CN104425802A - Silicon-based composite material and preparation method and application thereof and prepared lithium ion battery - Google Patents
Silicon-based composite material and preparation method and application thereof and prepared lithium ion battery Download PDFInfo
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- CN104425802A CN104425802A CN201310413507.5A CN201310413507A CN104425802A CN 104425802 A CN104425802 A CN 104425802A CN 201310413507 A CN201310413507 A CN 201310413507A CN 104425802 A CN104425802 A CN 104425802A
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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
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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
- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/58—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
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- 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 silicon-based composite material and a preparation method and application thereof and a prepared lithium ion battery. The preparation method comprises the following steps: mixing a base material and a conducting agent, spray-drying to obtain sphere-like particles, and sintering at temperature of 900-1100 DEG C for 6-10h; wherein the base material comprises silicon powder slurry, graphite and emulsified asphalt; the content of the silicon powder in the silicon powder slurry is 10-20 percent, the content of the graphite is 50-70 percent, the content of the emulsified asphalt is 10-30 percent, the content of the conducting agent is 0.5-3.0 percent, and the percentage is a percentage accounting for the total mass of the silicon powder, the graphite and the emulsified asphalt. The preparation method disclosed by the invention is simple, relatively low in cost, and suitable for industrialized production. Most of the silicon-based composite material is sphere-like particles, and the gram volume and the first-time coulombic efficiency are relatively high.
Description
Technical field
The present invention relates to silicon based composite material, its preparation method, application and obtained lithium ion battery thereof.
Background technology
Because the theoretical capacity of graphite is only 372mAh/g, and the theoretical capacity of silicon reaches 4200mAh/g, for improving lithium ion battery energy density, domestic and international more and more to siliceous negative material research in recent years, its research concentrates on again in the research to the volumetric expansion that silicon produces in charge and discharge process mostly.
For solving silicon charge and discharge process expansion issues, silicon based anode material is normally used preparation method comprise: form silicon thin film, synthesis silicon alloy and silicon-carbon compound etc.It is a kind of important method preparing silico-carbo compound that pyrolysis organic substance carries out the coated of amorphous carbon to silicon compound surface, amorphous carbon on the one hand can provide charge and discharge process ion channel, and in the reunion after Si powder can being suppressed to take off lithium on the other hand and cyclic process, active material comes off.With silicon in Chinese patent application CN201210303878.3, Si oxide is that initial feed is after ball milling, with graphite, spraying dry is carried out in conductive agent and pitch mixing, obtain spherical particle, carry out charing sintering again and obtain silicon-carbon composite cathode material, in this application, with the solid asphalt powder of routine for covering, by silicon-containing particles and graphite dispersion, be coated on wherein, but because pitch used is pressed powder, carry out in spraying preparation process be difficult to by silicon grain and graphite coat even, firmly, be not easy to obtain near-spherical grain products, and because of containing part oxygen in the silica adopted in this technical scheme, the existence of oxygen will consume the lithium in battery system more, cause the minimizing of the lithium of movement between both positive and negative polarity in system, and then the coulombic efficiency first of battery is on the low side, low the causing of efficiency will consume more positive electrode, battery cost etc. will significantly rise.
Use emulsified asphalt in the prior art of lithium ion battery negative material surface modification, generally that modification is carried out to graphite surface, as emulsified asphalt is coated on graphite outside by Chinese patent CN200710181735.9, being formed after heat treatment with carbon is the graphite material of coating layer, the material prepared in this way is made to have excellent performance as lithium ion battery negative material, but the power-carrying of graphite is only 372mAh/g at present, even if adopt the modified methods such as emulsified asphalt can improve the performance of graphite, effect is also not obvious, modified reversible gram volume only can improve several MAH (mAh).
Summary of the invention
Technical problem to be solved by this invention to be to overcome in the existing silicon based composite material of prior art silicon and the problem such as graphite dispersion effect is bad, Surface coating is uneven, efficiency is low first, reversible capacity is low, provides a kind of silicon based composite material and preparation method thereof.Preparation method's technique of the present invention is simple, cost is lower, and be applicable to suitability for industrialized production, silicon based composite material major part of the present invention is near-spherical particle, and gram volume and first coulombic efficiency are higher.
