CN107611416A - A kind of Si-C composite material, its preparation method and application - Google Patents
A kind of Si-C composite material, its preparation method and application Download PDFInfo
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- CN107611416A CN107611416A CN201710697692.3A CN201710697692A CN107611416A CN 107611416 A CN107611416 A CN 107611416A CN 201710697692 A CN201710697692 A CN 201710697692A CN 107611416 A CN107611416 A CN 107611416A
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Abstract
The invention discloses a kind of Si-C composite material, its preparation method and application, this method comprises the following steps：The homogeneously mixed product of glass and carbon material will be obtained after glass powder and lamella carbon material wet ball grinding, ingot is compacted after uniformly being mixed with magnesium powder, fused salt, generation magnesium thermit, reaction product pickling processes are obtained into sandwich-like porous silicon/class graphene-structured composite.The inventive step is simple and easy, raw material sources are extensive, above all through compacting process, after mixture making ingot, magnesium thermit is carried out again, considerably increase the tap density of silicon-carbon cathode material, improve the volume and capacity ratio of negative material, the electronic conductivity of material is also effectively improved with compound rear similar sandwich structures formed of carbon material such as graphite simultaneously, improve the compatibility of silica-base material and electrolyte, so as to improve the cycle performance of material and high rate performance, it can be applied to the lithium ion battery negative material of high power density and high-energy-density.
Description
Technical field
The invention belongs to lithium ion battery negative material field, more particularly, to a kind of Si-C composite material, its preparation
Methods and applications.
Background technology
Important energy storage device of the lithium ion battery due to having become mobile electronic device with high energy density, so
And should have higher specific capacity, energy compared to conventional batteries applied to the novel battery in emerging electric transportation system
Density and more preferable cycle life.In numerous lithium ion battery negative materials, silicon due to abnormal high specific capacity,
The reserves and the advantage of the manufacturing industry industrialization infrastructure of prosperity enriched in the earth's crust, are considered as most promising material.
The research history that silicon is used for lithium ion battery alreadys exceed 30 years, but the rapid decay of the mechanical crushing of silicon materials and capacity is tight
Its cycle performance is have impact on again, thus limits practical application of the silicon materials in lithium ion battery.Although carbon material specific capacity
It is not high but be thus main negative material in the market with extremely stable cycle characteristics.Carbon material has higher electricity
Electron conductivity, preferable electron channel is provided for composite；Silicon materials volume shape can be relaxed after carbon and silicon materials are compound simultaneously
Become the stress variation brought.The two is combined and prepares height ratio capacity and the lithium ion battery of long-life silicon/carbon compound cathode material
Material receives more and more attention.
At present Si-C composite material mainly have cladded type and embedded type both.The Si-C composite material of cladded type is in silicon
One layer of carbon of Surface coating, so as to play a part of buffer silicon bulk effect caused by phase transformation and provide electron propagation ducts.
