CN108736006A - A method of preparing silico-carbo composite material - Google Patents

A method of preparing silico-carbo composite material Download PDF

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CN108736006A
CN108736006A CN201810830729.XA CN201810830729A CN108736006A CN 108736006 A CN108736006 A CN 108736006A CN 201810830729 A CN201810830729 A CN 201810830729A CN 108736006 A CN108736006 A CN 108736006A
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silicon
composite material
nano
silico
carbo composite
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CN108736006B (en
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洪若瑜
高茂川
王芳芳
王为旺
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Fuzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Silico-carbo composite process is prepared the invention discloses a kind of, after bulk polycrystal silicon raw material Mechanical Crushing, powder is ground to using dry grinding and superfine communication technique, under the auxiliary of water soluble surfactant active, is ground by multistage and nano-silicon slurry is made；The graphene of proper proportion is uniformly mixed with nano-silicon using vacuum homogenate technology, then by processes such as spray drying, granulation and sievings, obtains silico-carbo composite material.The present invention is without the use of toxic reagent during preparing nano-silicon, and does not need the complex processes such as molten acid, etching and washing, and clean environment firendly, product purity are high, the method for being full blast and most value-for-money；And vacuum homogenate, spray drying, granulation, sieving etc. are all the ripe operations of industrialization, i.e. the scale industrial production of silico-carbo composite material may be implemented in the method, and by design technology parameter, prepares the silicon carbon material of different performance.

Description

A method of preparing silico-carbo composite material
Technical field
The present invention relates to lithium cell cathode material preparing technical fields, and in particular to a kind of silico-carbo composite material of preparing Method.
Background technology
Along with a large amount of uses of economic globalization and fossil fuel, the problem of environmental pollution and energy shortage, increasingly dashes forward Go out.Seek new alternative, renewable, sustainable new energy and be important developing direction, lithium ion battery is as new energy One important representative in field, has been widely used in the multiple fields such as life, production, military affairs and scientific research.And improve lithium from The specific capacity of sub- battery improves its cycle performance and extends battery life, has become the weight of lithium ion battery future development Point, the chemical property of negative material play the role of the industrialization of lithium ion battery and development prospect very important.
Negative material is one of critical material of lithium ion battery, from the point of view of the Development History of lithium ion battery, cathode material The development of material promotes lithium ion battery to enter commercial applications.Initial lithium ion battery is cathode material using lithium metal Material, but lithium metal easy tos produce Li dendrite in charging and leads to the safety problems such as on fire or explosion.Subsequent development lithium alloy Material, it is expected that above-mentioned safety issue is solved, but alloy material is easy to happen volume expansion in embedding and removing, causes to follow Ring performance declines.By further studying and comparing, commercialization of the graphited carbon as lithium ion battery is had finally chosen Negative material.Carbonaceous material mainly has the following advantages：Specific capacity is higher, electrode potential is low, cycle efficieny is high, cycle life It is long, but with the continuous improvement that new-energy automobile in practical applications requires course continuation mileage, power battery associated materials also to The direction for higher energy density is developed.The graphite cathode of conventional lithium ion battery can no longer meet existing demand, high-energy The negative material of density becomes the new hot spot that enterprise chases.
Graphene, because it is with excellent calorifics, electricity and mechanical characteristic, in materialogy, micro-nano technology, the energy, biology Medicine etc. is with important application prospects, from Univ Manchester UK physicist An Deliegaimu in 2004 and health Si Tandingnuowoxiao loves, with micromechanics stripping method for the first time after obtaining graphene in graphite, various countries' input pair energetically The research of graphene.Recent study find, graphene have excellent electronic conductivity energy, can between electrode material granules structure At three-dimensional electronic and ion transport network architecture.And lithium ion battery charge/discharge rates be by lithium ion transmission in the electrodes and Deintercalation speed is determined that is, grapheme material is applied in lithium battery, can significantly promote the charge/discharge rates of lithium ion battery, It realizes the quantum jump of battery technology, and New Energy Industry will be pushed to realize jump development.
However, this lithium ion battery is limited by the complexity of graphene preparation process, cost is more expensive；And graphene material Though material has very high conductive and heat conduction rate, when as lithium cell cathode material, exist cycle coulombic efficiency for the first time it is low, The problems such as charging and discharging curve lag is serious, therefore be difficult to be used separately as electrode material.Nevertheless, if graphene is unique Flexible structure and high power capacity metal or other Nanocomposites, are used as negative material, then have advantageous advantage.
