution, the powerful stirring 24 hours, the white suspension-turbid liquid that obtains is transferred in the water heating kettle that 200 ml have polytetrafluoroethylene ethene liner, in 50
oC thermostatted water heat treatment 48 hours.Naturally cooled liquid cleans and suction filtration 5 times repeatedly through alcohol and deionized water, and the white powder that obtains is dispersed in the beaker of 120 ml, powerful 30 min that stir.Take by weighing 1.0 g sucrose and be dissolved in the above-mentioned suspension-turbid liquid, be stirred to fully and carry out rotary evaporation after the dissolving, rotary speed is 100 rpm, and the waters temperature is 90
oC obtains white presoma product, and the presoma product is warming up to 800 under argon gas atmosphere
oC is incubated 1 h, cools to room temperature with the furnace and makes the inferior silicon-carbon composite cathode material powder of mesoporous oxidation.The 70 wt.% mesopore silicon oxide/carbon composites that make, the acetylene black of 15 wt.% and the CMC of 15 wt.% are mixed, make slurry, evenly be coated on the Copper Foil, be stamped into the circular electrode pole piece behind the vacuum drying, be to electrode with lithium metal, 1 mol/L LiPF
6/ EMC+DMC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, the charging/discharging voltage scope is 0.01 ~ 2.5 V, the result shows, it has better electrochemical performance, 0.1 under the current density of A/g, first discharge specific capacity is 1380 mAh/g, enclosed pasture efficient is 61 % first, circulating, the specific capacity of material is 750 mAh/g after 100 times, and the cyclical stability of material is fine; Capability retention shows good high rate performance with respect to 69% of 0.1 A/g under the current density of 1A/g.Fig. 1 is the nitrogen adsorption desorption curve that obtains the mesopore silicon oxide presoma of embodiment 1; As shown in the figure: the inferior silicon precursor of oxidation has IV type absorption loop line under the 0.4-0.8 relative pressure, illustrates that the inferior silicon carbon material presoma of synthetic oxidation has meso-hole structure.Fig. 2 is the transmission electron microscope picture of mesopore silicon oxide/carbon compound cathode materials of embodiment 1, as shown in the figure: the meso-hole structure that the inferior silicon carbon material of the mesoporous oxidation after process bag carbon and the heat treatment still remains intact, and the inferior silicon face of mesoporous oxidation coated one deck carbon film, and this plays a role to electronic conductivity and padded coaming volumetric expansion of improving material.Fig. 3 is the circulation volume figure of mesopore silicon oxide/carbon compound cathode materials of embodiment 1.As seen from Figure 3, material has good stable circulation performance and higher coulombic efficiency, 100 times the circulation after capacity be 92% of initial capacity, the coulombic efficiency except first is all more than 98%.
Embodiment 2:
Take by weighing 0.46 g dissolution of sodium hydroxide in 120 ml deionized waters, be stirred to dissolving fully; Take by weighing 1.0 g polyvinylpyrrolidones (PVP) and 1.30 g DTABs respectively and be dissolved in the above-mentioned solution, be stirred to dissolving fully.Measure 5.80 ml tetraethoxysilanes and slowly pouring in the above-mentioned solution, the powerful stirring 24 hours, the white suspension-turbid liquid that obtains is transferred in the water heating kettle that 200 ml have polytetrafluoroethylene ethene liner, in 80
oC thermostatted water heat treatment 48 hours.Naturally cooled liquid cleans and suction filtration 5 times repeatedly through alcohol and deionized water, and the white powder that obtains is dispersed in the beaker of 120 ml, powerful 30 min that stir.Take by weighing 1.0 g sucrose and be dissolved in the above-mentioned suspension-turbid liquid, be stirred to fully and carry out rotary evaporation after the dissolving, rotary speed is 100 rpm, and the waters temperature is 90
oC obtains white presoma product, and the presoma product is warming up to 800 under argon gas atmosphere
oC is incubated 1 h, cools to room temperature with the furnace and makes the inferior silicon-carbon composite cathode material powder of mesoporous oxidation.The 70 wt.% mesopore silicon oxide/carbon composites that make, the acetylene black of 15 wt.% and the CMC of 15 wt.% are mixed, make slurry, evenly be coated on the Copper Foil, be stamped into the circular electrode pole piece behind the vacuum drying, be to electrode with lithium metal, 1 mol/L LiPF
6/ EMC+DMC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, the charging/discharging voltage scope is 0.01 ~ 2.5 V, the result shows, it has better electrochemical performance, 0.1 under the current density of A/g, first discharge specific capacity is 1350 mAh/g, and enclosed pasture efficient is 60 % first, and circulating, the specific capacity of material is 729 mAh/g after 100 times.The cycle performance of material is better, and capability retention shows relatively poor high rate performance with respect to 71 % of 0.1 A/g under the current density of 1A/g.
