CN103165870B - A kind of silicon based composite material, lithium ion battery and its preparation method and application - Google Patents
A kind of silicon based composite material, lithium ion battery and its preparation method and application Download PDFInfo
- Publication number
- CN103165870B CN103165870B CN201110415070.XA CN201110415070A CN103165870B CN 103165870 B CN103165870 B CN 103165870B CN 201110415070 A CN201110415070 A CN 201110415070A CN 103165870 B CN103165870 B CN 103165870B
- Authority
- CN
- China
- Prior art keywords
- based composite
- silicon based
- composite material
- manufacturing process
- materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
The invention discloses a kind of manufacturing process of silicon based composite material: under the existence of the metal dust of submicron order, with peroxide initiation reaction raw material: Polycarbosilane and/or polysiloxanes carry out cross-linking polymerization and obtain crosslinking curing product; The molecular weight of Polycarbosilane or polysiloxanes is 800-5000g/mol; In described Polycarbosilane or polysiloxanes, at least there is an active H; Described crosslinking curing product is obtained intermediate materials in 600-1000 DEG C of roasting; By described intermediate materials, graphite and binding agent mixing also wet ball grinding, spraying dry obtains spherical particle; Described spherical particle is heat-treated in 400-800 DEG C.Present invention also offers the silicon based composite material and application thereof that are obtained by the method, and a kind of lithium ion battery using this silicon based composite material as negative material.The shape of silicon based composite material particle of the present invention is good, and have good initial charge/discharge performance and electric cycle performance, preparation method of the present invention is applicable to industry and changes into production, low to the pollution of environment, with low cost.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of silicon based composite material and its preparation method and application, the present invention relates to a kind of lithium ion battery containing described silicon based composite material.
Background technology
Mostly adopt graphite-like raw material as lithium ion battery negative material in the market, the relevant non-carbon negative material of research mainly comprises: nitride, silicon and silicide, tin-based oxide and tin compound, novel alloy, titanyl compound etc.Wherein silicon materials have the large advantage of specific capacity as lithium ion battery negative material, are one of focuses of high-capacity lithium-ion negative material research.Although silicon has maximum theoretical capacity 4200mAh/g, its poor efficiency first and cycle performance limit its commercial applications.For adapting to modern society to the needs of high power capacity, high-density lithium ion battery, a lot of technology need be adopted to be used for improving the above-mentioned defect of silicium cathode material.More typical technology has: nano Si and graphite-like are carried out mechanical compound; On silicon grain, carbon-coating is applied by chemical vapour deposition (CVD); Chemical reactive synthesis material is carried out by silicon-containing material.By material prepared by chemical synthesis means, because internal structure is relatively more even, material shows relatively excellent electric cycle performance.
Above-mentioned art methods adds charging/discharging capacity, energy density, first efficiency and cycle performance to a certain extent, but still can not meet the needs of market to such material, and therefore, current technology still needs further lifting.
Publication number is the patent of invention of CN101931076A, disclose a kind of preparation method and application of silicon carbide composite particles, solution containing silicon source and carbon source is carried out electrostatic spray, obtain spheric granules, described spheric granules is sintered under non-oxidizing atmosphere, obtain described silicon carbide composite particles, this its cycle performance of silica-base material of being obtained by mechanical compound is also unsatisfactory.The patent No. is the patent of invention of CN200510124903.1, disclose a kind of Si-C-O composite material, it take chloroplatinic acid as catalyst, with reactive silane and siloxanes for raw material, by the addition reaction of hydrogen, crosslinking curing generates containing Si-C-O composite material, and then sintering generates the cell negative electrode material of inorganic states.This technical scheme makes the cycle performance of material be improved to a certain extent, but it is high to react the catalyst chloroplatinic acid price that uses, and easily by the impact of market fluctuation, cause production cost high, be difficult to realize industrially scalable; In addition, reaction need use two kinds of raw materials: a kind of for providing silane or the siloxanes of activity hydrogen, and another kind of for providing the siloxanes of unsaturated group of aliphatic series, the degree of cross linking of its reaction is lower, reacts insufficient, affects the final performance of material; Finally, it is irregularly shaped for sintering the inorganic material particle obtained, and specific area is large, affects the cycle performance of material, cause hydraulic performance decline after making lithium cell cathode material." JournalofPowerSources " 196 (2011) 2875-2878 openly use t etram-ethyltetravinylcyclotetrasiloxane for reaction monomers, prepare containing Si-C-O composite material, although employing cheap cumyl peroxide is initator, but reaction principle is free radical causes double bond addition reaction, reactivity is lower, crosslinked insufficient, be difficult to form fine and close Si-C-O space structure, thus greatly have impact on the cycle performance of material.