An object of the present invention is, provides a kind of preparation method of silicon based composite material, and described preparation method comprises the following steps: by base-material and conductive agent mixing, spraying dry, obtain near-spherical particle, under temperature 900 DEG C of-1100 DEG C of conditions, sinter 6-10 hour; Wherein, described base-material comprises: silica flour slurry, graphite and emulsified asphalt; The content of the silica flour in described silica flour slurry is 10%-20%, and the content of described graphite is 50%-70%, and the content of described emulsified asphalt is 10%-30%; The content of described conductive agent is 0.5%-3.0%; Described percentage is the percentage of the gross mass accounting for silica flour, graphite and emulsified asphalt.
In the present invention, described silica flour slurry is the silica flour slurry of this area routine.Preferably, described silica flour slurry obtains for silica flour is carried out wet ball grinding.The method of described wet ball grinding and condition are method and the condition of this area routine.Described wet ball grinding is preferably for be milled to D50 particle diameter 100-350nm by silica flour.The content of the silica flour in described silica flour slurry is 10%-30%, and described percentage is the mass percent accounting for silica flour slurry.
The object of silica flour slurry is used to be in the present invention: usually easily to reunite together from the nano silica fume particle preservation process of the 100-350nm of market purchase, the present invention directly carries out follow-up batch mixing, spraying dry after adopting wet ball grinding silica flour, decrease nano pulp memory time, and slurry exist in liquid form also reduce silica flour particle to a certain extent reunion, increase dispersibility.
In the present invention, the particle diameter after silica flour ball milling is through the result that inventor's great many of experiments obtains.The particle diameter of silicon is less, and volumetric expansion change occurs less, be conducive to circulating battery, but Ball-milling Time needed for it is long, energy consumption is too high, is unfavorable for suitability for industrialized production; The particle diameter of silicon is excessive, and its volumetric expansion changes greatly, and battery capacity can be caused to decay rapidly, therefore selects the D50 particle diameter being milled to silica flour to be that 100-350nm can have technique industrialization concurrently and reduce the object of cell expansion degree, realizes better technique effect.
In the present invention, described graphite is generally Delanium and/or native graphite.The D of described graphite
50particle diameter is preferably 3-20 μm, is more preferably 5-10 μm.
In the present invention, described emulsified asphalt refers to and the pitch of fusing is dispersed in the emulsion be added with in the aqueous medium of emulsifying agent.The oil-water ratio of described emulsified asphalt is preferably 1:2-7:10.The quality of the emulsifying agent in described emulsified asphalt is the 0.2%-3% of the quality of pitch.Fine grain particle diameter in described emulsified asphalt is preferably 3-10 μm.The content of the ash content in described emulsified asphalt is preferably 0.01%-0.1%, and described percentage is the percentage accounting for fine particle gross mass in emulsified asphalt.
Emulsifying agent in described emulsified asphalt is this area conventional emulsifier.Emulsifying agent in described emulsified asphalt preferably comprises cationic surfactant.What the emulsifying agent in described emulsified asphalt was better comprises cationic surfactant (basic emulsifying agent) and coemulsifier, and described coemulsifier is non-ionic surface active agent.When emulsifying agent in described emulsified asphalt comprises cationic surfactant (basic emulsifying agent) and coemulsifier, the emulsifying agent in described emulsified asphalt is compound emulsifying agent.Better further, the emulsifying agent in described emulsified asphalt is OTAC and NPE.
Pitch in described emulsified asphalt is the pitch of this area routine.Pitch in described emulsified asphalt is preferably petroleum asphalt and/or coal tar pitch.The softening point of described pitch is preferably 50-150 DEG C.
The preparation method of described emulsified asphalt is the preparation method of this area routine.The preparation method of described emulsified asphalt is preferably: emulsifying agent is mixed to obtain mixed liquor with water, then is mixed with described mixed liquor by the pitch of melting, stirs 5-10min with the speed of 1000-3000rpm.
When described emulsifying agent be OTAC and NPE time, the preparation method of described emulsified asphalt is preferably: by the aqueous solution of OTAC and the aqueous solution of NPE even mixed liquor, again the pitch of melting is added in above-mentioned mixed liquor, 5-10min is stirred with the speed of 1000-3000rpm; The quality of described OTAC is the 0.1%-2% of asphalt quality, and the quality of described NPE is the 0.1%-1.0% of asphalt quality.