Embodiment 3:
Take by weighing 0.46 g dissolution of sodium hydroxide in 120 ml deionized waters, be stirred to dissolving fully; Take by weighing 1.0 g polyvinylpyrrolidones respectively, (PVP) be dissolved in the above-mentioned solution with 1.40 g softex kws, be stirred to dissolving fully.Measure 5.0 ml methyl silicates and slowly pouring in the above-mentioned solution, the powerful stirring 24 hours, the white suspension-turbid liquid that obtains is transferred in the water heating kettle that 200 ml have polytetrafluoroethylene ethene liner, in 80
oC thermostatted water heat treatment 48 hours.Naturally cooled liquid cleans and suction filtration 5 times repeatedly through alcohol and deionized water, and the white powder that obtains is dispersed in the beaker of 120 ml, powerful 30 min that stir.Take by weighing 1.0 g sucrose and be dissolved in the above-mentioned suspension-turbid liquid, be stirred to fully and carry out rotary evaporation after the dissolving, rotary speed is 100 rpm, and the waters temperature is 90
oC obtains white presoma product, and the presoma product is warming up to 800 under argon gas atmosphere
oC is incubated 1 h, cools to room temperature with the furnace and makes the inferior silicon-carbon composite cathode material powder of mesoporous oxidation.The 70 wt.% mesopore silicon oxide/carbon composites that make, the acetylene black of 15 wt.% and the CMC of 15 wt.% are mixed, make slurry, evenly be coated on the Copper Foil, be stamped into the circular electrode pole piece behind the vacuum drying, be to electrode with lithium metal, 1 mol/L LiPF
6/ EMC+DMC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, the charging/discharging voltage scope is 0.01 ~ 2.5 V, the result shows, it has better electrochemical performance, 0.1 under the current density of A/g, first discharge specific capacity is 1360 mAh/g, enclosed pasture efficient is 64 % first, circulating, the specific capacity of material is 750 mAh/g after 100 times, and the cyclical stability of material is better; Capability retention shows high rate performance preferably with respect to 63% of 0.1 A/g under the current density of 1 A/g.
Embodiment 4:
Take by weighing 0.46 g dissolution of sodium hydroxide in 120 ml deionized waters, be stirred to dissolving fully; Take by weighing 1.0 g polyvinylpyrrolidones (PVP) and 1.40 g softex kws respectively and be dissolved in the above-mentioned solution, be stirred to dissolving fully.Measure 5.80 ml tetraethoxysilanes and slowly pouring in the above-mentioned solution, the powerful stirring 24 hours, the white suspension-turbid liquid that obtains is transferred in the water heating kettle that 200 ml have polytetrafluoroethylene ethene liner, in 150
oC thermostatted water heat treatment 12 hours.Naturally cooled liquid cleans and suction filtration 5 times repeatedly through alcohol and deionized water, and the white powder that obtains is dispersed in the beaker of 120 ml, powerful 30 min that stir.Take by weighing 1.0 g sucrose and be dissolved in the above-mentioned suspension-turbid liquid, be stirred to fully and carry out rotary evaporation after the dissolving, rotary speed is 100 rpm, and the waters temperature is 90
oC obtains white presoma product, and the presoma product is warming up to 800 under argon gas atmosphere
oC is incubated 1 h, cools to room temperature with the furnace and makes the inferior silicon-carbon composite cathode material powder of mesoporous oxidation.The 70 wt.% mesopore silicon oxide/carbon composites that make, the acetylene black of 15 wt.% and the CMC of 15 wt.% are mixed, make slurry, evenly be coated on the Copper Foil, be stamped into the circular electrode pole piece behind the vacuum drying, be to electrode with lithium metal, 1 mol/L LiPF
6/ EMC+DMC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, the charging/discharging voltage scope is 0.01 ~ 2.5 V, the result shows, it has better electrochemical performance, 0.1 under the current density of A/g, first discharge specific capacity is 1020 mAh/g, enclosed pasture efficient is 60 % first, circulating, the specific capacity of material only is 430 mAh/g after 100 times, and the chemical property of material is relatively poor.