Different from the structure that carbon is compound according to silicon, cladded type Si-C composite material can be divided into three kinds of hud typed, fibrous type and porous type again；
Active silicon grain is embedded into the Si-C composite material that embedded type has just been obtained in structural conductive carbon base body.But these are made at present
The method of standby Si-C composite material, not only condition is harsh, costly, and step is complicated, and it is seriously polluted, be related to it is many poisonous
It is material, larger to people's harmfulness.Such as in document " preparation method of silicon-carbon cathode material " (CN104103821A), changing first
Learn and catalyst is placed in phase depositing reaction chamber；Heating chemical phase depositing reaction chamber, toward chemical vapor deposition reaction chamber in lead to
Enter reacting gas source and carrier gas, the process carboxylated that caused Si-SiOx in chemical gas phase reaction process is passed through into dynamic rotary
The carbon base body of processing, the presoma of silicon-carbon cathode material is made.Reacting gas source described herein is SiH4、SiH3R、SiH2R2、
SiHR3In one or more, carry out chemical vapor deposition.Its process hazard coefficient is high, and operation difficulty degree is big, and cost is high,
Be not suitable for large-scale production.A kind of and for example patent " preparation method of silicon-carbon cathode composite " (CN201710064083.4)
In, by hydro-thermal method in silicon powder surface carbon coated forerunner, then calcine under an inert atmosphere；Material after calcining is dispersed in mixing
In solution, drying process is carried out after disperseing at a high speed；Dried material is subjected to corrosion treatment with corrosive liquid.Existed using hydro-thermal method
Silicon face carbon coated, it is not only dangerous, and low yield, while the porous silicon obtained with corrosion corrosion, its pore passage structure are miscellaneous
Disorderly, still can efflorescence in cyclic process.Also carbon coating, such as document " One- are carried out to nano-silicon using laser treatment
Step Synthesis of Si@C Nanoparticles by Laser Pyrolysis:High Capacity Anode
Material for Lithium-Ion Batteries(ACS Appl.Mater.Interfaces 2015,7(12):6637-
6644), this method needs to be equipped with laser treatment instrument, it is desirable to which height will use acetylene gas, and higher to equipment requirement, price is held high
It is expensive, can not extensive extensive use.
In addition, the composite that above method is prepared also volume energy density be present and power energy density is low,
The defects of application requirement of cell negative electrode material can not be met.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of Si-C composite material, its preparation
Methods and applications, its object is to by the way that discarded silicate-based glasses powder is well mixed with sheet carbon material, Ran Houzai
Hydraulic pressure ingot carries out magnesium thermit and obtains Si-C composite material after being mixed with magnesium powder, fused salt, and preparation method is simple, process safety,
Cost is low, and the Si-C composite material being prepared has very high tap density and compacted density, is born as lithium ion battery
Pole material has good performance, thus solve prior art silicon-carbon cathode material preparation condition is harsh, costly, step
The problems such as complicated, seriously polluted, while the silicon-carbon cathode material volume energy density and power energy density that are prepared are low, no
The technical problems such as the application requirement of cell negative electrode material can be met.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of Si-C composite material, the silicon-carbon are answered
Condensation material includes the porous silicon and Sheet Graphite of three-dimensional insertion, wherein the porous silicon is between the Sheet Graphite, shape
Into sandwich structure, there is the porous silicon three-dimensional to run through pore structure；The weight/mass percentage composition of silicon is in the composite
20%~80%, surplus is carbon.
Preferably, porous silicon granular size is 1~5 micron in the composite, and the thickness of the Sheet Graphite is 10
~20 nanometers, size is 5~10 microns；The macroporous structure size of the composite is 50~200 nanometers, the chi of meso-hole structure
Very little is 2~6 nanometers.
Preferably, the tap density of the composite is 0.87~0.96g/cm3, compacted density is 1.36~1.54g/
cm3, specific surface area is 120~150m2g-1。
According to another aspect of the present invention, there is provided a kind of preparation method of Si-C composite material, comprise the following steps：
(1) wet ball grinding is carried out after mixing silicate glass powder and lamella carbon material, is dried after separation of solid and liquid, is obtained
The mixture of well mixed silicate glass powder and lamella carbon material；
(2) after the silicate glass powder that step (1) obtains is mixed with mixture, magnesium powder and the fused salt of lamella carbon material
Ingot is compacted, magnesiothermic reduction reaction then occurs under an inert atmosphere；It is compound that reaction product progress pickling processes are obtained into silicon-carbon
Material.
Preferably, the particle diameter of step (1) described silicate glass powder is 5~10 microns.
Preferably, the lamella carbon material is the carbon material with lamellar structure, including native graphite, Delanium or swollen
One or more in swollen graphite.
Preferably, the lamella carbon material is expanded graphite.
Preferably, the mass ratio of step (1) silicate glass powder and the lamella carbon material is 10:0.5~2.
Preferably, the time of step (1) described wet ball grinding is 6~12 hours, and the solvent used is alcohol.