Graphene-based composite material about negative electrode of lithium ion battery research report it is more, mainly with metal, metal Oxide or silicon etc. it is compound.And silicon is that energy density is highest in current numerous negative materials, the addition of graphene powder can To overcome silicium cathode material during battery charging and discharging stores up lithium since volume acutely expands, crushes, and then lead to battery The problem of lost of life and cyclical stability are deteriorated.The specific capacity of silicon materials is up to 4200 mAh/g simultaneously, and silicon materials Rich reserves, price are relatively low, green non-poisonous；I.e. graphene and silicon materials all have as the certain excellent of negative electrode of lithium ion battery Point, the two combination can make up respective deficiency, display one's respective advantages, prepare high-performance lithium cell negative electrode material.This silicon- Graphene composite material will be applied in the power lithium-ion battery field that high-energy density, high power density require, greatly The big comprehensive performance for promoting power battery, pushes the development in the fields such as electric tool, new-energy automobile, aerospace.
Have the method that many researcher propositions prepare silicon-graphene composite material, such as University of Electronic Science and Technology at present Disclose a kind of graphene-silicon composite and its preparation method and application（Number of patent application is 201611082895.3）, Method is and to make silicon and graphene using hydro-thermal reaction by the way that graphene oxide, nano-silicon are distributed in water under ultrasonic agitation Homoepitaxial is in nickel foam, then by vacuum freezedrying, and the high temperature reduction under protective atmosphere is needed to obtain composite material. On the one hand prepared by such method needs more harsh operating condition and environment, be difficult to apply to industrial production；On the other hand its Raw material selective oxidation graphene, behind need to carry out high temperature reduction, while graphene oxide preparation process at present, need by water Wash, pickling, ultrasound, centrifugation, the processes such as drying, production process will produce waste liquid, exhaust gas, pollutes environment.
In order to which improve composite material prepares environment and harsh conditions, Saic Chery Automobile Co., Ltd discloses a kind of silicon substrate Negative material and its preparation method and application（Number of patent application is 201410531148.8）, method is by silicon nanoparticle point It being dispersed in the ethanol solution of graphene, the graphene that nano-silicon is would be embedded with after separating, washing is added in the solution of metalline, And certain density hydrofluoric acid is added, centrifugation obtains the graphene embedded with nano-silicon and nano metal, then carries out calcining and obtain silicon Base negative material.Although such method overcomes preparation process exacting terms, but whole preparation process is complicated, and is difficult standard The case where really judging each step composite material, thus it is difficult to ensure that the quality of target product；Preparation process uses metal salt simultaneously Solution and hydrofluoric acid, washing separation process can both cause consumption and the waste water handling problem of great lot of water resources；Simultaneously it is remaining from Son can influence the subsequent application of composite material.
In order to make the preparation process of graphene-nanometer silicon composite material more be simple and efficient, clean environment firendly, Beijing Aviation boat Its university discloses a kind of method that liquid phase Physical prepares graphene/nanometer silicon lithium ion battery cathode material（Patent CN201510294379）, preparation method is then to filter centrifugation gained by ultrasonic graphite powder and nano silica fume dispersion liquid Supernatant liquor obtains the composite material of graphene and nano-silicon through calcination processing.This method is although simple for process, but due to Many nano-silicons are all exposed, thus capacity is low, Cycle Difference.
The present invention is using multistage grinding technique, by block-like polysilicon grinding at nano-silicon slurry, and in the proper ratio Graphene powder is added in the nano-silicon slurry obtained to grinding；Graphene is made by vacuum refiner under certain condition and is received Rice silicon is uniformly mixed, then can be obtained nano-silicon-graphene composite material by spray drying, granulation, sieving.
