CN107579214A - A kind of method, its product and application that Si-C composite material is prepared using silicate glass as raw material - Google Patents
A kind of method, its product and application that Si-C composite material is prepared using silicate glass as raw material Download PDFInfo
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Abstract
The invention discloses a kind of method, its product and application, this method that Si-C composite material is prepared using silicate glass as raw material to comprise the following steps：The homogeneously mixed product of glass and carbon material will be obtained after glass powder and carbon material wet ball grinding, be pressed into after uniformly being mixed with magnesium powder, fused salt after ingot and magnesium thermit occurs, reaction product pickling processes are then obtained into different structure carbon and silicon composite.The inventive step is simple and easy, raw material sources are extensive, above all through by 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, its electronic conductivity is also effectively improved with the Si-C composite material of the compound rear formation of graphited carbon material simultaneously, improve the compatibility of silica-base material and electrolyte, so as to improve the cycle performance of material and high rate performance, the lithium ion battery negative material of high power density and high-energy-density can be applied to.
Description
Technical field
The invention belongs to lithium ion battery negative material field, more particularly, to one kind using silicate glass as raw material
Prepare method, its product and the application of Si-C composite material.
Background technology
Today's society energy crisis increasingly highlights with environmental problem, and the storage of the novel clean energy and energy turns into people
The focus studied.Lithium ion battery because its high-energy-density, high power density, the long-life and it is environment-friendly the features such as,
The fields such as electric automobile, extensive energy storage device, distributing portable power source have broad application prospects.However, lithium-ion electric
The specific discharge capacity and energy density in pond need further raising, to meet portable type electronic product miniaturization and its navigate
My god, in terms of military, peak load regulation network and electric automobile application requirement.In numerous lithium ion battery negative materials, due to silicon
The advantage of manufacturing industry industrialization infrastructure with abnormal high specific capacity, the reserves enriched in the earth's crust and prosperity, quilt
It is considered the negative material of the great potentiality of lithium ion battery of future generation.Therefore, the lithium ion of height ratio capacity and high-energy-density is researched and developed
Battery material oneself turn into the very important research topic of work at present.However, the scale use of silicium cathode material should solve two
Individual key issue：Silicon grain in removal lithium embedded along with volumetric expansion and contraction caused by granule atomization, come off and electricity
Chemical property fails；The continued propagation of silicon grain surface solid dielectric substrate (SEI) is to electrolyte and the lithium source from positive pole
Irreversible consumption.It is one of the effective approach that solves the above problems to prepare Si-C composite material.
At present Si-C composite material mainly have cladded type and embedded type both.Wherein clad structure is in active material silicon
Coated with carbon bed, alleviate the bulk effect of silicon, strengthen its electric conductivity.According to clad structure and silicon grain pattern, clad structure
Hud typed, yolk-shell mould and porous type can be divided into.Clad structure is to coat carbon-coating in active material silicon face, alleviates silicon
Bulk effect, strengthen its electric conductivity.According to clad structure and silicon grain pattern, clad structure can be divided into hud typed, yolk-shell mould
And porous type.But current methods that these prepare Si-C composite material, not only condition is harsh, costly, and step is complicated,
And it is seriously polluted, be related to many noxious materials, be larger to people's harmfulness.Such as patent " preparation method of silicon-carbon cathode material "
(CN104103821A) in, catalyst is placed in chemical vapor deposition reaction chamber first；Heating chemical phase depositing reaction chamber,
Reacting gas source and carrier gas are passed through in toward chemical vapor deposition reaction chamber, by caused Si-SiOx in chemical gas phase reaction process
By the carbon base body handled by carboxylated of dynamic rotary, the presoma of obtained silicon-carbon cathode material.Its process hazard coefficient
Height, operation difficulty degree is big, and cost is high, is not suitable for large-scale production.A kind of and for example patent " system of polymer silicon carbon negative pole material
It is compound and then in the presence of various dispersants and binding agent using nano-silicon and graphite in Preparation Method " (CN106356520A)