Summary of the invention
Technical problem to be solved by this invention is to overcome the existing silicon based composite material cycle performance defect that still not ideal enough or production cost is higher, provides a kind of silicon based composite material and its production and use.Present invention also offers a kind of lithium ion battery containing described silicon based composite material.Silicon based composite material of the present invention has extraordinary cycle performance, is more suitable for using as li-ion electrode materials.Preparation method of the present invention is with low cost, is applicable to suitability for industrialized production.
The invention provides a kind of manufacturing process of silicon based composite material, it comprises the steps:
(1) under the existence of the metal dust of submicron order, with peroxide initiation reaction raw material: Polycarbosilane and/or polysiloxanes carry out the crosslinking curing product that cross-linking polymerization obtains tridimensional network; The molecular weight of Polycarbosilane or polysiloxanes is 800-5000g/mol; At least there is in described Polycarbosilane an active H, at least there is in described polysiloxanes an active H;
(2) described crosslinking curing product is obtained intermediate materials in 600-1000 DEG C of roasting under non-oxidizing atmosphere;
(3) by described intermediate materials, graphite and binding agent mixing also wet ball grinding, spraying dry obtains spherical particle;
(4) described spherical particle is heat-treated in 400-800 DEG C under non-oxidizing atmosphere, obtain described silicon based composite material.
After manufacturing process of the present invention is heat-treated at 400-800 DEG C, do not need to carry out again pulverizing or classification, silicon based composite material that is spherical or approximate sphericity can be obtained.
In step (1), described reaction raw materials is Polycarbosilane and/or polysiloxanes, is preferably Polycarbosilane or polysiloxanes, is more preferably polysiloxanes.
Described Polycarbosilane (being called for short PCS) is the high molecular polymer being formed main chain or side chain with Si-C key.
Described Polysiloxane is the organo-silicon compound being formed main chain or side chain with Si-O key.
Described active H refers to the H be connected with the Si in Si-O key or the H be connected with the Si in Si-C key.
In the present invention, described Polycarbosilane and/or polysiloxanes can be the high molecular polymer of various form, as long as it can carry out Raolical polymerizable thus obtain crosslinking curing product, as linear molecule, side chain molecule, ring molecule all can, be preferably linear molecule.
In the present invention one preferably execution mode, the structure shown in described Polycarbosilane and/or polysiloxanes have any one of general formula I ~ III:
general formula I
general formula I I
general formula III
Wherein, R
1~ R
16represent the alkyl of hydrogen atom or carbon number 1 ~ 12 respectively, R
1~ R
5can not be alkyl simultaneously, R
6~ R
12can not be alkyl simultaneously, R
13~ R
16can not be alkyl simultaneously.M and n is respectively the integer of 10 ~ 100, p and q is respectively the integer of 15 ~ 100.Described alkyl can be alkyl, thiazolinyl, alkynyl, aryl or aralkyl, is preferably alkyl, is more preferably the alkyl of carbon number 1 ~ 3, is methyl best.
In the execution mode that the present invention one is better, described polysiloxanes is polymethyl hydrogen siloxane, with single polymethyl hydrogen siloxane, for reaction raw materials can be formed, the degree of cross linking is larger, the more sufficient crosslinking curing product of reaction, decrease the existence of a large amount of low chain molecule in product simultaneously, avoid the volatilization of follow-up sintering process small molecular.
In step (1), described Polycarbosilane or the molecular weight of polysiloxanes are 800-5000g/mol.When molecular weight is lower than 800g/mol, the degree of polymerization of described cross-linking polymerization is low, is not enough to full cross-linked; When molecular weight is higher than 5000g/mol, raw material reaction activity is low, is also unfavorable for cross-linking polymerization.
In step (1), the metal dust of described submicron order to be average grain diameter the be metal dust of 100nm-1.0 μm.Described metal dust is for improving the conductibility (middle finger conductivity of the present invention) of described silicon based composite material, the various of this area routine use can be selected to have good conductive metal dust, being preferably one or more in copper powder, silver powder and magnesium powder, is more preferably copper powder.The consumption of described metal dust is preferably the 0.5-5% of described reaction raw materials quality.
In step (1), the various peroxide that described peroxide adopts this area to use as radical polymerization initiator are preferably cumyl peroxide and/or benzoyl peroxide, are more preferably cumyl peroxide.The consumption of described peroxide is the conventional amount used of this area initator, is preferably the 0.5-5% of described reaction raw materials quality.
In step (1), the reaction temperature of described cross-linking polymerization is the ordinary temperature of this type of reaction, and being preferably more than 170 DEG C, is more preferably 170-350 DEG C.When temperature is lower than 170 DEG C, described initator can not decompose generation free radical completely, and be unfavorable for the complete of reaction, temperature causes energy consumption high higher than when 350 DEG C.The reaction time of described cross-linking polymerization is advisable so that detection reaction consumption of raw materials is complete, is preferably more than 1 hour, is more preferably 1-8 hour.