Preferably, carbonization treatment is first carried out to the mixture of step (2) silicate glass powder and lamella carbon material,
Then mixed again with the magnesium powder and fused salt；The specific steps of the carbonization treatment are preferably：By the mixture in ar gas environment
Under with 1~10 DEG C/min programming rate be heated to 800~1200 DEG C insulation 1~3h, crushed after annealing.
Preferably, the quality of the mixture of step (2) silicate glass powder and lamella carbon material, magnesium powder and fused salt
Than for 1：0.3~0.4：3~5.
Preferably, step (2) described fused salt includes the one or more in magnesium chloride, sodium chloride and potassium chloride.
Preferably, the fused salt is the equal quality ratio mixture of sodium chloride and potassium chloride.
Preferably, the pressure limit that step (2) the compacting ingot uses is 10~50MPa.
Preferably, the compacting ingot is realized by using hydraulic press, forcing press or cold extrusion press.
Preferably, step (2) the magnesiothermic reduction reaction condition is：In argon gas atmosphere, with 2~10 DEG C/min heating
Speed is heated to 600~800 DEG C of 3~6h of insulation.
According to another aspect of the present invention, there is provided a kind of application of described Si-C composite material, for lithium ion
Cell negative electrode material.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect.
(1) Si-C composite material provided by the invention is the tool being compounded to form by the Sheet Graphite of porous silicon and class graphene
There is the silicon-carbon composite construction of similar sandwich structure, the composite has very high tap density and compacted density, possesses height
Specific discharge capacity and volume and capacity ratio, limited electrode expansion, superior cyclical stability, be as negative electrode of lithium ion battery
Ideal material.
(2) this invention takes compacting ingot technology, by the carbon materials such as silicate-based glasses and graphite it is well mixed after,
Ingot is first compacted with magnesium powder and fused salt, then carries out magnesium thermit again, pickling obtains Si-C composite material.Wherein being compacted ingot is
Under mechanical force, reactant and fused salt are mixed together compacting, compacting ingot causes graphite to be contacted more with silicate glass
Step up close, then using the fusing point of silicate glass, carry out magnesium thermits at 700 DEG C, it is entered under the molten condition of flowing
Row reaction, reaction is more abundant, and is easier to penetrate between graphite linings and reacts, and the sandwich-like porous silicon obtained after cooling/
Class graphene-structured composite possesses bigger tap density, in addition, forming the silicon-carbon composite construction of sandwich structure, favorably
In alleviating its volumetric expansion, the lithium of high volume energy density, long circulating performance and excellent high rate performance is possessed available for manufacture
Ion battery.
(3) present invention prepares Si-C composite material using discarded silicate glass and common carbon material as raw material, discards silicic acid
Salt glass and carbon material cost are cheap, rich content, are a kind of lithium ion battery silicon-carbon cathode raw materials for production of high quality and at a reasonable price.
(4) present invention uses the halide such as magnesium chloride, potassium chloride, sodium chloride as fused salt in preparation process, due to these
The fusing point of fused salt also between 600-750 DEG C, on the one hand ensures that reaction environment is stable, and avoid grain growth as heat absorbent
It hurry up, crystal grain thinning, product reunion sintering can also be prevented more to prevent accessory substance from producing to improve product purity so that entirely instead
It should be more easy to carry out, reaction is more abundant, and whole reaction is safer.
(5) silicate glass of the invention is in molten state at 600 DEG C -750 DEG C, and this temperature is also at range of reaction temperature
Interior and magnesium powder is also at liquid, is that a kind of " liquid-liquid " magnesium thermit is better than other " solid-liquid " magnesium thermits, therefore at 700 DEG C
Progress magnesium thermit, which can to react, fully carries out and obtains compound uniform celelular silica ink structure.