Nano-silicon is prepared using multistage grinding, relatively traditional preparation nanometer silicon technology has following advantage：First, making With multistage grinding technique SiH is used with industrial4、SiCl4Equal gases cracking production nano-silicon will be compared more safely, can be with Keep nano-silicon preparation process safer, no exhaust gas generates, more environmentally-friendly；Meet in the Ecological Civilization Construction that present country advocates Contain.Second is that can carry out continuous production using multistage grinding technique, equipment completely can be on the market needed for whole production line It obtains, and grinding prepares that nano-silicon production process is simple, does not need the working condition of complicated production process and more harshness, this So that nano-silicon grinding technique can be applied to industrialized production.Third, the nano-silicon prepared by multistage grinding, compared to it His production technology, purity is high, impurity is few, and impurity is mainly silicon carbide and zirconium oxide, to subsequently being applied in field of lithium Almost without influence.
The present invention selects graphene as the carbon source of silico-carbo composite material, mainly due to the high conductivity of graphene, high ratio Surface area, high-flexibility and laminated structure can be very good the electric conductivity for improving silicon carbon material and contain silicon in charge and discharge Volume change.The silicon of simultaneous selection Nano grade makes nano level silicon volume change in charge and discharge generate as silicon materials Stress disperse, and can well with graphene carry out it is compound, generating structure preferably and performance stabilization silico-carbo composite material. Although silico-carbo composite material prepared by the present invention is compared to the silicon carbon material of very-high performance, it is understood that there may be capacity is relatively low Situation, the present invention can be produced in batches industrially, and preparation process simple possible, and prepare silico-carbo composite material Performance is all significantly improved compared with being commercialized graphite cathode material in the specific capacity and cyclical stability of material, Ke Yiman The demand of sufficient power battery.
Invention content
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of method preparing silico-carbo composite material, the work Skill process includes two parts, when the preparation of nano-silicon slurry, second is that the preparation of silico-carbo composite material, is as follows：
（1）The preparation of nano-silicon slurry：By bulk polycrystal silicon raw material be put into full ceramic machinery it is broken after, use double roller high pressure abrasive Machine dry grinding pSi powder, then ultramicro grinding is carried out, under the auxiliary of water soluble surfactant active, respectively with horizontal grinding Machine and vertical circulation grinder carry out classification wet grinding, obtain nano-silicon slurry；
（2）The preparation of silico-carbo composite material：In the proper ratio to step（1）It grinds in the nano-silicon slurry obtained and stone is added Black alkene powder makes graphene be uniformly mixed with nano-silicon using vacuum refiner, obtains nano-silicon-graphene slurry；Pass through again Spray drying, granulation and sieving process, obtain silico-carbo composite material.
By bulk polycrystal silicon raw material be put into full ceramic machinery it is broken after, use double roller high pressure abrasive machine dry grinding polysilicon Powder, then carry out ultramicro grinding；Wherein chunk polysilicon grain size is ground in the mm of 30 mm ~ 250 using double roller high pressure abrasive machine dry method PSi powder is ground to the mm of 1 mm ~ 7, ultramicro grinding to grain size is 10 μm ~ 80 μm.
The water soluble surfactant active includes polyethylene glycol, water-soluble polyaniline.
Step（1）In, respectively classification wet grinding is carried out with horizontal mill and vertical circulation grinder；Wherein using sleeping Formula grinder milling time is 3 ~ 6 hours（It is preferred that 4 ~ 5.5 hours）, grain size is the nm of 300 nm ~ 600（It is preferred that 400 nm ~ 500 nm）；It it is 6 ~ 28 hours using vertical lapping machine milling time（It is preferred that 8 ~ 14 hours）, grain size is the nm of 60 nm ~ 160（It is preferred that 90 nm~140 nm）.
Step（2）In, the mass ratio of the nano-silicon and graphene is 0.5:9.5~6.5:3.5（It is preferred that 2.5:7.5~ 4.5:5.5）.
Step（2）Described in be spray-dried when air inlet temperature be 180 DEG C ~ 280 DEG C（It is preferred that 200 DEG C ~ 240 DEG C）, Outlet temperature is 90 DEG C ~ 170 DEG C（It is preferred that 110 DEG C ~ 130 DEG C）.