High temperature carbonization, polymer silicon carbon compound cathode materials are obtained in one layer of agraphitic carbon of its Surface coating and then spray drying, still
Contain dephasign in silicon-carbon cathode material prepared by the method, influence the performance of negative material.Utilization PAN also is to nano-silicon
Carbon coating, such as document " A strategy for suitable mass production of a hollow Si@C
Nanostructured anode for lithium ion batteries " (RSC Adv.2015,5,6782-6789), this
The Si-C composite material that kind method is prepared is because its core shell structure causes its volume energy density original that is not high, and using
Expect that price is relatively expensive, can not extensive extensive use.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides one kind using silicate glass as raw material system
Method, its product and the application of standby Si-C composite material, its object is to by by discarded silicate-based glasses powder and carbon materials
Material carries out carbonization treatment after being well mixed by wet ball grinding, and ingot is compacted after then being mixed again with magnesium powder, fused salt, carries out magnesium heat
Reaction obtains Si-C composite material, and preparation method is simple, and process safety, cost is low, and the Si-C composite material tool being prepared
There are very high tap density and compacted density, there is good performance as lithium ion battery negative material, thus solve existing
The problems such as silicon-carbon cathode material preparation condition of technology is harsh, costly, step is complicated, seriously polluted, is prepared simultaneously
Silicon-carbon cathode material volume energy density and the skill such as the low application requirement that can not meet cell negative electrode material of mass energy density
Art problem.
To achieve the above object, according to one 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 carbon material, dries and is mixed after separation of solid and liquid
The mixture of uniform silicate glass powder and carbon material；
(2) silicate glass powder and the mixture of carbon material obtained step (1) carries out carbonization treatment, will after annealing
The mixture is ground, and obtains the mixture of the silicate glass powder after carbonization treatment and carbon material；
(3) by the silicate glass powder after the carbonization treatment described in step (2) and the mixture of carbon material and magnesium powder and
Ingot is compacted after fused salt mixing, magnesiothermic reduction reaction then occurs under an inert atmosphere；Reaction product progress pickling processes are obtained
To Si-C composite material.
Preferably, the particle diameter of step (1) described silicate glass powder is 1~4 micron.
Preferably, the carbon material is carbon containing organic double compound or one-dimensional carbon material, and the carbon containing organic double compound includes
One or more in pitch, petroleum coke, coal tar, phenolic resin, graphene and biomass carbon；The one-dimensional carbon material includes
One or more in carbon fiber, bacteria cellulose and CNT.
Preferably, the mass ratio of step (1) silicate glass powder and the carbon material is 10:2~5.
Preferably, the time of step (1) described wet ball grinding is 6~12 hours, and the solvent used is n-amyl alcohol.
Preferably, step (2) carbonization treatment concretely comprises the following steps：With 1~5 DEG C/min heating under ar gas environment
Speed is heated to 400~550 DEG C of 1~3h of insulation, is then heated to 800~1000 DEG C again with 5~10 DEG C/min programming rate
It is incubated 2~4h.
Preferably, before step (2) described carbonization treatment, in addition to sub-step：By the silicate glass powder and carbon materials
The mixture of material carries out compacting ingot.
Preferably, the mixture of the silicate glass powder and carbon material be compacted to the pressure limit of ingot use
For 0.5~2MPa.
Preferably, the mixture of the silicate glass powder after step (3) described carbonization treatment and carbon material and magnesium powder and
The mass ratio of fused salt is 1：0.5~0.6：3~5.
Preferably, the compacting ingot is realized by forcing press, hydraulic press or cold extrusion press.
Preferably, the pressure limit that step (3) the compacting ingot uses is 1~5MPa.
Preferably, step (3) described fused salt includes the one or more in magnesium chloride, sodium chloride and potassium chloride.
Preferably, the dissolved salt is the equal quality ratio mixture of sodium chloride and potassium chloride.
Preferably, step (3) the magnesiothermic reduction reaction condition is：In argon gas atmosphere, with 2~5 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 Si-C composite material, the Si-C composite material is according to institute
The preparation method stated is prepared.
Preferably, the tap density of the composite is 1.03~1.27g/cm3, compacted density is 1.46~1.63g/
cm3, specific surface area is 100~150m2g-1。
Preferably, the content of silicon is 80~90wt% in the composite, and surplus is carbon.