Described conductive agent is the conductive agent of this area routine, is preferably one or more in carbon black, carbon nano-tube and carbon nano-fiber.
In the present invention, the method for described mixing is the method for this area routine.The method of described mixing is preferably substep mixing, and the step of described substep mixing is: first silica flour slurry, graphite and conductive agent are fully mixed to get mixture, then are poured in described mixture by emulsified asphalt, be uniformly dispersed.Described substep is mixed with and is beneficial to emulsified asphalt and is uniformly dispersed in mixed slurry in shorter time.Preferably, described when pouring into, the mixture described in stirring, the speed of described stirring is 30-100rpm, and the speed of this stirring is conducive to the breakdown of emulsion controlling emulsified asphalt.
In the present invention, described spray-dired method is the method for this area routine.Described spraying dry preferably carries out in spray dryer.The inlet temperature of described spray dryer is preferably 250-380 DEG C, and that better is 300-350 DEG C; The outlet temperature of described spray dryer is preferably 100-130 DEG C, and that better is 100-110 DEG C; The charging pump frequency of described spray dryer is preferably 5-15Hz; The atomizing disk frequency of described spray dryer is preferably 230-350Hz.
In the present invention, the method for described sintering is the method for this area routine.After described sintering, the outside pitch of nucleocapsid structure forms amorphous carbon.Preferably, described sintering carries out in retort.
By this area general knowledge, the atmosphere of described sintering is inert atmosphere.The inert gas of described inert atmosphere is the gas do not reacted with material of this area routine, is preferably nitrogen and/or argon gas.
Two of object of the present invention is, provides the silicon based composite material that the preparation method of above-mentioned silicon based composite material obtains.The particle diameter of described Si-C composite material is generally 10-25 μm.
Three of object of the present invention is, provides above-mentioned silicon based composite material preparing the application in lithium ion battery as negative material.
Four of object of the present invention is, provides a kind of lithium ion battery.Described lithium ion battery comprises above-mentioned silicon based composite material.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can combination in any, obtains each preferred embodiment of the present invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
1, silicon based composite material major part of the present invention is spherical particle, and tap density is high, and because covered effect is good, the silicon in silicon based composite material and graphite can be uniformly dispersed;
2, silicon based composite material of the present invention adopts the silicon based composite material that emulsified asphalt is covering, prepares with spray dried form, silicon can evenly be embedded in graphite material, graphite is the conductivity that good conductor not only can improve silicon, also can as the volumetric expansion of buffering matrix buffering silicon in charge and discharge process;
3, the amorphous carbon after the emulsified asphalt sintering in silicon based composite material of the present invention firmly can be coated on above-mentioned silicon, graphite mosaics outside as surface modifier, forms the nucleocapsid structure of silicon, graphite and amorphous carbon;
4, silicon based composite material of the present invention use liquid phase coating agent to make particle is more regular, covered effect is better, the outside amorphous carbon of nucleocapsid structure can ensure that inner silicon does not directly contact with electrolyte preferably, improve battery efficiency form good SEI film first, be conducive to following cycle performance;
5, coulombic efficiency is high first for the lithium ion battery that silicon based composite material of the present invention is obtained, is up to 88.5%; Capacity plays high, is up to more than 955mAh/g;
6, preparation method of the present invention is simple, cost is low, and applicable industry changes into production.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) figure of the silicon based composite material that embodiment 1 obtains.
Fig. 2 is the first charge-discharge curve chart of the lithium ion battery that embodiment 2 obtains.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
The purchase producer of the raw material used in following examples of the present invention and model as follows:
Silica flour: purchased from hair powder body Materials Co., Ltd of upper marine oil enterprise;
Delanium and native graphite: purchased from Shanghai Shanshan Science and Technology Co., Ltd; Wherein graphite is 3H series, and native graphite is MGS series;
Petroleum asphalt and coal tar pitch: purchased from Sinosteel Corporation; Described petroleum asphalt and the softening point of coal tar pitch are 50-150 DEG C.