The beneficial effects of the present invention are：
1）The present invention prepares nano-silicon by grinding, and toxic reagent is without the use of in preparation process, and does not need sour molten, etching With washing etc. complex processes, this method for being full blast and most value-for-money；Simultaneously by grinding the nano-silicon prepared Purity is high, few on follow-up influential impurity（A small amount of impurity is mainly silicon carbide and zirconium oxide）；And vacuum homogenate, spraying are done Dry, granulation, sieving are all the ripe operations of industrialization, i.e., the extensive of silico-carbo composite material may be implemented by such method Industrial production, and production process is more environmentally friendly, pollution is small, while can be easily achieved annual output by multistage grinding production nano-silicon 500 tons（Dry powder quality）, and then can ensure the production capacity of 1500 tons/year of silico-carbo composite materials；
2）It is directed to technical process simultaneously, the silico-carbo composite material of different performance can be prepared by adjusting technological parameter, for Middle and high end lithium battery material can prepare the smaller nano-silicon slurry of grain size, simultaneously by increasing nano-silicon multistage milling time The modes such as high-quality graphene powder, the ratio of control nano-silicon and graphene and increase vacuum Homogenization time can also be used, To obtain high performance silicon-carbon composite；Production technology i.e. of the present invention can take into account production cost and properties of product, can be according to not Same demand, can go the performance for producing the silico-carbo composite material of different performances with design technology parameter.
Description of the drawings
Fig. 1 is the nano-silicon slurry preparation flow figure in the embodiment of the present invention；
The scanning electron microscope (SEM) photograph of Fig. 2 silico-carbo composite materials；
TEM figures, AFM shape appearance figures and the elevation information figure of Fig. 3 silico-carbo composite materials；
Fig. 4 silico-carbo composite materials do test chart when cathode of lithium battery active material.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, those skilled in the art will manage Solution, following embodiment are merely a preferred embodiment of the present invention, and to more fully understand the present invention, thus should not be regarded as limiting this hair Bright range.
Embodiment 1
After the polycrystalline silicon raw material that grain size is about 15cm is put into complete ceramic crusher Mechanical Crushing, double roller high pressure abrasive machine dry method is used PSi powder is ground to about 2 mm of grain size, by ultramicro grinding to 500 mesh or so, in the poly- second of water soluble surfactant active two Under the auxiliary of alcohol, 4 hours are ground to 500 nm of grain size or so using horizontal mill；It is detached by tube centrifuge, by 500 Nm or more materials return to mixed grinding, and slurry of the grain size less than 500 nm is ground 8 hours in vertical lapping machine, and granulation diameter is about 140 nm, separation can be obtained nano-silicon slurry.With nano-silicon and graphene ratio for 2:8 ratio, into nano-silicon slurry Graphene powder is added, is uniformly mixed using vacuum refiner, then with inlet temperature for 260 DEG C, outlet temperature is 100 DEG C Condition is spray-dried, and is granulated, and be sieved, and silico-carbo composite material is just obtained.The scanning electricity of the silico-carbo composite material of preparation Mirror figure is as shown in Figure 2.
Embodiment 2
After the polycrystalline silicon raw material that grain size is about 18cm is put into complete ceramic crusher Mechanical Crushing, using using double roller high pressure abrasive machine Dry grinding pSi powder gathers by ultramicro grinding to 500 mesh or so in surfactant water-soluble to about 2 mm of grain size Under the auxiliary of aniline, 6 hours are ground to 350 nm of grain size or so using horizontal mill；It is detached by tube centrifuge, by 350 Nm or more materials return to mixed grinding, and slurry of the grain size less than 350 nm is ground 12 hours in vertical lapping machine, and granulation diameter is about For 100 nm, separation can be obtained nano-silicon slurry.With nano-silicon and graphene ratio for 2.5:7.5 ratio, to nano-silicon Graphene powder is added in slurry, is uniformly mixed using vacuum refiner, then with inlet temperature for 280 DEG C, outlet temperature is 110 DEG C of condition, is spray-dried, and is granulated, and be sieved, and silico-carbo composite material is just obtained.Prepare the TEM numbers of plies of product Figure, AFM shape appearance figures are as shown in Fig. 3.