According to another aspect of the present invention, there is provided a kind of application of described Si-C composite material, applied to lithium from
Sub- 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) preparation method of Si-C composite material of the present invention uses wet ball grinding, carbonization treatment and hydraulic technique successively, will
Silicate-based glasses and carbon material carry out carbonization treatment after wet ball grinding is well mixed, by the mixture hydraulic pressure ingot, move back
Mixed after fire with magnesium powder and fused salt, then be pressed into ingot, then carry out magnesium thermit, last pickling reaction product obtains silicon-carbon composite wood
Material.Wherein wet ball grinding ensures that silicate glass powder uniformly mixes with carbonaceous material, be final silicon and carbon in the composite
Be uniformly distributed and lay the first stone；The purpose of carbonization treatment is that high temperature cabonization is to strengthen on the basis of the two is well mixed
The crystallinity of carbon material, strengthen the electric conductivity of Si-C composite material；It is under mechanical force, by reactant to be compacted ingot technology
Compacting is mixed together with fused salt, the compound porous silicon ingot of the different structure carbon of densification, its tap density and pressure are obtained after thermal response
Real density is all no less than the level of current commercial graphite, and obtained composite volume density is remarkably enhanced.
(2) Si-C composite material provided by the invention is different according to the species of initial carbon material, and can obtain different knots
The Si-C composite material of structure.The composite has very high tap density and compacted density, possess high specific discharge capacity and
Volume and capacity ratio, limited electrode expansion, superior cyclical stability, it is the ideal material as negative electrode of lithium 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 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 600~800 DEG C, on the one hand ensures that reaction environment is stable, and avoid grain growth as heat absorbent
Too fast crystal grain thinning can also prevent product reunion sintering from more preventing accessory substance from producing to improve product purity so that entirely instead
Should more preferably it 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~800 DEG C, and this temperature is also at reaction temperature model
In enclosing 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 680 DEG C
The lower magnesium thermit that carries out can to react the Porous Silicon structures for fully carrying out and obtaining compound uniform agraphitic carbon cladding.
(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 porous silicon/agraphitic carbon composite that the embodiment of the present invention 1 is prepared；
Fig. 2 is the XRD spectrum for porous silicon/agraphitic carbon composite that the embodiment of the present invention 1 is prepared；
Fig. 3 is the transmission electron microscope picture for porous silicon/agraphitic carbon composite that the embodiment of the present invention 1 is prepared；
Fig. 4 is the electrochemistry cycle performance for porous silicon/agraphitic carbon composite that the embodiment of the present invention 1 is prepared
Figure；
Fig. 5 is the adsorption and desorption curve for porous silicon/agraphitic carbon composite that the embodiment of the present invention 1 is prepared
And pore size distribution curve；
Fig. 6 is the thermogravimetric curve for porous silicon/agraphitic carbon composite that the embodiment of the present invention 1 is prepared；
Fig. 7 is the scanning electron microscope (SEM) photograph for porous silicon/agraphitic carbon composite that the embodiment of the present invention 3 is prepared；
Fig. 8 is the scanning electron microscope (SEM) photograph for porous silicon/carbon nano tube compound material that the embodiment of the present invention 7 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.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
The preparation method of Si-C composite material provided by the invention, comprises the following steps：
(1) wet ball grinding is carried out after mixing silicate glass powder and carbon material, dries and is well mixed after filtering
Silicate glass powder and different carbon materials mixture.
In the present invention, the particle size range of silicate glass powder is preferably 1~4 micron.The acquisition of silicate glass powder
Method is：Glass is washed into drying by deionized water, then reduced the particle size of glass by the method for mechanical ball mill
Afterwards, 1000 mesh sieve, and filter out the satisfactory glass powder of particle size.The silicate glass is water soda glass or silicon
Sour lime glass.Carbon material can be carbon containing organic double compound or one-dimensional carbon material, and carbon containing organic double compound includes pitch, oil
One or more in Jiao, coal tar, graphene, phenolic resin and biomass carbon；One-dimensional carbon material includes bacteria cellulose, carbon
Fiber or CNT.The mass ratio of silicate glass powder and the carbon material is 10:2~5；The time of wet ball grinding is 6
~12 hours, the solvent used is ethanol or n-amyl alcohol, preferably n-amyl alcohol.Because n-amyl alcohol can be easier particle surface
Hydroxyl functional group, more preferably combined with carbon material.