Embodiment 1
(1) preparation of silica flour slurry: get 1Kg silica flour, is that to carry out wet ball grinding to D50 particle diameter be 100nm to medium with water, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 20%, and described percentage is the mass percent accounting for silica flour slurry;
(2) preparation of emulsified asphalt: by the aqueous solution of OTAC and the aqueous solution of NPE even mixed liquor, then the pitch of melting is added in above-mentioned mixed liquor, stirs 10min with the speed of 2000rpm and obtain; The quality of described OTAC is 1.5% of asphalt quality, and the quality of described NPE is 0.5% of asphalt quality; The oil-water ratio of obtained emulsified asphalt is 6:4, and the fine particle particle diameter in described emulsified asphalt is 3 μm, and the content of ash content is 0.05%, and percentage is the percentage accounting for fine particle gross mass in emulsified asphalt, softening point 50 DEG C;
(3) by the D of silica flour slurry obtained in step (1), 6Kg
50particle diameter is that the Delanium of 3 μm and 250g conductive black fully mix, is more slowly poured into wherein by emulsified asphalt 3.0Kg obtained in step (2), stirs slurry even to slurry with 50rpm speed simultaneously;
(4) spraying dry, the inlet temperature controlling spray dryer is 300 DEG C, and outlet temperature is 115 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains near-spherical particle;
(5) by the near-spherical particle described in step (4), in retort, under inert atmosphere (nitrogen), sinter 9 hours with the temperature of 1000 DEG C, naturally cool.
ESEM (SEM) figure of obtained silicon based composite material as shown in Figure 1.
Embodiment 2
(1) silicon based composite material method of 91 parts of embodiments 1 obtained and the aqueous solution of 200 parts of CMC/Super-P/SBR evenly, obtain slurry; Containing the CMC/Super-P/SBR of 9 parts in the aqueous solution of CMC/Super-P/SBR, and the mass ratio of CMC:Super-P:SBR is 4.5:2.0:2.5;
(2) slurry described in step (1) being coated on thickness is on the Copper Foil of 15 μm, and drying, roll-forming, obtain copper foil electrode; Be to electrode with lithium paper tinsel, form lithium rechargeable battery with copper foil electrode;
Electrolyte used, for containing solvent and electrolytical solution, specifically comprises following composition: 1. solvent: vinyl carbonate (EC)/dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC) (in solvent, the volume ratio of three is 1:1:1), 2. electrolyte: 1mol/L lithium hexafluoro phosphate (LiPF6); 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.
The initial capacity and the coulombic efficiency that measure described lithium ion battery are as shown in table 1.The first charge-discharge curve chart of obtained lithium ion battery as shown in Figure 2.
Embodiment 3
(1) preparation of silica flour slurry: get 2Kg silica flour, is that to carry out wet ball grinding to D50 particle diameter be 200nm to medium with water, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 10%, and described percentage is the mass percent accounting for silica flour slurry;
(2) preparation of emulsified asphalt: by the aqueous solution of OTAC and the aqueous solution of NPE even mixed liquor, then the petroleum asphalt of melting is added in above-mentioned mixed liquor, stirs 5min with the speed of 1500rpm and obtain; The quality of described OTAC is 2% of asphalt quality, and the quality of described NPE is 0.1% of asphalt quality; The oil-water ratio of obtained emulsified asphalt is 1:1, and the fine particle particle diameter in described emulsified asphalt is 5 μm, and the content of ash content is 0.01%, and percentage is the percentage accounting for fine particle gross mass in emulsified asphalt, softening point 70 DEG C;
(3) by the D of silica flour slurry obtained in step (1), 7Kg
50particle diameter is that the Delanium of 5 μm and 50g carbon nano-tube fully mix, is more slowly poured into wherein by cut oil pitch 1.0Kg obtained in step (2), stirs slurry even to slurry with 30rpm speed simultaneously;
(4) spraying dry, the inlet temperature controlling spray dryer is 250 DEG C, and outlet temperature is 100 DEG C, and supply disk frequency is 5Hz, and atomizing disk frequency is 230Hz, obtains near-spherical particle;
(5) by the near-spherical particle described in step (4), in retort, under inert atmosphere (nitrogen), sinter 10 hours with the temperature of 900 DEG C, naturally cool.