The concrete operations of step (1) are: described metal dust, described reaction raw materials and peroxide are mixed, under nitrogen protection in 170-350 DEG C of reaction 1-8 hour.
In step (2), the sintering temperature of described roasting is 600-1000 DEG C.The temperature retention time of described roasting is preferably 4-10 hour.The temperature retention time of described roasting refers to the time be incubated after being warming up to described sintering temperature.
Non-oxidizing atmosphere in step (2) can adopt the technological means of this area routine to realize, as carried out under nitrogen protection.
In step (3), the average grain diameter of described graphite is preferably 1-20 μm, is more preferably 3-10 μm.Graphite in the present invention is Delanium and/or native graphite.
In step (3), the mixing ratio of described graphite and described intermediate materials is preferably 1: 10-1: 1, is more preferably 1: 2-1: 1.
In step (3), described binding agent is the binding agent that this area routine uses, and is preferably contracting sodium carboxymethylcellulose pyce (being called for short CMC) and/or polyvinyl alcohol (being called for short PVA).The consumption of described binding agent is the conventional amount used of this area, is preferably the 0.1-10% of described intermediate materials and described graphite gross mass.
In step (3); described wet ball grinding decentralized medium used is the conventional dispersion medium of this area wet ball grinding; be preferably one or more in water, ethanol, cyclohexane, toluene and acetone, be more preferably water, be conducive to cost-saving, protection of the environment.The consumption of described decentralized medium is the conventional amount used of this area, preferably makes the solid content of ball milling slurry be 10-20wt%, to ensure that the viscosity of ball milling slurry is applicable to spray drying treatment.Described ball milling slurry comprises described intermediate materials, described graphite and described decentralized medium and binding agent.
In step (3), particle diameter is preferably milled to 1-10 μm by described wet ball grinding.When being greater than 10 μm, the spherical particle specific area formed after spraying dry is comparatively large, easily causes the electrical property of composite material to decline; When particle diameter is less than 1 μm, particle is easily reunited, and is unfavorable for dispersion.
In step (3), described spraying dry preferably makes the water content in described spherical particle be less than 5%.Described spraying dry preferably carries out in spray dryer or spray drying device, and the intake air temperature of described spray dryer or spray drying device is preferably 200-300 DEG C, is more preferably 220-270 DEG C; Air outlet temperature is preferably 90-150 DEG C, is more preferably 100-130 DEG C; Spraying frequency is preferably 250-350Hz.
Non-oxidizing atmosphere in step (4) can adopt the technological means of this area routine to realize, as carried out under nitrogen protection.
In step (4), described heat treatment makes remaining moisture and volatile matter removing, and the macromolecular chain in binding agent is ruptured, and finally forms amorphous carbon.The described heat treated processing time removes as stopping completely to detect volatile matter.
Present invention also offers a kind of silicon based composite material obtained by above-mentioned manufacturing process.In silicon based composite material of the present invention, the total content of element silicon is preferably 20-40wt%, and the total content of carbon is preferably 40-70wt%, and the total content of oxygen element is preferably 0-20wt%.
Present invention also offers the purposes of described silicon based composite material as ion cathode material lithium.
Present invention also offers made a kind of lithium ion battery, it is using silicon based composite material of the present invention as negative material.
In the present invention, above-mentioned optimum condition can combination in any on the basis meeting this area general knowledge, obtains each preferred embodiment of the present invention.
Raw material of the present invention and reagent are all commercially.
Positive progressive effect of the present invention is:
1, in silicon based composite material of the present invention, the shape of particle is good, for spherical or spheroidal, (initial charge capacity is higher than 1150mAh/g to have good initial charge/discharge performance, initial discharge capacity is higher than 870mAh/g), and good electric cycle performance (after circulating 100 weeks, residual capacity is higher than 85% of initial capacity).
2, preparation method of the present invention is applicable to industry and changes into production, low to the pollution of environment, with low cost.
3, silicon based composite material of the present invention can directly use as lithium-ion negative pole battery, does not need other materials that adulterate again.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the silicon based composite material that embodiment 3 obtains.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited, the raw material in embodiment is conventional commercial product.
The CMC used in following embodiment is purchased from Weifang Z-TEK composite material Co., Ltd, and its concentration is the viscosity of the aqueous solution of 20g/l is 400-800mp.s.
PVA2488 is purchased from Guangzhou Qi Sheng Chemical Co., Ltd..
Polycarbosilane is purchased from Suzhou Cerafil Ceramic Fiber Co., Ltd., and its fusing point is: 170 DEG C ~ 220 DEG C, and range of molecular weight distributions is 800-2000g/mol, and what wherein silicon atom connects is methyl and hydrogen.
