CN108269989A - A kind of carbon coating micron silicon, preparation method and application - Google Patents
A kind of carbon coating micron silicon, preparation method and application Download PDFInfo
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Abstract
The invention discloses one kind to belong to technical field of preparation for inorganic material, more particularly, to a kind of carbon coating micron silicon, preparation method and application.By magnesium silicide is reacted in the atmosphere containing carbon dioxide with carbon dioxide or magnesium silicide decompose after react with carbon dioxide, then carbon-coated micron silicon materials are obtained by pickling, preparation method is simple and practicable, production available for extensive carbon coating micron silicon, thus the technical issues of solving that prior art carbon coating micron silicon material preparation process is complicated, safety is poor, being unfavorable for large-scale production and application.
Description
Technical field
The invention belongs to technical field of preparation for inorganic material, more particularly, to a kind of carbon coating micron silicon, its preparation side
Method and application.
Background technology
In recent years, with the development of new energy technology, electronic equipment develops towards Intellectualized lightweight direction, to battery skill
The requirement of art is higher and higher, and the capacity of battery is high, and chemical property will be stablized.Therefore high specific energy lithium ion battery industry is met the tendency of
And it gives birth to.And the negative material used in lithium ion battery is one of key factor for determining its performance.At present, negative electrode of lithium ion battery
Material is mainly carbon material and non-carbon material, and in non-carbons negative material, silicon materials are since it is with high theoretical storage lithium appearance
It measures (4200mA h/g), is 11 times of commercial graphite cathode theoretical capacity, and the voltage platform of Si is slightly above graphite, is charging
The phenomenon that Shi Buyi causes surface to analyse lithium, security performance are high.But silicon is faced as semi-conducting material in lithium ion battery
It is the problem of poorly conductive is poor, and when removal lithium embedded occurs in charge and discharge process for silicon materials can be along with serious volume expansion
(volume change is between 300%-400%).These seriously affect the coulombic efficiency and stable circulation of battery, hinder its quotient
The development of industry.
Silicon materials problem encountered in lithium ion battery is solved, generally using compound method.Existing market or
The silicon-carbon cathode mainly reported in document is simply mixed or for nano-silicon and graphite after nano-silicon is attached to graphite surface,
Certain subsequent processing is carried out again.But this still unavoidable expansion for leading to electrode entirety by electrode material expansion, so as to band
Carry out safety accident.Such as：CN103474667A discloses a kind of Si-C composite material composite material and preparation method thereof, using receiving
Rice silicon adds graphite to be mixed, and then CVD coats one layer of carbon, then one layer of carbon of liquid phase coating, finally crushes and obtains final product,
Although the material that this method obtains has good cycle performance and high rate performance, preparation process is complicated, of high cost, uncomfortable
Close industrialized production.For another example patent " a kind of low thermal expansion porous silicon/graphite combination electrode material and preparation method thereof "
(CN106784743A), the method for having used removal alloying obtains porous silicon, then carry out again carbon coating or directly with commercialization
Graphite cathode is mixed to get final porous silicon/graphite composite material, but the method for chemical attack that the removal alloying used is,
And carbon coating process increases preparation process, limits its commercial Application.A kind of for another example patent " compound carbon-coated porous silicon
Negative material and preparation method thereof " (CN106935834A) is used based on the porous silicon of removal alloying, by graphene with
The compound carbon-coating cladding that high density carbon combines or low density carbon is combined with high density carbon, reaches double-deck carbon coating, finally obtains
Product there is good cycle performance, but the obtained Si-C composite material of this method needs to carry out packet carbon process twice, system
Standby program is cumbersome, and removal alloying is unfavorable for industrialized production using the method for chemical attack；Document " Facile
synthesis of Si nanoparticles using magnesium silicide reductionand its
Carbon composite as a high-performance anode for Li ion batteries " are reported by quotient
The SiO of industry2With Mg2Porous silicon is obtained by the reaction in Si, is then mixed with PVA, and the silicon-carbon that carbon coating porous silicon is obtained by the reaction after carbonization is answered
Condensation material, obtained Si-C composite material have good cycle performance, but to be used when washing reaction product HCl and
HF, corrosivity is big, is unfavorable for industrialized production.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of carbon-coated multi-pore micron silicon,
Preparation method and application, its object is to by the way that magnesium silicide oxygen occur with carbon dioxide in the atmosphere containing carbon dioxide
It reacts after changing reduction reaction or magnesium silicide decomposition with carbon dioxide, carbon-coated micron silicon material is then obtained by pickling
Material, preparation method is simple and practicable, available for the production of extensive carbon coating micron silicon, thus solves prior art carbon coating micron
Silicon materials preparation process is complicated, safety is poor, the technical issues of being unfavorable for large-scale production and application.