The method assembled battery identical according to embodiment 2 is also tested, and initial capacity and the coulombic efficiency of the lithium ion battery recorded are as shown in table 1.
Embodiment 4
(1) preparation of silica flour slurry: get 1.5Kg silica flour, is that to carry out wet ball grinding to D50 particle diameter be 250nm to medium with water, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 30%, and described percentage is the mass percent accounting for silica flour slurry;
(2) preparation of emulsified asphalt: by the aqueous solution of OTAC and the aqueous solution of NPE even mixed liquor, then the coal tar pitch of melting is added in above-mentioned mixed liquor, stirs 8min with the speed of 3000rpm and obtain; The quality of described OTAC is 0.1% of asphalt quality, and the quality of described NPE is 1% of asphalt quality.The oil-water ratio of described emulsified asphalt is 7:3, and the fine particle particle diameter in described emulsified asphalt is 6 μm, and the content of ash content is 0.1%, and percentage is the percentage accounting for fine particle gross mass in emulsified asphalt, and softening point is 90 DEG C;
(3) by the D of silica flour slurry obtained in step (1), 6.5Kg
50particle diameter is that the Delanium of 10 μm and 300g conductive black fully mix, is more slowly poured into wherein by emulsification coal tar pitch 2.0Kg obtained in step (2), stirs slurry even to slurry with 70rpm speed simultaneously;
(4) spraying dry, the inlet temperature controlling spray dryer is 350 DEG C, and outlet temperature is 120 DEG C, and supply disk frequency is 7Hz, and atomizing disk frequency is 300Hz, obtains near-spherical particle;
(5) by the near-spherical particle described in step (4), in retort, under inert atmosphere (nitrogen), sinter 6 hours with the temperature of 1100 DEG C, naturally cool.
The method assembled battery identical according to embodiment 2 is also tested, and initial capacity and the coulombic efficiency of the lithium ion battery recorded are as shown in table 1.
Embodiment 5
(1) preparation of silica flour slurry: get 2Kg silica flour, is that to carry out wet ball grinding to D50 particle diameter be 300nm to medium with water, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 15%, and described percentage is the mass percent accounting for silica flour slurry;
(2) by the D of silica flour slurry obtained in step (1), 5.5Kg
50particle diameter is that the native graphite of 20 μm and 150g conductive black fully mix, is more slowly poured into wherein by the emulsification coal tar pitch 2.5Kg of previously prepared good softening point 120 DEG C, stirs slurry even to slurry with 90rpm speed simultaneously;
(3) spraying dry, the inlet temperature controlling spray dryer is 320 DEG C, and outlet temperature is 130 DEG C, and supply disk frequency is 12Hz, and atomizing disk frequency is 350Hz, obtains near-spherical particle;
(4) by the near-spherical particle described in step (3), in retort, under inert atmosphere (nitrogen), sinter 7 hours with the temperature of 950 DEG C, naturally cool.
The method assembled battery identical according to embodiment 2 is also tested, and initial capacity and the coulombic efficiency of the lithium ion battery recorded are as shown in table 1.
Embodiment 6
(1) preparation of silica flour slurry: get 2.0Kg silica flour, is that to carry out wet ball grinding to D50 particle diameter be 350nm to medium with water, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 25%, and described percentage is the mass percent accounting for silica flour slurry;
(2) by the D of silica flour slurry obtained in step (1), 5.0Kg
50particle diameter is that the native graphite of 15 μm and 100g carbon nano-fiber fully mix, is more slowly poured into wherein by the cut oil pitch 3.0Kg of previously prepared good softening point 150 DEG C, stirs slurry even to slurry with 100rpm speed simultaneously;
(3) spraying dry, the inlet temperature controlling spray dryer is 280 DEG C, and outlet temperature is 110 DEG C, and supply disk frequency is 9Hz, and atomizing disk frequency is 270Hz, obtains near-spherical particle;
(4) by the near-spherical particle described in step (3), in retort, under inert atmosphere (nitrogen), sinter 8 hours with the temperature of 1050 DEG C, naturally cool.
The method assembled battery identical according to embodiment 2 is also tested, and initial capacity and the coulombic efficiency of the lithium ion battery recorded are as shown in table 1.
Embodiment 7
(1) preparation of silica flour slurry: get 1.7Kg silica flour, is that to carry out wet ball grinding to D50 particle diameter be 350nm to medium with water, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 20%, and described percentage is the mass percent accounting for silica flour slurry;
(2) by the D of silica flour slurry obtained in step (1), 6.8Kg
50particle diameter is that the native graphite of 15 μm and 200g conductive black fully mix, is more slowly poured into wherein by the cut oil pitch 1.5Kg of previously prepared good softening point 60 DEG C, stirs slurry even to slurry with 40rpm speed simultaneously;
(3) spraying dry, the inlet temperature controlling spray dryer is 280 DEG C, and outlet temperature is 105 DEG C, and supply disk frequency is 9Hz, and atomizing disk frequency is 270Hz, obtains near-spherical particle;
(4) by the near-spherical particle described in step (3), in retort, under inert atmosphere (argon gas), sinter 8 hours with the temperature of 1050 DEG C, naturally cool.
The method assembled battery identical according to embodiment 2 is also tested, and initial capacity and the coulombic efficiency of the lithium ion battery recorded are as shown in table 1.
Comparative example 1
Adopt pressed powder pitch to be covering, all the other are with embodiment 1; Specifically, its preparation method comprises the following steps:
(1) preparation of silica flour slurry: get 1Kg silica flour is that medium carries out wet ball grinding to D with water
50particle diameter is 100nm, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 20%, and described percentage is the mass percent accounting for silica flour slurry;
(2) by the D of silica flour slurry obtained in step (1), 6Kg
50particle diameter is the Delanium of 3 μm, the solid coal tar pitch powder 3.0Kg of softening point 50 DEG C and 250g conductive black fully mix;
(3) spraying dry, the inlet temperature controlling spray dryer is 300 DEG C, and outlet temperature is 110 DEG C, and supply disk frequency is 10Hz, and atomizing disk frequency is 250Hz, obtains random powder;
(4) by the random powder described in step (3) in retort, under inert atmosphere (nitrogen), with 1000 DEG C sintering 9 hours, naturally cooling.
The method assembled battery identical according to embodiment 2 is also tested, and its result is as shown in table 2.
Comparative example 2
Adopt pressed powder pitch to be covering, all the other are with embodiment 4; Specifically, its preparation method comprises the following steps:
(1) preparation of silica flour slurry: get 1.5Kg silica flour is that medium carries out wet ball grinding to D with water
50particle diameter is 350nm, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 30%, and described percentage is the mass percent accounting for silica flour slurry;
(2) by the D of silica flour slurry obtained in step (1), 6.5Kg
50particle diameter is that the Delanium of 10 μm and 300g conductive black fully mix, is more slowly poured into wherein by the solid coal tar pitch powder 2.0Kg of previously prepared good softening point 90 DEG C, stirs slurry even to slurry with 70rpm speed simultaneously;
(3) spraying dry, the inlet temperature controlling spray dryer is 350 DEG C, and outlet temperature is 120 DEG C, and supply disk frequency is 7Hz, and atomizing disk frequency is 300Hz, must obtain random powder;
(4) by the random powder described in step (3) in retort, under inert atmosphere, with 1100 DEG C sintering 6 hours, naturally cooling.
The method assembled battery identical according to embodiment 2 is also tested, and its result is as shown in table 2.
Comparative example 3
Adopt the coated replacement spraying dry of coated still, all the other are with embodiment 3; Specifically, its preparation method comprises the following steps:
(1) preparation of silica flour slurry: get 2Kg silica flour is that medium carries out wet ball grinding to D with water
50particle diameter is 200nm, obtains silica flour slurry; In silica flour slurry, the content of silica flour is 10%, and described percentage is the mass percent accounting for silica flour slurry;
(2) preparation of emulsified asphalt: by the aqueous solution of OTAC and the aqueous solution of NPE even mixed liquor, then the petroleum asphalt of melting is added in above-mentioned mixed liquor, stirs 5min with the speed of 1500rpm and obtain; The quality of described OTAC is 2% of asphalt quality, and the quality of described NPE is 0.1% of asphalt quality; The oil-water ratio of obtained emulsified asphalt is 1:1, and the fine particle particle diameter in described emulsified asphalt is 5 μm, and ash content is 0.01%, softening point 70 DEG C;
(3) by the D of silica flour slurry obtained in step (1), 7Kg
50particle diameter is that cut oil pitch 1.0Kg obtained in step (2) fully mixes by Delanium, 50g carbon nano-tube and the 1.0Kg of 5 μm in coated still;
(4) in coated still, be warming up to 150 DEG C while stirring under inert gas shielding and be incubated 3 hours, being then persistently overheatingly incubated 5 hours to 500 DEG C, being cooled to room temperature, obtaining random powder;
(5) by the powder described in step (4) in retort, under inert atmosphere (nitrogen), sinter 10 hours with the temperature of 900 DEG C, naturally cool.
The method assembled battery identical according to embodiment 2 is also tested, and its result is as shown in table 3.
Effect example 1
Initial discharge capacity and the coulombic efficiency of the lithium ion battery obtained by the silicon based composite material of embodiment 1,3-7 are as shown in table 1.
The initial discharge capacity of the lithium ion battery that the silicon based composite material of table 1 embodiment 1,3-7 obtains and coulombic efficiency
As seen from the above table: it is good that preparation method of the present invention prepares obtained silica-based composite negative pole material performance, capacity is large first for the lithium rechargeable battery using this silica-based composite negative pole material obtained, initial discharge capacity peak capacity reaches 955mAh/g, and coulombic efficiency is up to 88.5%.
Conventional according to this area, because the theoretical capacity of silicon is very high, in material, role is maximum, and different silicone contents is very large to Index Influences such as the capacity of material.Therefore, in following effect example, the initial discharge capacity of battery obtained after changing with unitary variant and coulombic efficiency, to further illustrate positive progressive effect of the present invention.
Effect example 2
Emulsified asphalt is on the impact of silicon based composite material.By embodiment 2 and comparative example 1, and embodiment 4 is made comparisons with comparative example 2, with the impact of the initial discharge capacity and coulombic efficiency that further illustrate the battery that emulsified asphalt obtains for silicon based composite material.Its result is as shown in table 2:
The initial discharge capacity of table 2 battery and coulombic efficiency
The covering used in comparative example 1 is pressed powder pitch, all the other raw materials and preparation technology and condition all with the preparation method of embodiment 2(and silicon based composite material except covering is pressed powder pitch, all the other are all with embodiment 1, and the assemble method of battery is with embodiment 2); The covering used in comparative example 2 is pressed powder pitch, and all the other raw materials and preparation technology and condition are all with embodiment 4.As shown in Table 2: under the condition that other parameters are all identical, use the negative material that general pressed powder pitch obtains, the initial discharge capacity of its obtained battery and coulombic efficiency are starkly lower than the silicon based composite material using emulsified asphalt to prepare.
Effect example 3
Spraying dry is for the impact of silicon based composite material.Embodiment 3 and comparative example 3 are made comparisons, with the impact of the initial discharge capacity and coulombic efficiency that further illustrate the battery that spraying dry obtains for silicon based composite material.Its result is as shown in table 3:
The initial discharge capacity of table 3 battery and coulombic efficiency
| Battery performance | Embodiment 3 | Comparative example 3 |
| Initial discharge capacity (mAh/g) | 955 | 835 |
| Coulombic efficiency (%) | 85.4 | 84.4 |
Adopt the coated mode of coated still to replace spraying dry in comparative example 3, all the other raw materials and preparation technology and condition are all with embodiment 3.As shown in Table 3: the initial discharge capacity of the battery that the silicon based composite material of comparative example 3 obtains is only 835mAh/g, coulombic efficiency is 84.4% first, the initial discharge capacity of the battery that the silicon based composite material of the embodiment 3 corresponding with it obtains up to 955mAh/g, the two capacity difference more than 100mAh/g.The coulombic efficiency first of the battery that the silicon based composite material simultaneously in embodiment 3 obtains is also higher than comparative example 3.Under the condition that other parameters are all identical, use the negative material that general spray dried form obtains, the initial discharge capacity of its obtained battery and coulombic efficiency are apparently higher than the silicon based composite material using the general coated preparation of coated still.
Should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. a preparation method for silicon based composite material, is characterized in that: described preparation method comprises the following steps: by base-material and conductive agent mixing, spraying dry, obtains near-spherical particle, under temperature 900 DEG C of-1100 DEG C of conditions, sinter 6-10 hour; Wherein, described base-material comprises: silica flour slurry, graphite and emulsified asphalt; The content of the silica flour in described silica flour slurry is 10%-20%, and the content of described graphite is 50%-70%, and the content of described emulsified asphalt is 10%-30%; The content of described conductive agent is 0.5%-3.0%; Described percentage is the percentage of the gross mass accounting for silica flour, graphite and emulsified asphalt.
2. preparation method as claimed in claim 1, is characterized in that: described silica flour slurry obtains for silica flour is carried out wet ball grinding; Preferably, wet ball grinding is to the D of silica flour
50particle diameter 100-350nm; The content of the silica flour in described silica flour slurry is 10%-30%, and described percentage is the mass percent accounting for silica flour slurry;
Described graphite is Delanium and/or native graphite; The D of described graphite
50particle diameter is preferably 3-20 μm, is more preferably 5-10 μm.
3. preparation method as claimed in claim 1, is characterized in that: the oil-water ratio of described emulsified asphalt is 1:2-7:10; The quality of the emulsifying agent in described emulsified asphalt is the 0.2%-3% of the quality of pitch; Fine grain particle diameter in described emulsified asphalt is 3-10 μm; The content of the ash content in described emulsified asphalt is 0.01%-0.1%, and described percentage is the percentage accounting for fine particle gross mass in emulsified asphalt;
Emulsifying agent in described emulsified asphalt comprises cationic surfactant, preferably comprises cationic surfactant and coemulsifier, and described coemulsifier is non-ionic surface active agent; What the emulsifying agent in described emulsified asphalt was better is OTAC and NPE;
Pitch in described emulsified asphalt is petroleum asphalt and/or coal tar pitch, and the softening point of described pitch is 50-150 DEG C;
The preparation method of described emulsified asphalt is: emulsifying agent is mixed to obtain mixed liquor with water, then is mixed with described mixed liquor by the pitch of melting, stirs 5-10min with the speed of 1000-3000rpm;
Preferably, when described emulsifying agent be OTAC and NPE time, the preparation method of described emulsified asphalt is: by the aqueous solution of OTAC and the aqueous solution of NPE even mixed liquor, again the pitch of melting is added in above-mentioned mixed liquor, 5-10min is stirred with the speed of 1000-3000rpm; The quality of described OTAC is the 0.1%-2% of asphalt quality, and the quality of described NPE is the 0.1%-1.0% of asphalt quality.
4. preparation method as claimed in claim 1, is characterized in that: described conductive agent is one or more in carbon black, carbon nano-tube and carbon nano-fiber.
5. preparation method as claimed in claim 1, it is characterized in that: the method for described mixing is substep mixing, the step of described substep mixing is: first silica flour slurry, graphite and conductive agent are fully mixed to get mixture, again emulsified asphalt is poured in described mixture, be uniformly dispersed;
Preferably, described when pouring into, the mixture described in stirring, the speed of described stirring is 30-100rpm.
6. preparation method as claimed in claim 1, is characterized in that: described spraying dry carries out in spray dryer; The inlet temperature of described spray dryer is 250-380 DEG C, is preferably 300-350 DEG C; The outlet temperature of described spray dryer is 100-130 DEG C, is preferably 100-110 DEG C; The charging pump frequency of described spray dryer is 5-15Hz; The atomizing disk frequency of described spray dryer is 230-350Hz;
Described sintering carries out in retort; The atmosphere of described sintering is inert atmosphere, and the inert gas of described inert atmosphere is nitrogen and/or argon gas.
7. the silicon based composite material that the preparation method according to any one of claim 1-6 obtains.
8. Si-C composite material as claimed in claim 7, is characterized in that: the particle diameter of described Si-C composite material is 10-25 μm.
9. silicon based composite material is preparing the application in lithium ion battery as negative material as claimed in claim 7 or 8.
10. a lithium ion battery, is characterized in that: described lithium ion battery comprises silicon based composite material as claimed in claim 7 or 8.
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