(6) present invention designs and develops a kind of simpler, more green synthetic method the porous silicon-carbon that is prepared
Compound is used as lithium ion battery negative material reversible capacity height, and cycle performance is excellent, and this is inexpensive, easy to operate and can amplify life
The method for preparing high performance silicon carbon negative pole material of production will be helpful to the development of lithium ion battery of future generation.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the porous silicon graphite composite material that the embodiment of the present invention 1 is prepared；
Fig. 2 is the XRD spectrum for the porous silicon graphite composite material that the embodiment of the present invention 1 is prepared；
Fig. 3 is the transmission electron microscope picture for the porous silicon graphite composite material that the embodiment of the present invention 1 is prepared；
Fig. 4 is the electrochemistry cycle performance figure for the porous silicon graphite composite material that the embodiment of the present invention 1 is prepared；
Fig. 5 be the adsorption and desorption curve of porous silicon graphite composite material that the embodiment of the present invention 1 is prepared and
Pore size distribution curve；
Fig. 6 is the thermogravimetric analysis figure for the porous silicon graphite composite material that the embodiment of the present invention 1 is prepared.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
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.In addition, in each embodiment of invention described below, as long as involved technical characteristic
Conflict can is not formed each other to be mutually combined.
Si-C composite material provided by the invention, include the porous silicon and Sheet Graphite of three-dimensional insertion, wherein described three
Porous silicon is tieed up between the Sheet Graphite, forms sandwich structure, the porous silicon is along growth of graphite and with three
Dimension runs through pore structure, and its granular size is 1~5 micron, and the thickness of the Sheet Graphite is 10~20 nanometers, and size is 5~10
Microns.The macropore of the composite is that the pore structure size of porous silicon is 50~200 nanometers, and the size of meso-hole structure is
2~6 nanometers.Silicon weight/mass percentage composition is 20%~80% in the composite, and surplus is carbon.The vibration density of the composite
Spend for 0.87~0.96g/cm3, compacted density is 1.36~1.54g/cm3, specific surface area is 120~150m2g-1。
The preparation method of the Si-C composite material, it is characterised in that comprise the following steps：
(1) wet ball grinding is carried out after closing silicate glass powder and lamella carbon material, drying, which obtains, after filtering mixes
The mixture of even silicate glass powder and lamella carbon material.
As preferable technical scheme, the particle diameter of silicate glass powder is 5~10 microns.Silicate glass powder obtains
The method is taken to be：Glass is washed into drying by deionized water, then dropped the particle size of glass by the method for mechanical ball mill
After low, the sieving of 1000 mesh, the satisfactory glass powder of particle size is filtered out so that compound more equal in subsequent preparation process
It is even.The silicate glass is water soda glass or calcic silicate glass.
Lamella carbon material is in the carbon material with lamellar structure, including native graphite, Delanium or expanded graphite
One or more, preferably expanded graphite, expanded graphite possess extremely strong resistance to pressure, pliability, plasticity and compatibility, energy
Enough fine and compound composition electrode materials of silicon materials.The mass ratio of silicate glass powder and lamella carbon material is 10:0.5~2.
The time of wet ball grinding is 6~12 hours, and the solvent of use is preferably alcohol.
(2) after the silicate glass powder that step (1) obtains is mixed with mixture, magnesium powder and the fused salt of lamella carbon material
Ingot is compacted, magnesiothermic reduction reaction then occurs under an inert atmosphere；It is compound that reaction product progress pickling processes are obtained into silicon-carbon
Material.