Embodiment 1
Get polymethyl hydrogen siloxane and 10g cumyl peroxide (0.5wt%) that 2000g mean molecule quantity is 800g/mol; add the copper powder that 10g (0.5wt%) particle diameter is 0.5 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 1 hour after temperature reaction still to 170 DEG C gradually, is cooled to discharging after room temperature.Afterwards by the charing kiln roasting 6 hour of above-mentioned crosslinking curing product at 600 DEG C.Get the graphite that cooled discharging 1000g and 1000g particle diameter are 3 μm to mix, the aqueous solution 10kg simultaneously added containing 2g (0.1wt%) CMC carries out wet ball grinding.Be milled to when particle diameter is 1 μm and carry out spraying dry, controlling spray dryer intake air temperature is 200 DEG C, and air outlet temperature is 100 DEG C, and spraying frequency is 250Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 400 DEG C and heat treatment 4 hours under nitrogen protection.
Embodiment 2
Get polymethyl hydrogen siloxane and 100g cumyl peroxide (5wt%) that 2000g mean molecule quantity is 5000g/mol; add the copper powder that 100g (5wt%) particle diameter is 1 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 8 hours after temperature reaction still to 350 DEG C gradually, is cooled to discharging after room temperature.Afterwards by the charing kiln roasting 6 hour of above-mentioned crosslinking curing product at 1000 DEG C.Get the graphite that cooled discharging 1000g and 1000g particle diameter are 8 μm to mix, the aqueous solution 10kg simultaneously added containing 200g (10wt%) CMC carries out wet ball grinding.Be milled to when particle diameter is 10 μm and carry out spraying dry, controlling spray dryer intake air temperature is 300 DEG C, and air outlet temperature is 150 DEG C, and spraying frequency is 350Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 800 DEG C and heat treatment 10 hours under nitrogen protection.
Embodiment 3
Get polymethyl hydrogen siloxane and 50g (2.5wt%) cumyl peroxide that 2000g mean molecule quantity is 2000g/mol; add the copper powder that 40g (2wt%) particle diameter is 0.5 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, is cooled to discharging after room temperature.Afterwards by the charing kiln roasting 6 hour of above-mentioned crosslinking curing product at 800 DEG C.Get the graphite that cooled discharging 1000g and 1000g particle diameter are 5 μm to mix, the aqueous solution 10kg simultaneously added containing 100g (5wt%) CMC carries out wet ball grinding.Be milled to when particle diameter is 4 μm and carry out spraying dry, controlling spray dryer intake air temperature is 250 DEG C, and air outlet temperature is 125 DEG C, and spraying frequency is 300Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 600 DEG C and heat treatment 5 hours under nitrogen protection.
Embodiment 4
(fusing point is: 170 DEG C ~ 220 DEG C to get the Polycarbosilane that 2000g mean molecule quantity is 1000g/mol; Suzhou Cerafil Ceramic Fiber Co., Ltd.) and 50g (2.5wt%) benzoyl peroxide; add the copper powder that 40g (2wt%) particle diameter is 0.1 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, is cooled to discharging after room temperature.Afterwards by the charing kiln roasting 6 hour of above-mentioned crosslinking curing product at 800 DEG C.Get the graphite that cooled discharging 1000g and 500g particle diameter are 1 μm to mix, the aqueous solution 6kg simultaneously added containing 75g (5wt%) CMC carries out wet ball grinding (solid content of ball milling slurry is 20%).Be milled to when particle diameter is 4 μm and carry out spraying dry, controlling spray dryer intake air temperature is 250 DEG C, and air outlet temperature is 125 DEG C, and spraying frequency is 300Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 600 DEG C and heat treatment 5 hours under nitrogen protection.
Embodiment 5
Get polymethyl hydrogen siloxane and 50g (2.5wt%) cumyl peroxide that 2000g mean molecule quantity is 2000g/mol; add the magnesium powder that 40g (2wt%) particle diameter is 1 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, is cooled to discharging after room temperature.Afterwards by the charing kiln roasting 6 hour of above-mentioned crosslinking curing product at 800 DEG C.Get the graphite that cooled discharging 1000g and 100g particle diameter are 20 μm to mix, the aqueous solution 10.5kg simultaneously added containing 75g (5wt%) PVA2488 carries out wet ball grinding (solid content of ball milling slurry is 10%), be milled to when particle diameter is 4 μm and carry out spraying dry, controlling spray dryer intake air temperature is 250 DEG C, air outlet temperature is 125 DEG C, and spraying frequency is 300Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 600 DEG C and heat treatment 5 hours under nitrogen protection.