To achieve the above object, one side according to the invention provides a kind of preparation method of carbon coating micron silicon,
It is characterised in that it includes following steps：
(1) it using magnesium silicide as raw material, reacts in the atmosphere containing carbon dioxide in 400~800 DEG C 2~24 small
When, obtain the crude product containing magnesia and carbon-coated silicon；The atmosphere containing carbon dioxide for carbon dioxide atmosphere or
The mixed atmosphere of carbon dioxide and inert gas；
(2) step (1) crude product is subjected to pickling processes, to remove magnesia and remaining silication magnesium raw material, obtained
To carbon-coated three-dimensional perforation multi-pore micron silicon.
Preferably, the grain size of step (1) described magnesium silicide is 0.2~10 micron.
Preferably, step (1) the silication magnesium raw material obtains as follows：By business silicon particle and magnesium powder according to matter
Measure ratio 1:1.5~2 mixing in 400~700 DEG C under inert gas shielding, are reacted 4~12 hours, after obtained product cooling
It carries out ball milling and obtains the silication magnesium raw material.
Preferably, the flow velocity of gas is 30ml/min~100ml/ in the atmosphere containing carbon dioxide described in step (1)
Min, the volumetric concentration of carbon dioxide is not less than 10% in the atmosphere.
Preferably, step (1) the silication magnesium raw material is placed in the U-shaped casing placed in opposite directions, to increase carbon dioxide
Residence time.
Preferably, the U-shaped casing is two, and the openend of the U casings is inside, and closed end is outside.
Other side according to the invention provides a kind of carbon coating multi-pore micron silicon, according to the preparation method system
It is standby to obtain.
Preferably, the carbon coating multi-pore micron silicon, is carbon-coated multi-pore micron silicon, and the size of the micron silicon is
1~3 micron, the thickness of the carbon-coating is 10nm~30nm, the specific surface area of the carbon coating multi-pore micron silicon for 20~
100m2/g。
Preferably, the carbon coating multi-pore micron silicon, carbon content are 10wt%~20wt%, and surplus is silicon.
Other side according to the invention provides a kind of application of the carbon coating multi-pore micron silicon, for making
Standby lithium ion battery negative material.
In general, by the above technical scheme conceived by the present invention compared with prior art, it can obtain down and show
Beneficial effect：
(1) the present invention provides a kind of preparation method of carbon coating micron silicon, by the way that magnesium silicide is being contained titanium dioxide
It reacts after redox reaction or magnesium silicide decomposition occurs with carbon dioxide in the atmosphere of carbon with carbon dioxide, Ran Houtong
Overpickling obtains carbon-coated micron silicon materials, and preparation method is simple and practicable, the production available for extensive carbon coating micron silicon.
(2) present invention in the preparation process of carbon coating micron silicon by controlling the flow velocity of carbon dioxide, concentration, reaction temperature
The conditions such as degree, while the improvement of complex reaction device extend the residence time of carbon dioxide, promote carbon dioxide and reaction raw materials
Contact, considerably increase the yields of carbon coating micron silicon materials.
(3) atmosphere used in preparation process of the present invention in carbon coating micron silicon is GHG carbon dioxide, can realize CO2
Efficiently, high value utilizes, at low cost, can realize energy-saving and emission-reduction.
(4) silicon carbon material prepared by the present invention is three-dimensional perforation multi-pore micron, and structure not only improves electrode material and electrolysis
The contact of liquid also alleviates electrode material and expands outward, improves the stability of lithium ion battery, the carbon coating knot being additionally formed
Structure also greatly improves the electric conductivity of electrode material, is more advantageous to the conduction of electronics.