Wherein, as preferable scheme, the matter of the mixture of silicate glass powder and lamella carbon material, magnesium powder and fused salt
Amount is than being 1：0.3~0.4：3~5.Fused salt is the one or more in magnesium chloride, sodium chloride and potassium chloride, preferably sodium chloride
With the equal quality ratio mixture of potassium chloride.The pressure limit that compacting ingot uses is 10~50MPa, magnesiothermic reduction reaction condition
For：In argon gas atmosphere, 600-800 DEG C of 3~6h of insulation is heated to 2-10 DEG C/min programming rate.The temperature of magnesium thermit
Preferably 700 DEG C, reactant is reacted in the molten state, bigger bulk density is possessed after cooled and solidified.Present invention compacting
The pressure limit that ingot uses is less than for 10~50MPa or beyond this pressure limit, can not all obtain complete column ingot, make
Integral avalanche；Reactant and fused salt are mixed together compacting, the celelular silica china ink stick of densification, its vibration density are obtained after thermal response
Degree and compacted density are all no less than the level of current commercial graphite；Compacting ingot can pass through hydraulic press, forcing press, cold extrusion press
Or other press devices are realized.On the other hand, the pressure also directly affects the specific surface area of final obtained Si-C composite material,
With the increase of pressure, composite mesopore volume diminishes, and influences its specific surface area, the composite that the pressure limit obtains
Specific surface area be not it is too high also will not be too low, disclosure satisfy that negative material to its specific surface area for lithium ion battery negative material
Requirement.
Acid pickling step is specially：8~12h is cleaned under stirring condition in 0.5mol/L hydrochloric acid, then in 0.5mol/L
Hydrofluoric acid in clean, be dried to obtain porous silicon graphite combination product.
Carbonization treatment, Ran Houzai are first carried out to the mixture of step (2) silicate glass powder and lamella carbon material
Mixed with the magnesium powder and fused salt；The specific steps of the carbonization treatment are preferably：By the mixture under ar gas environment with 1~
10 DEG C/min programming rate is heated to 800~1200 DEG C of 1~3h of insulation, is crushed after annealing.The effect of carbonization treatment is so that
Lamella carbon material graphitization as far as possible, remove the organo-functional group of carbon material surface.
It actually discloses a kind of method that silicon-carbon cathode material is prepared using silicate-based glasses as raw material to the present invention, should
Method comprises the following steps：Silicate-based glasses are milled by mechanical ball mill broken, after by glass powder and graphite according to certain
Ratio, by the use of alcohol as solvent, filtering drying obtains the homogeneously mixed product of glass and graphite after wet ball grinding, then will
The sample arrived is with certain temperature carbonization treatment under ar gas environment, and sample grinding after annealing is broken and magnesium powder, fused salt are according to one
Ingot is compacted after fixed ratio uniform mixing, reacts (M under an inert gasxSiO3+ 2Mg=2MgO+Si+MxO, M=Na, Ca,
Al), reaction product pickling processes are then obtained into sandwich-like porous silicon/class graphene-structured composite.Inventive step letter
Single easy, raw material sources are extensive, cheap, it is most important that by simple hydraulic process, by mixture make ingot it
Afterwards, then magnesium thermit is carried out, considerably increases the tap density of silicon-carbon cathode material, improve the volume specific volume of negative material
Amount, and the Porous Silicon structures of obtained three-dimensional crosslinking structure can effectively alleviate lithium ion de- one it is embedding during silicon materials body
Product expansion, at the same it is compound with the carbon material such as graphite after the structure of similar sandwich structure that is formed also be effectively improved material
Electronic conductivity, the compatibility of silica-base material and electrolyte is improved, so as to improve the cycle performance of material and high rate performance,
It can be applied to the lithium ion battery negative material of high power density and high-energy-density.Silicon lithium ion it is embedding it is de- during volume become
Change it is big (>300%) cause the efflorescence of electrode and the electrical contact of silicon and collector to reduce, cause electric conductivity variation and the utilization rate of silicon
Reduce, and carbon material has higher electronic conductance, and preferable electron channel is provided for composite, while by carbon and silicon materials
The stress variation that silicon materials volume deformation is brought can be relaxed after compound；In addition, lamella carbon material can effectively stabilized electrodes material with
The interface of electrolyte, make SEI films are stable to grow, these features are all beneficial to the chemical property for improving silicium cathode.