Embodiment 6
Get polymethyl hydrogen siloxane and 50g (2.5wt%) cumyl peroxide that 2000g mean molecule quantity is 2000g/mol; add the copper powder that 40g (2wt%) particle diameter is 0.5 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, is cooled to discharging after room temperature.Afterwards by the charing kiln roasting 6 hour of above-mentioned crosslinking curing product at 800 DEG C.Get the graphite that cooled discharging 1000g and 1000g particle diameter are 5 μm to mix, adding 10kg cyclohexane is that decentralized medium carries out ball milling (solid content of ball milling slurry is 16.7%), when ball milling particle diameter to 4 μm, ball milling terminates, and the cyclohexane removed in slurry, add the aqueous solution 10kg (solid content of slurry is 16.7%) containing 100g (5wt%) CMC afterwards wherein and stir and carry out spraying dry, controlling spray dryer intake air temperature is 250 DEG C, air outlet temperature is 125 DEG C, and spraying frequency is 300Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 600 DEG C and heat treatment 5 hours under nitrogen protection.
Comparative example 1
Get polymethyl hydrogen siloxane and 50g cumyl peroxide (2.5wt%) that 2000g mean molecule quantity is 2000g/mol; add the copper powder that 40g (2wt%) particle diameter is 0.5 μm simultaneously; put into reactor after mixing to stir; and pass into nitrogen protection; insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, is cooled to discharging after room temperature.Discharging is pulverized and controlled particle diameter is 6 μm, afterwards above-mentioned crushed material is placed in carbide furnace 800 DEG C of heat treatments and obtains composite material in 6 hours.
Comparative example 2
Get polymethyl hydrogen siloxane and the different acene of 50g peroxidating two (2.5wt%) that 2000g mean molecule quantity is 2000g/mol; put into reactor after mixing to stir; and pass into nitrogen protection, insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, be cooled to discharging after room temperature.Afterwards by above-mentioned crosslinking curing product carbonization treatment 6 hours in the retort of 800 DEG C.Get the graphite that cooled discharging 1000g and 1000g particle diameter are 5 μm to mix, the aqueous solution 10kg simultaneously added containing 100g (5wt%) CMC carried out wet ball grinding and carry out spraying dry when particle diameter is 5 μm, controlling spray dryer intake air temperature is 250 DEG C, air outlet temperature is 125 DEG C, and spraying frequency is 300Hz.Obtain spherical particle product in whirlwind material, to be put in the carbide furnace of 600 DEG C and under nitrogen protection carbonization 5 hours silicon based composite material.
Comparative example 3
Get 2000g t etram-ethyltetravinylcyclotetrasiloxane (LS-8670; chemical company of SHIN-ETSU HANTOTAI) mix with the different acene of 50g peroxidating two (2.5wt%); be placed in reactor to stir; under nitrogen protection; insulation reaction 4 hours after temperature reaction still to 250 DEG C gradually, is cooled to discharging after room temperature.Afterwards by above-mentioned crosslinking curing product carbonization treatment 6 hours in the retort of 800 DEG C.Discharging is pulverized and controlled particle diameter is 6 μm, afterwards above-mentioned crushed material is placed in carbide furnace 800 DEG C of heat treatments and obtains composite material in 6 hours.
Comparative example 4
Get 1200g t etram-ethyltetravinylcyclotetrasiloxane (LS-8670; chemical company of SHIN-ETSU HANTOTAI) and the mixing of 800g polymethyl hydrogen siloxane; add the aqueous solution 100g containing 1g chloroplatinic acid afterwards; under nitrogen protection, 250 DEG C carry out Si―H addition reaction cross-linking reaction in a kettle.; and be incubated 4 hours, be cooled to discharging after room temperature.Discharging is pulverized and controlled particle diameter is 6 μm, afterwards above-mentioned crushed material is placed in carbide furnace 800 DEG C of heat treatments and obtains composite material in 6 hours.
Effect example 1 battery testing
(1) silicon based composite material of above-described embodiment 1-6 and obtained 93 parts, the composite material of comparative example 1-4 is directly got, add the aqueous solution 200 parts containing 7 parts of CMC/Super-P/SBR (mass ratio 2.5: 2.5: 2) wherein, after mixing, form slurry;
(2) described slurry being coated on thickness is on the Copper Foil of 15 μm, and drying, roll forming are electrode slice.Be to electrode with lithium paper tinsel, form lithium-ions battery with above-mentioned obtained copper foil electrode.Electrolyte used is for containing solvent vinyl carbonate (EC)/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) (volume ratio is 1: 1: 1), containing electrolyte 1mol/L lithium hexafluoro phosphate (LiPF
6) solution that is mixed with.Adopt polypropylene, polyethylene/polypropylene (PP/PE/PP) three layers of micro-pore septum, thickness is 20 μm.Test charging and discharging currents density is 0.6mA/cm
2, cut-off charging/discharging voltage is 0.005-2.000V.Measuring the starting efficiency of described lithium-ions battery, doing by repeating above-mentioned bath, described lithium-ions battery carries out charge/discharge and tests 50 times and 100 circulations, test result is in table 1.
Table 1
Remarks: due in the battery testing process of comparative example, capacity attenuation is very fast, when circulation surplus does not arrive 0, end loop.