Embodiment 5:
Take by weighing 0.46 g dissolution of sodium hydroxide in 120 ml deionized waters, be stirred to dissolving fully; (PVP K30) is dissolved in the above-mentioned solution with 1.40 g softex kws, is stirred to dissolving fully to take by weighing 1.0 g polyvinylpyrrolidones respectively.Measure 5.80 ml tetraethoxysilanes and slowly pouring in the above-mentioned solution, the powerful stirring 24 hours, the white suspension-turbid liquid that obtains is transferred in the water heating kettle that 200 ml have polytetrafluoroethylene ethene liner, in 80
oC thermostatted water heat treatment 48 hours.Naturally cooled liquid cleans and suction filtration 5 times repeatedly through alcohol and deionized water, and the white powder that obtains is dispersed in the beaker of 120 ml, powerful 30 min that stir.The suspension that this is scattered is rotated evaporation, and rotary speed is 100 rpm, and the waters temperature is 90
oC obtains white presoma product, and the presoma product is warming up to 800 under argon gas atmosphere
oC is incubated 1 h, cools to room temperature with the furnace and makes the inferior silicon-carbon composite cathode material powder of mesoporous oxidation.The 70 wt.% mesopore silicon oxide/carbon composites that make, the acetylene black of 15 wt.% and the CMC of 15 wt.% are mixed, make slurry, evenly be coated on the Copper Foil, be stamped into the circular electrode pole piece behind the vacuum drying, be to electrode with lithium metal, 1 mol/L LiPF
6/ EMC+DMC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, the charging/discharging voltage scope is 0.01 ~ 2.5 V, the result shows, it has better electrochemical performance, 0.1 under the current density of A/g, first discharge specific capacity is 970 mAh/g, and enclosed pasture efficient is 58 % first, and circulating, the specific capacity of material is 429 mAh/g after 100 times.The chemical property of material is relatively poor.
Embodiment 6:
Take by weighing 0.46 g dissolution of sodium hydroxide in 120 ml deionized waters, be stirred to dissolving fully; Take by weighing 1.0 g polyvinylpyrrolidones (PVP) and 1.40 g softex kws respectively and be dissolved in the above-mentioned solution, be stirred to dissolving fully.Measure 5.80 ml tetraethoxysilanes and slowly pouring in the above-mentioned solution, the powerful stirring 24 hours, the white suspension-turbid liquid that obtains is transferred in the water heating kettle that 200 ml have polytetrafluoroethylene ethene liner, in 80
oC thermostatted water heat treatment 48 hours.Naturally cooled liquid cleans and suction filtration 5 times repeatedly through alcohol and deionized water, and the white powder that obtains is dispersed in the beaker of 120 ml, powerful 30 min that stir.Take by weighing 1.0 g sucrose and be dissolved in the above-mentioned suspension-turbid liquid, be stirred to fully and carry out rotary evaporation after the dissolving, rotary speed is 100 rpm, and the waters temperature is 90
oC obtains white presoma product, and the presoma product is warming up to 1200 under nitrogen atmosphere
oC is incubated 5 h, cools to room temperature with the furnace and makes the inferior silicon-carbon composite cathode material powder of mesoporous oxidation.The 70 wt.% mesopore silicon oxide/carbon composites that make, the acetylene black of 15 wt.% and the CMC of 15 wt.% are mixed, make slurry, evenly be coated on the Copper Foil, be stamped into the circular electrode pole piece behind the vacuum drying, be to electrode with lithium metal, 1 mol/L LiPF
6/ EMC+DMC+EC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, the charging/discharging voltage scope is 0.01 ~ 2.5 V, the result shows, it has better electrochemical performance, 0.1 under the current density of A/g, first discharge specific capacity is 1020 mAh/g, enclosed pasture efficient is 60 % first, circulating, the specific capacity of material is 490 mAh/g after 100 times, and the chemical property of material is relatively poor.
Claims (7)
1. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of a lithium ion battery, it is characterized in that: composite negative pole material is to be made of two kinds of components of SiOx, C, and the quality percentage composition of C in the SiOx/C composite negative pole material is 1 ~ 30%, and processing step is:
(1) with polyvinylpyrrolidone (PVP) as the auxiliary template agent, be dissolved in a certain amount of sodium hydrate aqueous solution, be stirred to fully dissolving;
(2) agent joins above-mentioned making in the settled solution as template with organic surface active agent, and brute force is stirred to dissolving fully;
(3) the organosilicon source is joined in the solution that described step (2) makes powerful the stirring 24 hours;
(4) solution that described step (3) is made moves on in the band teflon-lined water heating kettle of a constant volume, 50-150 in insulating box
oReact 12 ~ 48 h under the C, obtain mesopore silicon oxide white presoma;
(5) after the repeatedly washing and suction filtration of white powder through ethanol and deionized water that step (4) is made, join in a certain amount of deionized water, brute force is stirred to even dispersion;
(6) carbon source is joined in the solution that step (5) makes, brute force is stirred to carbon source and fully dissolves;
(7) aforesaid liquid is rotated dry processing of evaporation bag carbon; Temperature is 90
oC, rotating speed are 90-100 rmp;
(8) under the inertia protective atmosphere, with the powder of step (7) gained with 5
oC/min speed is warming up to 800 ~ 1200
oC insulation 1 ~ 5 hour, temperature programmed control cools off or cools to room temperature with the furnace then, can obtain mesoporous SiOx/C composite material.
2. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of lithium ion battery according to claim 1, it is characterized in that: in the described step (1), the addition that is formulated as NaOH of sodium hydrate aqueous solution is 2.5-4.0 mg/ml; Described polyvinylpyrrolidone, its addition that joins in the sodium hydrate aqueous solution is 5.0-12.0 mg/ml.
3. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of lithium ion battery according to claim 1, it is characterized in that: the surfactant in the step (2) is one or more in DTAB, softex kw (CTAB), octadecyl trimethylammonium bromide, poly(ethylene oxide), the myristyl betaine (TB); The addition of surfactant is 8.0-12 mmol/L.
4. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of lithium ion battery according to claim 1, it is characterized in that: the silicon source in the step (3) is methyl silicate or tetraethoxysilane (TEOS); Silicon source addition is 0.02-0.05 mol/L.
5. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of lithium ion battery according to claim 1, it is characterized in that: the hydrothermal temperature in the step (4) is 50-150
oC.
6. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of lithium ion battery according to claim 1, it is characterized in that: the described carbon source of step (6) is sucrose, the sucrose addition is the theoretical 0-30% that generates the silicon dioxide quality in organosilicon source.
7. the preparation method of the inferior silicon-carbon composite cathode material of the mesoporous oxidation of lithium ion battery according to claim 1, it is characterized in that: the described inertia protective atmosphere of step (8) is one or both in nitrogen, the argon gas, and calcinating system is with 5
oC/min speed is warming up to 800 ~ 1200
oC insulation 1 ~ 5 hour.
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