Description of the drawings
Fig. 1 is 1 reaction unit illustraton of model of embodiment；
Fig. 2 is 1 magnesium silicide of embodiment in 700 DEG C and CO2The XRD diagram of reaction product；
Fig. 3 is that the scanning electron microscope (SEM) photograph that carbon coating three-dimensional penetrates through multi-pore micron silicon is prepared in embodiment 1；
Fig. 4 is that the transmission electron microscope picture that carbon coating three-dimensional penetrates through multi-pore micron silicon is prepared in embodiment 1；
Fig. 5 is that the cycle performance figure that carbon coating three-dimensional penetrates through multi-pore micron silicon is prepared in embodiment 1.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The present invention provides a kind of preparation methods of carbon coating micron silicon, include the following steps：
(1) it using magnesium silicide as raw material, reacts in the atmosphere containing carbon dioxide in 400~800 DEG C 2~24 small
When, obtain the crude product containing magnesia and carbon-coated silicon；Atmosphere containing carbon dioxide is carbon dioxide atmosphere or dioxy
Change the mixed atmosphere of carbon and inert gas.Using magnesium silicide as raw material, the reaction that occurs in the atmosphere containing carbon dioxide can be with
For magnesium silicide and the redox reaction Mg of carbon dioxide2Si+CO2→Si+2MgO+C；When temperature is increased to 750 DEG C or more,
It may also happen that the decomposition reaction of magnesium silicide, generates magnesium vapor and elementary silicon, and magnesium vapor may be further anti-with carbon dioxide
Magnesia and carbon should be generated, what it is due to generation is reaction in-situ, and the surface for reacting the silicon of generation has coated one layer of carbon-coating.Silicon
Change ranging from 0.2~10 micron of the preferable particle size of magnesium.
One of difficult point present in the preparation process of carbon coating micron silicon of the present invention is to need to control to be passed through CO2Rate,
It is passed through CO2Rate is too fast to lead to extra CO2It is reacted with generated in-situ C, causes the consumption of C in situ, while generated toxic
CO；The flow velocity of suitable gas is 30ml/min~100ml/min in atmosphere of the present invention containing carbon dioxide, dioxy in atmosphere
The volumetric concentration for changing carbon cannot be below 10%.
The preparation of carbon coating micron silicon of the present invention can carry out in tube furnace, but how allow Mg2Si and CO2Fully connect
It touches, them is made to react more complete, to increase the conversion ratio and yield of reaction, the present invention is improved reaction unit, magnesium silicide
Raw material is placed in the U-shaped casing that opposition is placed in opposite directions, to increase the residence time of carbon dioxide, improves magnesium silicide and carbon dioxide
Touch opportunity, U-shaped casing can be two or more, and the openend of U casings is inside, and closed end is outside.
The selection of reaction temperature of the present invention is also very crucial, and temperature is too low, and reaction is insufficient；Temperature is excessively high, and there will be dephasigns
(mainly SiC) is generated, and influences the purity of product, and suitable temperature range is 400~800 DEG C.
(2) step (1) crude product is subjected to pickling processes, to remove magnesia and remaining silication magnesium raw material, obtained
To carbon-coated three-dimensional perforation multi-pore micron silicon.
The present invention passes through the integrated artistic flow and the Parameter Conditions of each reaction step to silicon-carbon key preparation method
Etc. being improved, compared with prior art, the outstanding advantages for having preparation method simple and practicable, it is only necessary to by magnesium silicide in CO2
(or CO2With the mixed gas of inert gas) in directly heat and can obtain a large amount of carbon coating three-dimensionals perforation multi-pore micron silicon,
Yield is up to more than 70%.