Embodiment 1,2,3 is respectively corresponding is raw material with polymethyl hydrogen siloxane, take cumyl peroxide as initator, carry out at different conditions after adding copper powder being cross-linked, carbonize the silica-based spherical particle compound material that process, ball milling and spray drying experiment obtain.
Embodiment 4 is: be raw material with Polycarbosilane, take benzoyl peroxide as initator, carries out at different conditions being cross-linked, carbonizes the silica-based spherical particle compound material that process, ball milling and spray drying experiment obtain after adding copper powder.
Embodiment 5 is: be raw material with polymethyl hydrogen siloxane, take cumyl peroxide as initator, carry out at different conditions being cross-linked, carbonizing process, ball milling after adding magnesium powder, and take PVA as the silica-based spherical particle compound material that binding agent carries out spraying dry and obtains.
Embodiment 6 is: be raw material with polymethyl hydrogen siloxane, take cumyl peroxide as initator, carry out at different conditions being cross-linked, carbonizing process after adding copper powder, and be that dispersant carries out ball milling with cyclohexane, finally by the silica-based spherical particle compound material that spraying dry obtains.
Comparative example 1 is: be raw material with polymethyl hydrogen siloxane, take cumyl peroxide as initator, carries out being cross-linked, carbonizing process, the composite material of the silica-based irregular shape not adopting drying process with atomizing to obtain after adding copper powder.
Comparative example 2 is: be raw material with polymethyl hydrogen siloxane, take cumyl peroxide as initator, does not add copper powder and carries out being cross-linked, carbonizes the silica-based spherical particle compound material that process, ball milling and spray drying experiment obtain.
Comparative example is implemented: be raw material with t etram-ethyltetravinylcyclotetrasiloxane, take cumyl peroxide as initator, carry out being cross-linked, carbonizing process, the composite material of the silica-based irregular shape not adopting drying process with atomizing to obtain.
Comparative example 4 is: with t etram-ethyltetravinylcyclotetrasiloxane and polymethyl hydrogen siloxane be raw material, with chloroplatinic acid for catalyst, carry out Si―H addition reaction cross-linking reaction, charing process, the composite material of the silica-based irregular shape not adopting drying process with atomizing to obtain.
Effect example 2SEM observes
SEM observation is carried out to the silicon based composite material of embodiment 3, the results are shown in Figure 1.As seen from Figure 1, silicon based composite material granular size of the present invention is comparatively even, is all spherical or spheroidal particle.The SEM of embodiment 1-2 and 4-6 schemes same Fig. 1.
Claims (22)
1. a manufacturing process for silicon based composite material, it comprises the steps:
(1) under the existence of the metal dust of submicron order, with peroxide initiation reaction raw material: Polycarbosilane and/or polysiloxanes carry out cross-linking polymerization and obtain crosslinking curing product; The molecular weight of Polycarbosilane or polysiloxanes is 800-5000g/mol; At least there is in described Polycarbosilane an active H, at least there is in described polysiloxanes an active H;
(2) described crosslinking curing product is obtained intermediate materials in 600-1000 DEG C of roasting under non-oxidizing atmosphere;
(3) by described intermediate materials, graphite and binding agent mixing also wet ball grinding, spraying dry obtains spherical particle;
(4) described spherical particle is heat-treated in 400-800 DEG C under non-oxidizing atmosphere, obtain described silicon based composite material.
2. the manufacturing process of silicon based composite material as claimed in claim 1, is characterized in that: the structure shown in described Polycarbosilane and/or polysiloxanes have any one of general formula I ~ III:
Wherein, R
1~ R
16represent the alkyl of hydrogen atom or carbon number 1 ~ 12 respectively, R
1~ R
5can not be alkyl simultaneously, R
6~ R
12can not be alkyl simultaneously, R
13~ R
16can not be alkyl simultaneously; M and n is respectively the integer of 10 ~ 100, p and q is respectively the integer of 15 ~ 100.
3. the manufacturing process of silicon based composite material as claimed in claim 2, is characterized in that: described alkyl is alkyl, thiazolinyl, alkynyl, aryl or aralkyl.
4. the manufacturing process of silicon based composite material as claimed in claim 3, is characterized in that: described alkyl is the alkyl of carbon number 1 ~ 3.
5. the manufacturing process of silicon based composite material as claimed in claim 4, is characterized in that: described alkyl is methyl.
6. the manufacturing process of silicon based composite material as claimed in claim 2, is characterized in that: described polysiloxanes is polymethyl hydrogen siloxane.
7. the manufacturing process of the silicon based composite material as described in any one of claim 1 ~ 6, is characterized in that: in step (1), and described metal dust is one or more in copper powder, silver powder and magnesium powder; The consumption of described metal dust is the 0.5-5% of described reaction raw materials quality; Described peroxide is cumyl peroxide and/or benzoyl peroxide; The consumption of described peroxide is the 0.5-5% of described reaction raw materials quality.