Embodiment 3
After the polycrystalline silicon raw material that grain size is about 12cm is put into complete ceramic crusher Mechanical Crushing, double roller high pressure abrasive machine dry method is used PSi powder is ground to about 2 mm of grain size, by ultramicro grinding to 500 mesh or so, in surfactant water-soluble polyaniline Auxiliary under, grind 6 hours to 350 nm of grain size or so using horizontal mill；It is detached by tube centrifuge, by 350 nm The above material returns to mixed grinding, and slurry of the grain size less than 350 nm is ground 18 hours in vertical lapping machine, and granulation diameter is about 70 nm, separation can be obtained nano-silicon slurry.With nano-silicon and graphene ratio for 3.5:6.5 ratio, to nano-silicon slurry Middle addition graphene powder is uniformly mixed using vacuum refiner, then with inlet temperature for 240 DEG C, and outlet temperature is 120 DEG C Condition, be spray-dried, be granulated, and be sieved, just obtain silico-carbo composite material.It prepares silico-carbo composite material and does lithium battery Shown in test chart attached drawing 4 when negative electrode active material.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification should all belong to the covering scope of the present invention.

Claims (9)

1. a kind of method preparing silico-carbo composite material, it is characterised in that：Process includes preparation and the silico-carbo of nano-silicon slurry The preparation of composite material, is as follows：
（1）The preparation of nano-silicon slurry：By bulk polycrystal silicon raw material be put into full ceramic machinery it is broken after, use double roller high pressure abrasive Machine dry grinding pSi powder, then ultramicro grinding is carried out, under the auxiliary of water soluble surfactant active, respectively with horizontal grinding Machine and vertical circulation grinder carry out classification wet grinding, obtain nano-silicon slurry；
（2）The preparation of silico-carbo composite material：To step（1）It grinds in the nano-silicon slurry obtained and graphene powder is added, use Vacuum refiner, makes graphene be uniformly mixed with nano-silicon, obtains nano-silicon-graphene slurry；Again by being spray-dried, being granulated With sieving process, silico-carbo composite material is obtained.
2. a kind of method preparing silico-carbo composite material according to claim 1, it is characterised in that：By chunk polysilicon Raw material be put into full ceramic machinery it is broken after, using double roller high pressure abrasive machine dry grinding pSi powder, then carry out ultramicro grinding； Wherein chunk polysilicon grain size uses double roller high pressure abrasive machine dry grinding pSi powder to 1 mm ~ 7 in the mm of 30 mm ~ 250 Mm, ultramicro grinding to grain size are 10 μm ~ 80 μm.
3. a kind of method preparing silico-carbo composite material according to claim 1, it is characterised in that：The water solubility table Face activating agent includes polyethylene glycol, water-soluble polyaniline.
4. a kind of method preparing silico-carbo composite material according to claim 1, it is characterised in that：Step（1）In, point Classification wet grinding is not carried out with horizontal mill and vertical circulation grinder；Wherein utilize horizontal mill milling time be 3 ~ 6 hours, grain size was the nm of 300 nm ~ 600；It it is 6 ~ 28 hours using vertical lapping machine milling time, grain size is 60 nm ~ 160 nm。
5. a kind of method preparing silico-carbo composite material according to claim 4, it is characterised in that：It is ground respectively with horizontal Grinding machine and vertical circulation grinder carry out classification wet grinding；It is 4 ~ 5.5 hours wherein to utilize horizontal mill milling time, grain Diameter is the nm of 400 nm ~ 500；It it is 8 ~ 14 hours using vertical lapping machine milling time, grain size is the nm of 90 nm ~ 140.
6. a kind of method preparing silico-carbo composite material according to claim 1, it is characterised in that：Step（2）In, institute The mass ratio for stating nano-silicon and graphene is 0.5:9.5~6.5:3.5.
7. a kind of method preparing silico-carbo composite material according to claim 6, it is characterised in that：The nano-silicon slurry The mass ratio of material and graphene powder is 2.5:7.5~4.5:5.5.
8. a kind of method preparing silico-carbo composite material according to claim 1, it is characterised in that：Step（2）Described in Air inlet temperature is 180 DEG C ~ 280 DEG C when spray drying, and outlet temperature is 90 DEG C ~ 170 DEG C.
9. a kind of method preparing silico-carbo composite material according to claim 8, it is characterised in that：When spray drying into Gas port temperature is 200 DEG C ~ 240 DEG C, and outlet temperature is 110 DEG C ~ 130 DEG C.
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CN117174885A (en) * 2023-11-03 2023-12-05 琥崧科技集团股份有限公司 Silicon-carbon negative electrode material and preparation method and application thereof
CN117174885B (en) * 2023-11-03 2024-01-26 琥崧科技集团股份有限公司 Silicon-carbon negative electrode material and preparation method and application thereof

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