(2) silicate glass powder and the mixture compacted ingot of carbon material obtained step (1) carries out carbonization treatment,
The mixture ingot is ground after annealing, obtains the compound of the silicate glass powder after carbonization treatment and different structure carbon.
Carbonization treatment concretely comprises the following steps：Under ar gas environment 400~550 are heated to 1~5 DEG C/min programming rate
DEG C insulation 1~3h, then again with 5~10 DEG C/min programming rate be heated to 800~1000 DEG C insulation 2~4h.Carbonization treatment
Effect be to make carbonaceous material better crystallinity degree at high temperature, strengthen the electric conductivity of carbon material, and then strengthen product silicon-carbon composite wood
The electric conductivity of material.
(3) by the silicate glass powder after the carbonization treatment described in step (2) and the compound and magnesium of different structure carbon
Ingot is compacted after powder and fused salt mixing, magnesiothermic reduction reaction then occurs under an inert atmosphere；Reaction product is carried out at pickling
Reason obtains Si-C composite material.
The mass ratio of the compound of silicate glass powder after carbonization treatment and different structure carbon, magnesium powder and fused salt is 1：
0.5~0.6：3~5.Fused salt includes the one or more in magnesium chloride, sodium chloride and potassium chloride, preferably sodium chloride and chlorination
The equal proportion mixture of potassium.It is the pressurize regular hour, such as 1~20 second under pressure to be compacted ingot, makes material pressure
Real ingot shape, it can be realized by hydraulic press, forcing press, cold extrusion press or other press devices.The present invention is using hydraulic pressure twice
Ingot causes the composite tap density finally obtained and compacted density to greatly improve, before step (2) carbonization treatment hydraulic pressure into
The pressure limit that ingot uses can be with more smaller, for example is 0.5~2MPa；Step (3) be pressed into pressure limit that ingot uses for 1~
5MPa.It is less than under 1~5MPa pressure limit or the effect of the super ingot that goes beyond the scope will be undesirable, or can not obtains complete
Column ingot, or cause mass failure, reactant and fused salt be mixed together compacting, the different structure of densification is obtained after thermal response
The porous silicon ingot of carbon, its tap density and compacted density are all no less than the level of current commercial graphite.On the other hand, the pressure is also straight
Connecing influences the specific surface area of final obtained Si-C composite material, and with the increase of pressure, composite mesopore volume diminishes, shadow
Ring its specific surface area, the pressure limit obtain composite specific surface area be not it is too high also will not be too low, for lithium ion
Cell negative electrode material disclosure satisfy that requirement of the negative material to its specific surface area.
Magnesiothermic reduction reaction condition is：In argon gas atmosphere, 600~800 are heated to 2~5 DEG C/min programming rate
DEG C insulation 3~6h.The temperature of magnesium thermit is preferably 680 DEG C, reactant is reacted in the molten state, is possessed after cooled and solidified
Bigger bulk density.
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 different structure carbon porous silicon combination product.
During using carbon containing organic double compound as carbon material, it can be obtained using above-mentioned preparation method and be coated by agraphitic carbon
Si-C composite material, the composite includes the porous silicon and agraphitic carbon of three-dimensional insertion, and wherein agraphitic carbon is coated on
The porous silicon surface, the porous silicon are ant nest shape, and its granular size is 1~5 micron, and the thickness of agraphitic carbon is received for 10~20
Rice, is coated on porous silicon surface, and the macroporous structure size of composite is 100~200 nanometers, the size of meso-hole structure for 10~
20 nanometers.The tap density of the composite is 1.03~1.17g/cm3, compacted density is 1.56~1.63g/cm3, compare surface
Product is 120~150m2g-1, the content of silicon is 80~90wt% in the composite, and surplus is carbon.
When using carbon fiber or CNT as carbon material, it can be obtained by one-dimensional carbon nanocoils using above-mentioned preparation method
Or the Si-C composite material of network structure that nanotube and silicon mosaic are interwoven, the composite includes porous silicon and carbon is received
The network structure that mitron or carbon nano-fiber, wherein CNT or carbon nano-fiber are interwoven, some are embedded into silicon grain
In, it will be connected between particle and particle, parcel weave in, the length of its carbon fiber or CNT is micro- for 10~20
Rice, a diameter of 10~20 nanometers.The tap density of the composite is 1.13~1.27g/cm3, compacted density be 1.46~
1.60g/cm3, specific surface area is 100~120m2g-1, the content of silicon is 85~92wt% in the composite, and surplus is carbon.
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 carbon material according to one
Fixed ratio, by the use of n-amyl alcohol as solvent, filtering drying obtains the uniform mixing production of glass powder and carbon material after wet ball grinding
Thing, obtained sample liquid is then pressed into ingot, with certain temperature carbonization treatment, sample grinding after annealing under ar gas environment
Broken and magnesium powder, fused salt react (M under an inert gas according to hydraulic pressure ingot after certain ratio uniform mixingxSiO3+ 2Mg=
2MgO+Si+MxO, M=Na, Ca, Al), reaction product pickling processes are then obtained into the Si-C composite material of different structure.Should
Inventive step is simple and easy, and raw material sources are extensive, cheap, it is most important that by simple hydraulic process, by mixture
Make ingot and then carry out magnesium thermit, considerably increase the tap density of silicon-carbon cathode material, improve negative material
Volume and capacity ratio, and the Porous Silicon structures of obtained three-dimensional crosslinking structure can effectively alleviate lithium ion de- one it is embedding during silicon
The volumetric expansion of material, while by carbonization treatment, make carbon material graphitization, finally formed with graphitized carbon material after compound
Its electronic conductivity of Si-C composite material also greatly improves, and improves the compatibility of silica-base material and electrolyte, so as to improve
The cycle performance and high rate performance of material, 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 Changes it is big (>300%) efflorescence of electrode and the electrical contact of silicon and collector is caused to reduce,
Cause electric conductivity to be deteriorated reduces with the utilization rate of silicon, and carbon material has higher electronic conductance, is provided preferably for composite
Electron channel, while by carbon and silicon materials it is compound after can relax the stress variation that silicon materials volume deformation brings；In addition, carbon is made
For covering material can the effective interface of stabilized electrodes material and electrolyte, make SEI films are stable to grow, these features are all beneficial to improve
The chemical property of silicium cathode.
The present invention is reacted using low temperature magnesiothermic reduction and prepared by wet ball grinding, high annealing (carbonization) and hydraulic pressure ingot
Obtain porous silicon/carbon composite material.Wet ball grinding causes silicon materials and carbon material to be first sufficiently mixed, and is evenly distributed；Then hydraulic pressure
Ingot carries out carbonization treatment so that carbon material graphitization；Uniform mixed glass powder and carbon materials after having handled again
The mixture of material mixes with magnesium powder, fused salt, pushes ingot in mechanical force, then carries out magnesium thermit under an inert gas,
Silicate glass reacts in the liquid state with fused salt, magnesium powder, Si-C composite material is formed in situ after pickling, the silicon that the method is made is not
Only there is loose structure, and further improved by the front and rear ingot of hydraulic pressure twice technology and that graphitized carbon material is formed is compound
The tap density and compacted density of material, possess high specific discharge capacity and volume and capacity ratio, and limited electrode expansion is 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.
The present invention Si-C composite material preparation method in wet ball grinding, high temperature cabonization, hydraulic pressure ingot, magnesium thermit and
Last acid pickling step, these steps can not exchange order, and wet ball grinding ensure that glass powder mixes with the uniform of carbon material,
Only first be well mixed subsequently be carbonized again, briquetting, reduction and pickling, just can guarantee that silicon in final obtained composite
With being uniformly distributed for carbon, ensure the good properties of composite；Similarly, carburising step also must be in wet ball grinding step
Afterwards, before hydraulic pressure ingot step, its effect in target product Si-C composite material is prepared otherwise can not be realized, that is, is ensured
Silicon and carbon are evenly distributed in the final product, and obtain good electric conductivity, and magnesium thermit process does not have impurity interference, without pair
Reaction occurs, and further ensures that the ordered structure and superperformance of target product Si-C composite material, each step coordinated, is total to
It is same to form a set of independent, complete technical scheme so that final to obtain with very high tap density and compacted density, well
The silicon-carbon of electronic conductivity, high specific discharge capacity and volume and capacity ratio, limited electrode expansion and superior cyclical stability
Composite is possibly realized.
It is embodiment below：
Embodiment 1
(1) 1~4 micron of glass and pitch are shone into mass ratio 10：3 ratio, using n-amyl alcohol as ball milling agent, it is put into
Mechanical ball mill 8h in agate pot, obtain the mixture of glass and carbonaceous organic material；
(2) by the glass and the mixture of pitch that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon gas ring
500 DEG C of insulation 2h are heated to 2 DEG C/min programming rate under border, then continue to be heated to 800 with 5 DEG C/min programming rate
DEG C carry out carbonization treatment；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.5：After 3 even mixing
Hydraulic pressure ingot under 4MPa 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 680 DEG C of insulation 4h, 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/agraphitic carbon composite is obtained after pickling.
From Fig. 1 scanning electron microscope (SEM) photograph, the silicon that the present embodiment is prepared belongs to the three-dimensional porous of 1~5 micron level
The silicon of structure, similar to ant nest shape, surface has one layer of agraphitic carbon to be wrapped in, and forms clad structure.
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 agraphitic carbon peak position of steamed bun shape is obvious, and substantially without dephasign.
From Fig. 3 transmission electron microscope picture, three-dimensional porous silicon that the present embodiment is prepared has excellent pore passage structure
And overall interpenetrate is not destroyed, and wherein aperture is 100~200 nanometers, the agraphitic carbon of porous silicon particle surface cladding
Thickness be 10~20 nanometers.This structure alleviates the volumetric expansion in charge and discharge process well, and adds electric conductivity,
The reason for can reveal that its superior performance.
The excellent electrochemistry cycle performance of porous silicon shown in Fig. 4, initial coulombic efficiency are up to 89.9%, circulate 300 times still
There is a higher capacity (1230mAh/g), conservation rate is up to 83%, good cycling stability, therefore the present invention can industrially big rule
Mould produces and application.
As shown in figure 5, the specific surface area of the porous silicon composite material of agraphitic carbon cladding is 130m2g-1, its intermediary hole
Aperture is 2~6 nanometers.The tap density of the composite is 1.16g/cm after tested3, compacted density 1.58g/cm3.This side
The porous silicon of method synthesis has suitable specific surface area and excellent pore structure, is suitable for lithium cell cathode material.
From Fig. 6 thermogravimetric curve, silicone content is 85wt%, carbon content 15wt% in the composite.
Embodiment 2
(1) 1~4 micron of glass and pitch are shone into mass ratio 10：3 ratio, using n-amyl alcohol as ball milling agent, it is put into agate
Mechanical ball mill 6h in Nao tanks, obtains the mixture of glass and pitch；
(2) by the glass and the mixture of pitch that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon gas ring
550 DEG C of insulation 2h are heated to 2 DEG C/min programming rate under border, then continue to be heated to 850 with 7 DEG C/min programming rate
DEG C carry out carbonization treatment；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.5：4 uniformly mixing after
Hydraulic pressure ingot under 3MPa 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 1.5mol/L hydrochloric acid.Then exist
Cleaned 30 minutes in 0.2mol/L hydrofluoric acid, porous silicon/agraphitic carbon composite is obtained after pickling.
Embodiment 3
(1) 1~4 micron of glass and coal tar are shone into mass ratio 10：4 ratio, using n-amyl alcohol as ball milling agent, it is put into
Mechanical ball mill 10h in agate pot, obtain the mixture of glass and coal tar；
(2) by the glass and the mixture of pitch that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon gas ring
400 DEG C of insulation 3h are heated to 1 DEG C/min programming rate under border, then continue to be heated to 900 with 6 DEG C/min programming rate
DEG C carry out carbonization treatment；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.55：3 uniformly mixing after
Hydraulic pressure ingot under 5MPa 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 780 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 10 hours in 2.5mol/L hydrochloric acid.Then exist
Cleaned 60 minutes in 0.5mol/L hydrofluoric acid, porous silicon/agraphitic carbon composite is obtained after pickling.
From Fig. 7 scanning electron microscope (SEM) photograph, the silicon that the present embodiment is prepared belongs to the three-dimensional porous of 1~5 micron level
The silicon of structure, surface have one layer of agraphitic carbon to be wrapped in, and form clad structure.
Embodiment 4
(1) 1~4 micron of glass and coal tar are shone into mass ratio 10：5 ratio, using n-amyl alcohol as ball milling agent, it is put into
Mechanical ball mill 12h in agate pot, obtain the mixture of glass and coal tar；
(2) by the glass and the mixture of pitch that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon gas ring
550 DEG C of insulation 1h are heated to 1 DEG C/min programming rate under border, then continue to be heated to 10 DEG C/min programming rate
1000 DEG C of progress carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.6：4 uniformly mixing after
Hydraulic pressure ingot under 4.5MPa 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 680 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 1 hour in 2mol/L hydrochloric acid.Then exist
Cleaned 15 minutes in 0.4mol/L hydrofluoric acid, porous silicon/agraphitic carbon composite is obtained after pickling.
Embodiment 5
(1) by 1~4 micron of glass and petroleum coke according to mass ratio 10：3 ratio, using n-amyl alcohol as ball milling agent, put
Enter mechanical ball mill 8h in agate pot, obtain the mixture of glass and petroleum coke；
(2) by the glass and the mixture of pitch that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon gas ring
500 DEG C of insulation 2h are heated to 5 DEG C/min programming rate under border, then continue to be heated to 900 with 5 DEG C/min programming rate
DEG C carry out carbonization treatment；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.6：5 uniformly mixing after
Hydraulic pressure ingot under 3MPa 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 5h, 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/agraphitic carbon composite is obtained after pickling.
Embodiment 6
(1) 1~4 micron of glass and petroleum coke are shone into mass ratio 10：4 ratio, using n-amyl alcohol as ball milling agent, it is put into
Mechanical ball mill 12h in agate pot, obtain the mixture of glass and petroleum coke；
(2) by the glass and the mixture of pitch that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon gas ring
550 DEG C of insulation 2h are heated to 3 DEG C/min programming rate under border, then continue to be heated to 10 DEG C/min programming rate
850 DEG C of progress carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.55：5 uniformly mixing after
Hydraulic pressure ingot under 5MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 3 DEG C/min programming rate
To 680 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 5 hours in 0.2mol/L hydrochloric acid.Then exist
Cleaned 30 minutes in 0.5mol/L hydrofluoric acid, porous silicon/agraphitic carbon composite is obtained after pickling.
Embodiment 7
(1) by 1~4 micron of glass and CNT according to mass ratio 10：1 ratio, using n-amyl alcohol as ball milling agent,
Mechanical ball mill 12h in agate pot is put into, obtains the mixture of glass and CNT；
(2) by the glass and the mixture of CNT that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot, in argon
550 DEG C of insulation 2h are heated to 3 DEG C/min programming rate under compression ring border, then continue to heat with 10 DEG C/min programming rate
To 850 DEG C of progress carbonization treatments；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.55：5 uniformly mixing after
Hydraulic pressure ingot under 5MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 3 DEG C/min programming rate
To 680 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 5 hours in 0.2mol/L hydrochloric acid.Then exist
Cleaned 30 minutes in 0.5mol/L hydrofluoric acid, porous silicon/carbon nano tube compound material is obtained after pickling.
From Fig. 8 scanning electron microscope (SEM) photograph, CNT and silicon mosaic are woven into network structure, and the composite includes more
Hole silicon and CNT, wherein CNT are interwoven three-dimensional net structure, and silicon is distributed in the space of these network structures
In, part CNT is embedded into silicon grain, will be connected between particle and particle, wraps up weave in, forms one
Individual three-dimensional connected stereochemical structure, the length of its CNT is 10~20 microns, through the tap density for measuring the composite
For 1.13~1.27g/cm3, compacted density is 1.46~1.60g/cm3, specific surface area 105m2g-1。
Embodiment 8
(1) by 1~4 micron of glass and bacteria cellulose according to mass ratio 10：3 ratio, ball milling is used as using n-amyl alcohol
Agent, mechanical ball mill 12h in agate pot is put into, obtains the mixture of glass and bacteria cellulose；
(2) by the glass and the mixture of bacteria cellulose that are obtained in step (1) under 1MPa pressure after hydraulic pressure ingot,
550 DEG C of insulation 2h are heated to 3 DEG C/min programming rate under ar gas environment, then continue to add with 10 DEG C/min programming rate
Heat carries out carbonization treatments to 850 DEG C；
(3) the sample grinding obtained step (2) is broken and magnesium powder, fused salt are according to mass ratio 1：0.55：5 uniformly mixing after
Hydraulic pressure ingot under 5MPa pressure；
(4) the sample ingot that step (3) obtains is put into the tube furnace full of argon gas and heated with 3 DEG C/min programming rate
To 680 DEG C of insulation 6h, reacted mixture is obtained；
(5) the reacted mixture that step (4) obtains first is cleaned 5 hours in 0.2mol/L hydrochloric acid.Then exist
Cleaned 30 minutes in 0.5mol/L hydrofluoric acid, porous silicon/carbon nano-fiber 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)
1. 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 carbon material, dries, is well mixed after separation of solid and liquid
Silicate glass powder and carbon material mixture；
(2) silicate glass powder and the mixture of carbon material obtained step (1) carries out carbonization treatment, mixes this after annealing
Compound is ground, and obtains the mixture of the silicate glass powder after carbonization treatment and carbon material；
(3) by the silicate glass powder after the carbonization treatment described in step (2) and the mixture of carbon material and magnesium powder and fused salt
Ingot is compacted after mixing, magnesiothermic reduction reaction then occurs under an inert atmosphere；Reaction product progress pickling processes are obtained into silicon
Carbon composite.
2. preparation method as claimed in claim 1, it is characterised in that the carbon material is carbon containing organic double compound or one-dimensional carbon
Material, the carbon containing organic double compound include one in pitch, petroleum coke, coal tar, phenolic resin, graphene and biomass carbon
Kind is a variety of；The one-dimensional carbon material includes the one or more in carbon fiber, bacteria cellulose and CNT.
3. preparation method as claimed in claim 1, it is characterised in that step (1) silicate glass powder and the carbon
The mass ratio of material is 10:2~5.
4. preparation method as claimed in claim 1, it is characterised in that step (2) carbonization treatment concretely comprises the following steps：
400~550 DEG C of 1~3h of insulation are heated to 1~5 DEG C/min programming rate under ar gas environment, then again with 5~10 DEG C/min
Programming rate be heated to 800~1000 DEG C insulation 2~4h.
5. preparation method as claimed in claim 1, it is characterised in that before step (2) described carbonization treatment, in addition to sub-step
Suddenly：The mixture of the silicate glass powder and carbon material is subjected to compacting ingot, the pressure model that the compacting ingot uses
Enclose preferably 0.5~2MPa.
6. preparation method as claimed in claim 1, it is characterised in that the silicate glass after step (3) described carbonization treatment
The mixture of powder and carbon material is 1 with the mass ratio of magnesium powder and fused salt：0.5~0.6：3~5.
7. the preparation method as described in claim 1 or 5, it is characterised in that step (3) pressure limit for being pressed into ingot use
For 1~5MPa；The compacting ingot is preferably realized by forcing press, hydraulic press or cold extrusion press.
8. preparation method as claimed in claim 1, it is characterised in that step (3) the magnesiothermic reduction reaction condition is：In argon
In gas atmosphere, 600~800 DEG C of 3~6h of insulation are heated to 2~5 DEG C/min programming rate.
9. a kind of Si-C composite material, it is characterised in that the Si-C composite material is according to any one of such as claim 1~8 institute
The preparation method stated is prepared.
10. a kind of application of Si-C composite material as claimed in claim 9, it is characterised in that for negative electrode of lithium ion battery
Material.
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| CN110289408A (en) * | 2019-06-26 | 2019-09-27 | 东北大学 | Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon |
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