8. the manufacturing process of the silicon based composite material as described in any one of claim 1 ~ 6, is characterized in that: in step (1), and the reaction temperature of described cross-linking polymerization is more than 170 DEG C; The reaction time of described cross-linking polymerization is more than 1 hour.
9. the manufacturing process of silicon based composite material as claimed in claim 8, it is characterized in that: in step (1), the reaction temperature of described cross-linking polymerization is 170-350 DEG C.
10. the manufacturing process of silicon based composite material as claimed in claim 8, it is characterized in that: in step (1), the reaction time of described cross-linking polymerization is 1-8 hour.
The manufacturing process of 11. silicon based composite materials as described in any one of claim 1 ~ 6, it is characterized in that: in step (2), the temperature retention time of described roasting is 4-10 hour.
The manufacturing process of 12. silicon based composite materials as described in any one of claim 1 ~ 6, it is characterized in that: in step (3), the average grain diameter of described graphite is 1-20 μm; Described binding agent is contracting sodium carboxymethylcellulose pyce and/or polyvinyl alcohol; Described wet ball grinding decentralized medium used is one or more in water, ethanol, cyclohexane, toluene and acetone.
The manufacturing process of 13. silicon based composite materials as claimed in claim 12, is characterized in that: in step (3), the average grain diameter of described graphite is 3-10 μm.
The manufacturing process of 14. silicon based composite materials as claimed in claim 12, is characterized in that: in step (3), the mixing ratio of described graphite and described intermediate materials is 1:10-1:1.
The manufacturing process of 15. silicon based composite materials as claimed in claim 14, is characterized in that: in step (3), the mixing ratio of described graphite and described intermediate materials is 1:2-1:1.
The manufacturing process of 16. silicon based composite materials as claimed in claim 12, is characterized in that: in step (3), the consumption of described binding agent is the 0.1-10% of described intermediate materials and described graphite gross mass.
The manufacturing process of 17. silicon based composite materials as claimed in claim 12, is characterized in that: in step (3), and the consumption of described decentralized medium is make the solid content of ball milling slurry be 10-20wt%; Described ball milling slurry comprises described intermediate materials, described graphite and described decentralized medium.
The manufacturing process of 18. silicon based composite materials as described in any one of claim 1 ~ 6, is characterized in that: adopt wet ball grinding by size controlling at 1-10 μm; Described spraying dry carries out in spray dryer or spray drying device, and the intake air temperature of described spray dryer or spray drying device is 200-300 DEG C; Air outlet temperature is 90-150 DEG C; Spraying frequency is 250-350Hz.
The manufacturing process of 19. silicon based composite materials as claimed in claim 18, is characterized in that: the intake air temperature of described spray dryer or spray drying device is 220-270 DEG C; Air outlet temperature is 100-130 DEG C.
The silicon based composite material that 20. 1 kinds of manufacturing process according to any one of claim 1 ~ 19 are obtained.
21. silicon based composite materials as claimed in claim 20 are as the purposes of lithium ion battery negative material.
22. 1 kinds of lithium ion batteries, is characterized in that: it is using silicon based composite material according to claim 20 as negative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110415070.XA CN103165870B (en) | 2011-12-13 | 2011-12-13 | A kind of silicon based composite material, lithium ion battery and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110415070.XA CN103165870B (en) | 2011-12-13 | 2011-12-13 | A kind of silicon based composite material, lithium ion battery and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103165870A CN103165870A (en) | 2013-06-19 |
| CN103165870B true CN103165870B (en) | 2016-03-16 |
Family
ID=48588763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110415070.XA Active CN103165870B (en) | 2011-12-13 | 2011-12-13 | A kind of silicon based composite material, lithium ion battery and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103165870B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2492167C (en) | 2011-06-24 | 2018-12-05 | Nexeon Ltd | Structured particles |
| KR20140133529A (en) | 2012-01-30 | 2014-11-19 | 넥세온 엘티디 | Composition of si/c electro active material |
| GB2499984B (en) | 2012-02-28 | 2014-08-06 | Nexeon Ltd | Composite particles comprising a removable filler |
| GB2502625B (en) | 2012-06-06 | 2015-07-29 | Nexeon Ltd | Method of forming silicon |
| GB2507535B (en) | 2012-11-02 | 2015-07-15 | Nexeon Ltd | Multilayer electrode |
| KR101567203B1 (en) | 2014-04-09 | 2015-11-09 | (주)오렌지파워 | Negative electrode material for rechargeable battery and method of fabricating the same |
| KR101604352B1 (en) | 2014-04-22 | 2016-03-18 | (주)오렌지파워 | Negative electrode active material and rechargeable battery having the same |