The present invention is reacted using low temperature magnesiothermic reduction and prepared by wet ball grinding, high annealing (carbonization) and compacting ingot
Obtain porous silicon/graphite composite material.Wet ball grinding causes silicon materials and carbon material to be first sufficiently mixed, and is evenly distributed；Then enter
Row carbonization treatment so that carbon material graphitization, remove the organo-functional group of carbon material surface；It is uniformly mixed after having handled again
Glass powder after conjunction mixes with the mixture of carbon material with magnesium powder, fused salt, ingot is compacted under mechanical force, then lazy
Magnesium thermit is carried out under property gas, silicate glass reacts in the liquid state with fused salt, magnesium powder, is formed in situ after pickling with similar
The Si-C composite material of sandwich structure, the silicon that the method is made not only have loose structure, and compound with graphite formation
Material has very high tap density and compacted density, possesses high specific discharge capacity and volume and capacity ratio, limited electrode is swollen
Swollen, superior cyclical stability, it is the ideal material as negative electrode of lithium ion battery, suitable for commercially producing.
The Si-C composite material preparation method of the present invention using silicate glass as the silicon source in Si-C composite material, its
Participating in magnesium thermit can exist in liquid form in itself, therefore applicant of the present invention is creatively proposed in magnesium thermit
Ingot is compacted after silicate glass powder is uniformly mixed with carbon material before, magnesium thermit is then carried out again, so finally obtains
The density of the Si-C composite material obtained is just improved, and is finally applied to its energy bulk density and power during cell negative electrode material
Energy density significantly improves.Each step can not exchange order, each step collaboration in the preparation method of Si-C composite material of the present invention
Coordinate, collectively form a set of independent, complete technical scheme so that final obtain has very high tap density and be compacted close
The Si-C composite material of degree, high specific discharge capacity and volume and capacity ratio, limited electrode expansion and superior cyclical stability
It is possibly realized.
It is embodiment below：
Embodiment 1
(1) by 5~10 microns of glass powder after ball milling and expanded graphite according to mass ratio 10：1 ratio, with alcohol
As ball milling agent, mechanical ball mill 10h in agate pot is put into, obtains the mixture of glass and graphite；
(2) by the glass and the mixture of graphite that are obtained in step (1) under ar gas environment with 5 DEG C/min programming rate
It is heated to 1000 DEG C of insulation 2h carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.35：4 uniformly mixing after
Hydraulic pressure ingot under 40MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 5 DEG C/min programming rate
To 700 DEG C of insulation 3h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 5 hours in 1mol/L hydrochloric acid.Then exist
Cleaned 10 minutes in 0.5mol/L hydrofluoric acid, porous silicon/graphite composite material is obtained after pickling.
From Fig. 1 scanning electron microscope (SEM) photograph, silicon that the present embodiment is prepared belong to 1~5 micron level along graphite
Piece growth has the three-dimensional porous silicon for running through structure, and the porous silicon is the block structure that particle is connected, due in magnesium thermit
During reactant be in molten state, can penetrate into graphite linings, the silicon generated in reduction process stays in graphite layers, graphite flake
Size be 5~10 microns, in Fig. 1, it can be clearly seen that graphite flake and porous silicon are uniformly compound, formed sandwich-like.
From Fig. 2 XRD diffracting spectrums, in 28.4 °, 47.3 ° and 56.1 ° of three strongest peak and silicon (JCPDS No.27-
1402) three strongest peak is corresponding, and the G peaks of graphite are obvious, and substantially without dephasign.
From Fig. 3 transmission electron microscope picture, three-dimensional porous silicon, is in the Si-C composite material that the present embodiment is prepared
Between class graphene sheet layer, the sandwich of similar sandwich is formed, the thickness of the graphite flake is between 10~20 nanometers, Fig. 3
The illustration in the upper left corner shows that the porous silicon has excellent pore passage structure and overall interpenetrate is not destroyed, and wherein aperture
For 50~200 nanometers.This structure alleviates the volumetric expansion in charge and discharge process well, and adds electric conductivity, can be with
The reason for disclosing its superior performance.
The excellent electrochemistry cycle performance of porous silicon shown in Fig. 4, circulating 100 times still has higher capacity (850mAh/g),
Good cycling stability, therefore the present invention industrially can be mass produced and applied.
As shown in figure 5, the specific surface area of the sandwich-like porous silicon/class graphene-structured composite is 130m2g-1, wherein
Mesoporous pore size is 2~6 nanometers.The tap density of the multi-pore micron silicon/graphite composite material is 0.96g/cm after tested3, compacting
Density is 1.42g/cm3, the method synthesis porous silicon/carbon composite material have superelevation specific surface area and excellent hole knot
Structure, it is suitable for lithium cell cathode material.
Fig. 6 thermogravimetric analysis understands that carbon content is 55wt%, silicone content 45wt% in the composite.
Embodiment 2
(1) by 5~10 microns of glass powder after ball milling and expanded graphite according to mass ratio 10：0.8 ratio, with wine
Essence is used as ball milling agent, is put into mechanical ball mill 10h in agate pot, obtains the mixture of glass and graphite；
(2) by the glass and the mixture of graphite that are obtained in step (1) under ar gas environment with 5 DEG C/min programming rate
It is heated to 850 DEG C of insulation 2h carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.35：5 uniformly mixing after
Hydraulic pressure ingot under 12MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 5 DEG C/min programming rate
To 700 DEG C of insulation 3h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 3 hours in 2mol/L hydrochloric acid.Then exist
Cleaned 30 minutes in 0.2mol/L hydrofluoric acid, porous silicon/graphite composite material is obtained after pickling.
Embodiment 3
(1) by 5~10 microns of glass powder after ball milling and expanded graphite according to mass ratio 10：0.5 ratio, with wine
Essence is used as ball milling agent, is put into mechanical ball mill 8h in agate pot, obtains the mixture of glass and graphite；
(2) by the glass and the mixture of graphite that are obtained in step (1) under ar gas environment with 3 DEG C/min programming rate
It is heated to 800 DEG C of insulation 1h carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.3：4 uniformly mixing after
Hydraulic pressure ingot under 10MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 5 DEG C/min programming rate
To 600 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 10 hours in 0.5mol/L hydrochloric acid.Then exist
Cleaned 60 minutes in 0.1mol/L hydrofluoric acid, porous silicon/graphite composite material is obtained after pickling.
Embodiment 4
(1) by 5~10 microns of glass powder after ball milling and expanded graphite according to mass ratio 10：1 ratio, with alcohol
As ball milling agent, mechanical ball mill 8h in agate pot is put into, obtains the mixture of glass and graphite；
(2) by the glass and the mixture of graphite that are obtained in step (1) under ar gas environment with 10 DEG C/min heating speed
Degree is heated to 850 DEG C of insulation 1h carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.5：5 uniformly mixing after
Hydraulic pressure ingot under 20MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and added with 10 DEG C/min programming rate
Heat obtains reacted mixture to 750 DEG C of insulation 4h；
(5) the reacted mixture that step (4) obtains first is cleaned 1 hour in 3mol/L hydrochloric acid.Then exist
Cleaned 20 minutes in 0.4mol/L hydrofluoric acid, porous silicon/graphite composite material is obtained after pickling.
Embodiment 5
(1) by the glass powder of the 5-10 microns after ball milling and electrographite according to mass ratio 10：1.5 ratio, with wine
Essence is used as ball milling agent, is put into mechanical ball mill 10 in agate pot, obtains the mixture of glass and graphite；
(2) by the glass and the mixture of graphite that are obtained in step (1) under ar gas environment with 5 DEG C/min programming rate
It is heated to 1000 DEG C of insulation 1h carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.4：5 uniformly mixing after
Hydraulic pressure ingot under 30MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 5 DEG C/min programming rate
To 750 DEG C of insulation 3h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 10 hours in 2mol/L hydrochloric acid.Then exist
Cleaned 5 minutes in 1mol/L hydrofluoric acid, porous silicon/graphite composite material is obtained after pickling.
Embodiment 6
(1) by 5~10 microns of glass powder after ball milling and native graphite according to mass ratio 10：2 ratio, with alcohol
As ball milling agent, mechanical ball mill 12h in agate pot is put into, obtains the mixture of glass and graphite；
(2) by the glass and the mixture of graphite that are obtained in step (1) under ar gas environment with 10 DEG C/min heating speed
Degree is heated to 1200 DEG C of insulation 2h carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.35：3 uniformly mixing after
Hydraulic pressure ingot under 50MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 5 DEG C/min programming rate
To 800 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 5 hours in 1.5mol/L hydrochloric acid.Then exist
Cleaned 30 minutes in 0.5mol/L hydrofluoric acid, porous silicon/graphite composite material is obtained after pickling.
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 within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (10)
- A kind of 1. Si-C composite material, it is characterised in that the Si-C composite material includes porous silicon and Sheet Graphite, wherein The porous silicon forms sandwich structure between the Sheet Graphite, and there is the porous silicon three-dimensional to run through pore structure；Institute The weight/mass percentage composition for stating silicon in composite is 20%~80%, and surplus is carbon.
- 2. composite as claimed in claim 1, it is characterised in that porous silicon granular size is 1~5 in the composite Micron, the thickness of the Sheet Graphite is 10~20 nanometers, and size is 5~10 microns；The macroporous structure chi of the composite Very little is 50~200 nanometers, and the size of meso-hole structure is 2~6 nanometers.
- 3. composite as claimed in claim 1, it is characterised in that the tap density of the composite be 0.87~ 0.96g/cm3, compacted density is 1.36~1.54g/cm3, specific surface area is 120~150m2g-1。
- 4. a kind of preparation method of Si-C composite material, it is characterised in that comprise the following steps：(1) wet ball grinding is carried out after mixing silicate glass powder and lamella carbon material, dries, is mixed after separation of solid and liquid The mixture of uniform silicate glass powder and lamella carbon material；Preferably, the particle diameter of the silicate glass powder be 5~ 10 microns；(2) it is compacted after the silicate glass powder that step (1) obtains is mixed with mixture, magnesium powder and the fused salt of lamella carbon material Ingot, magnesiothermic reduction reaction then occurs under an inert atmosphere；Reaction product progress pickling processes are obtained into Si-C composite material.
- 5. preparation method as claimed in claim 4, it is characterised in that the lamella carbon material is the carbon materials with lamellar structure Material, including the one or more in native graphite, Delanium or expanded graphite, preferably expanded graphite.
- 6. preparation method as claimed in claim 4, it is characterised in that step (1) silicate glass powder and described The mass ratio of layer carbon material is 10:0.5~2.
- 7. preparation method as claimed in claim 4, it is characterised in that to step (2) silicate glass powder and lamella The mixture of carbon material first carries out carbonization treatment, is then mixed again with the magnesium powder and fused salt；The specific step of the carbonization treatment It is rapid to be preferably：The mixture is heated to 800~1200 DEG C of insulations 1 under ar gas environment with 1~10 DEG C/min programming rate ~3h, crushed after annealing.
- 8. preparation method as claimed in claim 4, it is characterised in that step (2) silicate glass powder and lamella carbon The mass ratio of the mixture of material, magnesium powder and fused salt is 1：0.3~0.4：3~5.
- 9. preparation method as claimed in claim 4, it is characterised in that the pressure limit that step (2) the compacting ingot uses For 10~50MPa, the compacting ingot is preferably realized by using hydraulic press, forcing press or cold extrusion press.
- A kind of 10. application of Si-C composite material as described in claims 1 to 3 any one, it is characterised in that for lithium from Sub- cell negative electrode material.
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