A kind of carbon coating multi-pore micron silicon being prepared according to the method described above, for carbon-coated multi-pore micron silicon, institute
It is 1~3 micron to state the size of micron silicon, and the thickness of the carbon-coating is 10nm~30nm, the ratio of the carbon coating multi-pore micron silicon
Surface area is 20~100m2/g.Carbon content is 10~20wt%, and surplus is silicon.The carbon coating multi-pore micron silicon can be used as lithium from
Sub- cell negative electrode material, it is demonstrated experimentally that the carbon coating multi-pore micron silicon that the present invention is prepared is used as negative electrode of lithium ion battery
Material, carbon coating structure not only improve contact of the electrode material with electrolyte, also alleviate electrode material and expand outward, improve
The stability of lithium ion battery, the carbon coating structure being additionally formed also greatly improve the electric conductivity of electrode material, more have
Conducive to the conduction of electronics, excellent performance is shown as battery material.
It is embodiment below：
Embodiment 1
(1) by business silicon particle and magnesium powder in mass ratio 1：1.8 be uniformly mixed be put into container；
(2) container equipped with reactant is put into the high temperature furnace full of inert gas and is added with the heating rate of 5 DEG C/min
For heat to 700 DEG C, soaking time obtains product magnesium silicide for 6h, is taken out after product cools to room temperature with the furnace；
(3) products therefrom in (2) is put into the ball grinder of argon gas protection and carries out ball milling, then screened, obtained not
With the magnesium silicide micron particles of size, granular size is 0.2-10 microns.
(4) the good magnesium silicide 2g of ball milling in (3) is placed in tube furnace, as shown in FIG. 1, FIG. 1 is tube furnaces for specific device
Mounted cast figure, the crucible for filling sample are entangled by two U-shaped stainless steels, increase sample and CO2Reaction, make reaction more thorough.
700 DEG C of reaction temperatures are heated in carbon dioxide atmosphere, keep the temperature 3h, the flow velocity of carbon dioxide is 50ml/min, treats product with stove
It is taken out after being cooled to room temperature；
(5) will after the chlorohydric acid pickling of products therefrom in (4) removes magnesia and the complete magnesium silicide of unreacted, cleaning, filtering,
Carbon coating three-dimensional perforation multi-pore micron silicon is obtained after drying.
By sample XRD diffracting spectrums after being reacted in Fig. 2 it is found that in 28.4 °, 47.3 ° and 56.1 ° of three strongest peak and silicon
The three strongest peak of (JCPDS No.27-1402) is corresponding, the dephasign Mg complete for unreacted2The Si and MgO of generation, is easily removed.
By scanning electron microscope (SEM) photograph and Fig. 4 (including Fig. 4 A, Fig. 4 B) transmission electron microscope pictures of Fig. 3 (including Fig. 3 A, Fig. 3 B) it is found that originally
The final product that embodiment is prepared penetrates through multi-pore micron silicon structure for carbon coating three-dimensional.It follows that products therefrom is tool
Micron particles of Nano grade pore space structure (acid etching technique falls what is formed after MgO) and be that silicon-carbon production is prepared in a step
Object.It is 70.1% that carbon coating micron silicon yield, which is prepared, in the present embodiment, and the size of micron silicon is 1~3 micron, the thickness of carbon-coating
For 20nm, specific surface area 31.2m2/ g, carbon content 14wt%, surplus are silicon.
Fig. 5 is the cycle performance that carbon coating three-dimensional penetrates through porous silicon, carbon coating three-dimensional perforation multi-pore micron after recycling 400 times
The capacity of silicon is 79% up to 1000mA h/g, for the first time coulombic efficiency, shows prominent cyclical stability.
Embodiment 2
(1) by business silicon particle and magnesium powder in mass ratio 1：1.5 be uniformly mixed be put into container；
(2) container equipped with reactant is put into the high temperature furnace full of inert gas and is added with the heating rate of 5 DEG C/min
For heat to 400 DEG C, soaking time obtains product magnesium silicide for 12h, is taken out after product cools to room temperature with the furnace；
(3) products therefrom in (2) is put into the ball grinder of argon gas protection and carries out ball milling, then screened, obtained not
With the magnesium silicide micron particles of size, granular size is 1-8 microns.
(4) the good magnesium silicide 2g of ball milling in (3) is placed in tube furnace, as shown in FIG. 1, FIG. 1 is tube furnaces for specific device
Mounted cast figure, the crucible for filling sample are entangled by two U-shaped stainless steels, increase sample and CO2Reaction, make reaction more thorough.
750 DEG C of reaction temperatures are heated in carbon dioxide atmosphere, keep the temperature 3h, the flow velocity of carbon dioxide is 30ml/min, treats product with stove
It is taken out after being cooled to room temperature；
(5) after products therefrom in (4) being removed magnesia with chlorohydric acid pickling, carbon coating three is obtained after cleaning, filtering, drying
Dimension perforation multi-pore micron silicon.
Products therefrom is the micron particles with Nano grade pore space structure and is that silicon-carbon product is prepared in a step.This
It is 71.6% that carbon coating micron silicon yield, which is prepared, in embodiment, and the size of micron silicon is 3~4 microns, and the thickness of carbon-coating is
15nm, specific surface area 28.6m2/ g, carbon content 12wt%, surplus are silicon.
Embodiment 3
(1) by business silicon particle and magnesium powder in mass ratio 1：2 be uniformly mixed be put into container；
(2) container equipped with reactant is put into the high temperature furnace full of inert gas and is added with the heating rate of 5 DEG C/min
For heat to 600 DEG C, soaking time obtains product magnesium silicide for 4h, is taken out after product cools to room temperature with the furnace；
(3) products therefrom in (2) is put into the ball grinder of argon gas protection and carries out ball milling, then screened, obtained not
With the magnesium silicide micron particles of size, granular size is 0.5-4 microns.
(4) the good magnesium silicide 2g of ball milling in (3) is placed in tube furnace, as shown in FIG. 1, FIG. 1 is tube furnaces for specific device
Mounted cast figure, the crucible for filling sample are entangled by two U-shaped stainless steels, increase sample and CO2Reaction, make reaction more thorough.
Person is heated to 800 DEG C of reaction temperatures in carbon dioxide atmosphere, keeps the temperature 3h, and the flow velocity of carbon dioxide is 100ml/min, treat product with
Stove takes out after being cooled to room temperature；
(5) after products therefrom in (4) being removed magnesia with chlorohydric acid pickling, carbon coating three is obtained after cleaning, filtering, drying
Dimension perforation multi-pore micron silicon.
Gained final product is the micron particles with Nano grade pore space structure and is that silicon-carbon production is prepared in a step
Object.It is 73.3% that carbon coating micron silicon yield, which is prepared, in the present embodiment, and the size of micron silicon is 1~3 micron, the thickness of carbon-coating
For 12nm, specific surface area 24m2/ g, carbon content 10wt%, surplus are silicon.
Embodiment 4
(1) by business silicon particle and magnesium powder in mass ratio 1：1.8 be uniformly mixed be put into container；
(2) container equipped with reactant is put into the high temperature furnace full of inert gas and is added with the heating rate of 5 DEG C/min
For heat to 700 DEG C, soaking time obtains product magnesium silicide for 6h, is taken out after product cools to room temperature with the furnace；
(3) products therefrom in (2) is put into the ball grinder of argon gas protection and carries out ball milling, then screened, obtained not
With the magnesium silicide micron particles of size, granular size is 0.2-10 microns.
(4) the good magnesium silicide 2g of ball milling in (3) is placed in tube furnace, as shown in FIG. 1, FIG. 1 is tube furnaces for specific device
Mounted cast figure, the crucible for filling sample are entangled by two U-shaped stainless steels, increase sample and CO2Reaction, make reaction more thorough.
700 DEG C of reaction temperatures are heated in the mixed atmosphere of carbon dioxide and argon gas, keep the temperature 3h, the gas flow rate of wherein carbon dioxide is
20ml/min, the gas flow rate of argon gas is 30ml/min, is taken out after product cools to room temperature with the furnace；
(5) will after the chlorohydric acid pickling of products therefrom in (4) removes magnesia and the complete magnesium silicide of unreacted, cleaning, filtering,
Carbon coating three-dimensional perforation multi-pore micron silicon is obtained after drying.
Gained final product is the micron particles with Nano grade pore space structure and is that silicon-carbon production is prepared in a step
Object.It is 74.9% that carbon coating micron silicon yield, which is prepared, in the present embodiment, and the size of micron silicon is 1~3 micron, the thickness of carbon-coating
For 10nm, specific surface area 20m2/ g, carbon content 8wt%, surplus are silicon.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of carbon coating micron silicon, which is characterized in that include the following steps：
(1) it using magnesium silicide as raw material, reacts 2~24 hours, obtains in 400~800 DEG C in the atmosphere containing carbon dioxide
To the crude product containing magnesia and carbon-coated silicon；The atmosphere containing carbon dioxide is carbon dioxide atmosphere or titanium dioxide
The mixed atmosphere of carbon and inert gas；
(2) step (1) crude product is subjected to pickling processes, to remove magnesia and remaining silication magnesium raw material, obtains carbon
The three-dimensional perforation multi-pore micron silicon of cladding.
2. preparation method as described in claim 1, which is characterized in that the grain size of step (1) described magnesium silicide is micro- for 0.2~10
Rice.
3. preparation method as described in claim 1, which is characterized in that step (1) the silication magnesium raw material is as follows
It obtains：By business silicon particle and magnesium powder according to mass ratio 1:1.5~2 mixing, in 400~700 DEG C under inert gas shielding, instead
It answers 4~12 hours, carrying out ball milling after obtained product cooling obtains the silication magnesium raw material.
4. preparation method as described in claim 1, which is characterized in that gas in the atmosphere containing carbon dioxide described in step (1)
The flow velocity of body is 30ml/min~100ml/min, and the volumetric concentration of carbon dioxide is not less than 10% in the atmosphere.
5. preparation method as described in claim 1, which is characterized in that step (1) the silication magnesium raw material is placed in opposite placement
U-shaped casing in, to increase the residence time of carbon dioxide.
6. preparation method as claimed in claim 5, which is characterized in that the U-shaped casing is two, and the U casings
Openend is inside, and closed end is outside.
7. a kind of carbon coating multi-pore micron silicon, which is characterized in that according to the preparation method as described in claim 1~6 any one
It is prepared.
8. carbon coating multi-pore micron silicon as claimed in claim 7, which is characterized in that it is carbon-coated multi-pore micron silicon, institute
It is 1~3 micron to state the size of micron silicon, and the thickness of the carbon-coating is 10nm~30nm, the ratio of the carbon coating multi-pore micron silicon
Surface area is 20~100m2/g。
9. carbon coating multi-pore micron silicon as claimed in claim 7, which is characterized in that carbon content is 10wt%~20wt%, remaining
It measures as silicon.
10. the application of a kind of carbon coating multi-pore micron silicon as described in claim 7~9 any one, which is characterized in that be used for
Prepare lithium ion battery negative material.
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| CN110589831A (en) * | 2019-08-26 | 2019-12-20 | 浙江工业大学 | Method for preparing silicon/silicon carbide material at low temperature |
| CN111162266A (en) * | 2020-03-02 | 2020-05-15 | 山东大学 | Carbon-coated two-dimensional silicon and preparation method and application thereof |
| CN111211306A (en) * | 2020-01-14 | 2020-05-29 | 山东大学 | MXene @ carbon @ porous silicon material and preparation method and application thereof |
| CN111477849A (en) * | 2020-04-14 | 2020-07-31 | 厦门理工学院 | Preparation method of porous Si/SiC/C material and negative electrode material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2358042Y (en) * | 1997-11-05 | 2000-01-12 | 梁双林 | Carbon dioxide generator |
| US20040146453A1 (en) * | 2003-01-24 | 2004-07-29 | Bailey Wade H. | Process for the synthesis of BrSF5 |
| CN202582331U (en) * | 2012-04-18 | 2012-12-05 | 南京斯迈柯特种金属装备股份有限公司 | Corrosion-resistant titanium U-shaped pipe heat exchanger pipe plate structure |
| CN104986768A (en) * | 2015-05-18 | 2015-10-21 | 中国科学技术大学 | Method for synthesizing silicon nanopowder through nitridation, and application thereof |
| CN105826527A (en) * | 2016-03-22 | 2016-08-03 | 浙江大学 | Porous silicon-carbon composite material and preparation method and application thereof |
-
2018
- 2018-02-09 CN CN201810135903.9A patent/CN108269989B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2358042Y (en) * | 1997-11-05 | 2000-01-12 | 梁双林 | Carbon dioxide generator |
| US20040146453A1 (en) * | 2003-01-24 | 2004-07-29 | Bailey Wade H. | Process for the synthesis of BrSF5 |
| CN202582331U (en) * | 2012-04-18 | 2012-12-05 | 南京斯迈柯特种金属装备股份有限公司 | Corrosion-resistant titanium U-shaped pipe heat exchanger pipe plate structure |
| CN104986768A (en) * | 2015-05-18 | 2015-10-21 | 中国科学技术大学 | Method for synthesizing silicon nanopowder through nitridation, and application thereof |
| CN105826527A (en) * | 2016-03-22 | 2016-08-03 | 浙江大学 | Porous silicon-carbon composite material and preparation method and application thereof |
Cited By (19)
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| CN110589831B (en) * | 2019-08-26 | 2021-10-15 | 浙江工业大学 | Method for preparing silicon/silicon carbide material at low temperature |
| CN110589831A (en) * | 2019-08-26 | 2019-12-20 | 浙江工业大学 | Method for preparing silicon/silicon carbide material at low temperature |
| EP4051634A4 (en) * | 2019-10-29 | 2024-04-17 | Battelle Memorial Institute | Stabilized porous silicon structure for highly stable silicon anode and methods of making |
| CN112094105A (en) * | 2020-01-10 | 2020-12-18 | 武汉科技大学 | Low-carbon magnesia carbon brick and preparation method thereof |
| CN112094124A (en) * | 2020-01-10 | 2020-12-18 | 武汉科技大学 | Carbon source for refractory material and preparation method thereof |
| CN111211306A (en) * | 2020-01-14 | 2020-05-29 | 山东大学 | MXene @ carbon @ porous silicon material and preparation method and application thereof |
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| CN111477849A (en) * | 2020-04-14 | 2020-07-31 | 厦门理工学院 | Preparation method of porous Si/SiC/C material and negative electrode material |
| CN111477849B (en) * | 2020-04-14 | 2021-08-17 | 厦门理工学院 | Preparation method of porous Si/SiC/C material and negative electrode material |
| CN111584838A (en) * | 2020-05-06 | 2020-08-25 | 厦门大学 | Porous silicon/silicon-carbon composite material and preparation method and application thereof |
| CN111584838B (en) * | 2020-05-06 | 2021-03-16 | 厦门大学 | Porous silicon/silicon-carbon composite material and preparation method and application thereof |
| CN113725409A (en) * | 2021-07-29 | 2021-11-30 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode material and preparation method thereof |
| CN114050251A (en) * | 2021-11-18 | 2022-02-15 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
| CN114050251B (en) * | 2021-11-18 | 2024-01-19 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
| CN114094087A (en) * | 2021-11-25 | 2022-02-25 | 武汉科技大学 | Externally coated porous silicon material, preparation method and application thereof |
| CN114105145A (en) * | 2021-11-25 | 2022-03-01 | 武汉科技大学 | Carbon-coated three-dimensional porous silicon negative electrode material and preparation method and application thereof |
| CN114105145B (en) * | 2021-11-25 | 2023-10-10 | 武汉科技大学 | Carbon-coated three-dimensional porous silicon anode material and preparation method and application thereof |
| CN114094087B (en) * | 2021-11-25 | 2024-03-05 | 武汉科技大学 | Externally coated porous silicon material, preparation method and application thereof |
| CN114477184A (en) * | 2022-01-12 | 2022-05-13 | 浙江工业大学 | Preparation method of silicon carbide powder |
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Application publication date: 20180710 Assignee: Hubei Benxing Carbon Material Co.,Ltd. Assignor: WUHAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2022420000139 Denomination of invention: Carbon coated micro silicon, its preparation method and application Granted publication date: 20200428 License type: Exclusive License Record date: 20221206 |