| GB2533161C (en) | 2014-12-12 | 2019-07-24 | Nexeon Ltd | Electrodes for metal-ion batteries |
| GB2536435B (en) * | 2015-03-16 | 2018-02-28 | Nexeon Ltd | Electroactive materials for metal-ion batteries |
| CN105428610A (en) * | 2015-10-16 | 2016-03-23 | 常州大学 | Preparation method of composite anode material for lithium-ion battery |
| JP6867821B2 (en) * | 2016-02-23 | 2021-05-12 | 信越化学工業株式会社 | Negative electrode active material, mixed negative electrode active material material, negative electrode for non-aqueous electrolyte secondary battery, negative electrode for lithium ion secondary battery, lithium ion secondary battery, negative electrode active material manufacturing method, negative electrode manufacturing method, and lithium ion secondary Battery manufacturing method |
| US11158855B2 (en) * | 2017-02-09 | 2021-10-26 | Wacker Chemie Ag | Polymer-grafted silicon particles |
| CN110416523A (en) * | 2019-08-05 | 2019-11-05 | 北方奥钛纳米技术有限公司 | A kind of Si-O-C composite material and preparation method, Si-C composite material |
| CN112174674B (en) * | 2020-09-30 | 2022-07-01 | 厦门大学深圳研究院 | Preparation method of silicon-oxygen-carbon type lithium ion battery cathode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1758466A (en) * | 2004-07-30 | 2006-04-12 | 信越化学工业株式会社 | Si-C-O composite, making method, and non-aqueous electrolyte secondary cell negative electrode material |
| CN102195038A (en) * | 2010-03-05 | 2011-09-21 | 宁波杉杉新材料科技有限公司 | Lithium ion battery as well as negative material and preparation method thereof |
-
2011
- 2011-12-13 CN CN201110415070.XA patent/CN103165870B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1758466A (en) * | 2004-07-30 | 2006-04-12 | 信越化学工业株式会社 | Si-C-O composite, making method, and non-aqueous electrolyte secondary cell negative electrode material |
| CN102195038A (en) * | 2010-03-05 | 2011-09-21 | 宁波杉杉新材料科技有限公司 | Lithium ion battery as well as negative material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103165870A (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103165870B (en) | A kind of silicon based composite material, lithium ion battery and its preparation method and application | |
| CN113078318B (en) | Three-dimensional porous silicon-carbon composite material, preparation method and application thereof | |
| JP5680191B2 (en) | Composite hard carbon negative electrode material for lithium ion battery and manufacturing method thereof | |
| CN103311522B (en) | A kind of silicon/carbon composite microsphere negative electrode material and its production and use | |
| JP4998662B2 (en) | Si-C-O-based composite, production method thereof, and negative electrode material for non-aqueous electrolyte secondary battery | |
| KR101310531B1 (en) | SiCO-Li COMPOSIT, MAKING METHOD, AND NON-AQUEOUS ELECTROLYTE SECONDARY CELL NEGATIVE ELECTRODE MATERIAL | |
| CN113097487B (en) | Silicon-carbon composite material with highly compact structure, and preparation method and application thereof | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| EP2466670A1 (en) | Electrode active material, electrode, and electricity storage device | |
| CN103311514B (en) | A kind of preparation method of modification lithium-ion battery graphite cathode material | |
| CN102299306A (en) | Nano-silicon composite lithium ion battery cathode material with poly (3,4-ethylenedioxythiophene) as coating and carbon source and preparation method thereof | |
| CN104362315A (en) | Low-cost preparing method of silicon and carbon compound cathode material for lithium ion battery | |
| CN107464926B (en) | Core-shell structure of nano silicon energy storage material and lithium ion battery comprising core-shell structure | |
| KR102331277B1 (en) | Polymer-modified silicon-carbon composite and use thereof | |
| CN104617261A (en) | Method for preparing composite cathode material of silicon-carbon nanotube of lithium ion battery | |
| WO2012105669A1 (en) | Method for manufacturing a carbon surface-coated silicon-containing carbon-based composite material | |
| CN107093711B (en) | Monodispersed SiOxThe magnanimity preparation method of-C complex microsphere | |
| Shao et al. | Novel core–shell structured Si/S-doped-carbon composite with buffering voids as high performance anode for Li-ion batteries | |
| CN112510185A (en) | Silicon-carbon composite negative electrode material and manufacturing method thereof | |
| CN115714170B (en) | Preparation method of high-energy-density quick-charge anode material | |
| CN104752691B (en) | A kind of Si/C Composite Negative Electrode Material for Lithium Ion Batteries and preparation method thereof | |
| WO2012105672A1 (en) | Silicon-containing carbonaceous composite material | |
| CN111081976B (en) | Silicon-carbon-polymer composite electrode of lithium secondary battery and preparation method thereof | |
| CN107925073A (en) | The method and silicon-carbon compound of carbon coating are prepared on silica-base material | |
| KR20140103653A (en) | Si/C COMPOSITE, PREPARATION METHOD OF THEREOF, AND ANODE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERY COMPRISING THE SAME |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |