CN103400970B - Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof - Google Patents
Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nanometer silicon/graphene lithium ion battery cathode material and a preparation method thereof. The cathode material comprises nanometer silicon and graphene, wherein the granularity of nanometer silicon granules is 10-100nm, and the mass ratio of nanometer silicon to graphene is 1:(5-10). The preparation method of the nanometer silicon/graphene lithium ion battery cathode material comprises the following steps of: preparing an electron solution; reducing a silicon tetrachloride liquid phase into nanometer silicon; preparing a graphene oxide glue sample solution; loading the graphene oxide glue sample solution on nanometer silicon; and drying and sintering the semi-finished product of the composite electrode material. According to the preparation method, after the nanometer silicon granules the granularity of which can be controlled are obtained through a liquid phase reducing method; in a mode that a glue body is separated out through replacing a solvent graphene is reduced and a glue layer is formed at the same time, and moreover the glue layer is adsorbed on an existing nanometer silicon glue nucleus; the obtained nanometer silicon has a better size and a better structure, can combine graphene and nanometer silicon efficiently in the term of molecule size; the obtained silicon carbon material has stable circulation performance and excellent electric conducting performance.
Description
Technical field
The invention belongs to electrochemistry and new energy materials field, be specifically related to a kind of nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof.
Background technology
Since Japanese Sony Corporation in 1991 releases commercial lithium ion battery product first, lithium ion battery is developed so far, and has gone through more than 20 years.Lithium ion battery has the Mechanism of electrochemical behaviors of anhydrous of unique embedding/deviate from lithium ion, and thus more similar battery product, it has the advantages such as specific capacity is large, operating voltage is high, fail safe is high, environmental pollution is little.As the exploitation of the negative material of lithium ion battery storage lithium main body, just become the key point improving the total specific capacity of lithium ion battery, discharge and recharge and cycle performance.
In early days, the negative material of lithium ion battery is based on lithium alloy, and main problem is cycle performance difference and irreversible capacity is large first.Its basic reason is that negative material exists the restructuring of crystal structure in charge and discharge process, causes larger volumetric expansion; In addition, alternate change in volume is also had to cause the loss of embedding lithium material.So, in the commercial batteries after industrialization, abandon the high alloy material of theoretical specific capacity and used the graphite-like material with carbon element inserting compound with lithium ion formation layer instead.Because graphite-like material with carbon element can hold lithium ion by its graphite gaps, thus solve the problem of volumetric expansion.And the graphite-like material with carbon element of this kind of excellent electrochemical performance, also just become modal negative material in present commodity lithium ion battery.
But graphite-like material with carbon element storage lithium theoretical capacity is low, is the problem of an essence all the time.The theoretical specific capacity of general graphite-like material with carbon element is only 372mAh/g, and has reached 370mAh/g in practical application, basic close to theoretical level.Even the graphite-like material with carbon element of modification, its capacity also just 450mAh/g.Therefore, although graphite ensure that the cycle performance of lithium ion battery, greatly limit its total specific capacity, and this does not catch up with now for the functional requirement of lithium ion battery far away yet.So, have high power capacity, the exploitation of lithium ion battery negative material beyond graphite-like material with carbon element, become the task of top priority.
Under comparing, silicon based anode material is in non-carbon class negative material, and its performance then seems advantageously.It has the highest theoretical capacity ratio and (forms Li4.4Si, theoretical capacity is up to 4200mAh/g) and relatively low intercalation potential, also better stability and fail safe is had compared with other metal materials, the source of raw material is also abundanter, therefore, the research of silicon based anode material is being carried out all the time.But it also also exists the bulk effect (cubical expansivity > 300%) in charge and discharge process, and cause that the recurring structure of material in charge and discharge process own collapses, efflorescence gradually, active material and the electrical contact forfeiture of collector, the forfeiture of conductivity ability, finally result in the loss of reversible capacity.
But, the technical problem existed for silica-base material at present there has also been certain solution.By by silicon process to nanoscale, its absolute volume can be made to change greatly decline, or adopt the methods such as surface modification, doping, compound to form system that is coated or high degree of dispersion, thus improve the mechanical property of material, to alleviate the internal stress of volumetric expansion generation in removal lithium embedded process to the destruction of material structure, this just can eliminate the impact of bulk effect, thus reaches the object improving its electrochemical cycle stability.But then, pure nano-silicon is easily reunited again, and utilizes the silica-base material of existing surface modification and doping techniques modified, there is again high cost or doped level is bad, the inhomogenous new problem of product.Therefore, the lithium ion battery being negative material with the silica-base material of pure nano-silicon or modified, can only lie under lab all the time, and can not successfully industrialization.
In addition, the research and development of chemical property good carbon class material also have breakthrough.Use single-layer graphene instead as after the negative material of lithium ion battery, its theoretical capacity ratio can reach 744mAh/g, and has the Graphene negative material of report, its first discharge capacity can reach 650mAh/g, after 100 circulations, its capacity still remains on the level of 460mAh/g.Therefore, although Graphene theoretical capacity compares some metals and silica-base material is more weak, if its high power capacity with silica-base material closely can be combined, the cycle performance of silica-base material just can be improved.In research report, silica flour (~ 40nm) and Graphene are ground according to the ratio mechanical mixture of mass ratio 1:1, first discharge specific capacity is 2158mAh/g, and the specific discharge capacity after 30 circulations also can reach 1168mAh/g, is still three times of existing material with carbon element specific capacity.
Therefore, the nano-silicon of high theoretical capacity ratio and Graphene being combined, is exactly the present emphasis for non-carbon negative material research.Now main combination is all the time still on mechanical yardstick, mainly with ball-milling method, Graphene and nano-silicon are combined, although certain effect can be played, because mechanical yardstick mixing is uneven, the performance of Graphene cannot be allowed all the time to give full play to.And the heat treating process energy consumption that can reach molecular scale combination is high, COD chemical vapour deposition technique involves great expense again, is not suitable for commercial development.Therefore, the combination technology carrying out a kind of Graphene effectively and nano-silicon be necessary very much and have far-reaching.The level of this combination is higher, more can improve the performance of the pole piece material of new silico-carbo matrix.Raw material and preparation method more cheap, more easily carry out industrialization promotion.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide the nanometer silicon/graphene lithium ion battery cathode material of a kind of electric conductivity excellence, stable cycle performance.
Another object of the present invention is to the preparation method that a kind of nanometer silicon/graphene lithium ion battery cathode material is provided.
For solving the problem, the technical solution adopted in the present invention is as follows:
A kind of nanometer silicon/graphene lithium ion battery cathode material, it comprises nano-silicon and Graphene, and wherein, nano-silicon particle size is 10 ~ 100nm, mass ratio 1:5 ~ 10 of nano-silicon and Graphene.
It is less that theoretical specific capacity (~ 700mAh/g) due to Graphene compares nano-silicon, excessive Graphene can cause the Average specific capacities of material monolithic to decline, therefore, when the ratio of nano-silicon and Graphene is greater than 1:10, the specific capacity of material monolithic just starts to have occurred decay.In addition, if nano-silicon and Graphene containing quantity not sufficient 1:5, Graphene can be caused cannot to cover nano-silicon completely, make between nano-silicon particle, still to there is the possibility of reuniting and losing electrical contact, thus cause the cycle performance of material to be affected further.
A preparation method for nanometer silicon/graphene lithium ion battery cathode material, comprises the following steps:
(1) preparation of electronics solution: under argon shield, lithium metal and cosolvent are dissolved in the first kind solvent anhydrated, magnetic agitation dissolve, to be dissolved complete after, containing when measuring the electronics of ratio with lithium metal etc. in solution, stand-by under being kept at ar gas environment;
(2) silicon tetrachloride liquid-phase reduction becomes nano-silicon: under argon shield, to in the reactor that the obtained electronics solution of step (1) is housed, dropwise add and account for the silicon tetrachloride that electronics total solution weight is 5% ~ 20%, simultaneously with magnetic agitation or electric stirring, after silicon tetrachloride dropwises, obtain the suspension-turbid liquid that the granularity be in electronics solution is the nano-silicon particle of 10 ~ 100nm, preferably, the rotating speed of stirring maintains 100 ~ 300 revs/min;
(3) preparation of graphene oxide glue sample solution: using water as dispersant, the configuration graphite oxide aqueous solution or Graphene suspension-turbid liquid, add nitric acid again, the graphite oxide aqueous solution or Graphene suspension-turbid liquid are mixed with nitric acid, after From Solution Under Ultrasound Treatment, centrifuge washing repeatedly, system is washed pH close to after neutrality, vacuumize, then by the desciccate that obtains and the process of Equations of The Second Kind solvent supersonic, be made into glue sample solution;
(4) graphene oxide glue sample solution loadings is in nano-silicon: by extremely even for the nano-silicon suspension-turbid liquid high-speed stirred be in step (2) in electronics solution, and add electronics solution and dilute as reducing agent, start again to be slowly added dropwise to the obtained graphene oxide glue sample solution of step (3), the addition of graphene solution is determined by the mass ratio of nano-silicon and Graphene, stir, adjoint first kind solvent mixes indigenous graphite alkene gradually with Equations of The Second Kind solvent, after graphene solution is added dropwise to complete, again through ultrasonic process, dispersing nanometer silicon and Graphene, preferably, the rotating speed stirred is 150 ~ 300 revs/min,
(5) the half-finished drying of combination electrode material and sintering: the mixed solution that step (4) obtains is separated through differential centrifugation; after vacuum filtration and drying; be placed in quartz boat; be positioned in the tube furnace of argon shield; control gas flow rate; calcining, by the product grinding and sieving obtained, obtains combination electrode material.
As further technical scheme of the present invention, cosolvent described in step (1) is the organic compound of multiring aromatic hydrocarbon, described first kind solvent is ethers or amine organic compound, and the Equations of The Second Kind solvent described in step (3) is amine or alcohols solvent.
Polycyclic aromatic hydrocarbon is embedded in fragrant layer as the lithium ion that cosolvent can make lithium metal be formed upon dissolution, thus dissolution equilibrium is moved, and promotes the formation of solvated electron in solvent further.Because amine and ethers do not exist active hydrogen, solvated electron has longer life, has been enough to reduction process, therefore selects amine and ether compound as first kind solvent.Because amine or alcohols can form π-hydrogen bond with graphite and Graphene, also can form traditional hydrogen bond with the site of graphite and the oxidation of Graphene upper part, thus effectively can assist the dissolving of graphite and Graphene, therefore select alcohols or amine as Equations of The Second Kind solvent.
Preferably, the cosolvent described in step (1) is biphenyl, 4,4 '-benzidine, 4,4 '-dimethoxy-biphenyl and analog, the one in anthracene, naphthalene, phenanthrene and Graphene or two or more.
Preferably, described first kind solvent is one in ethylenediamine, tripropyl amine (TPA), morpholine, dicyclohexyl ether, glycol dimethyl ether and ether or two or more.
Preferably, the Equations of The Second Kind solvent described in step (3) is one in ethanol, ethylenediamine, tripropyl amine (TPA), cyclohexanol and ethylene glycol or two or more.
As further technical scheme of the present invention, described in step (1), the consumption of lithium metal is 1% ~ 5% of electronics total solution weight, and the consumption of cosolvent is 0% ~ 5% of electronics total solution weight.Do not add the formation that cosolvent also can cause solvated electron, just reaction is carried out slower.
As further technical scheme of the present invention, described in step (3), the mass fraction of the graphite oxide aqueous solution or Graphene suspension-turbid liquid is 0.5 ~ 1.5g/L, the mass concentration of described nitric acid is 60% ~ 70%, and the volume ratio of the graphite oxide aqueous solution or Graphene suspension-turbid liquid and nitric acid is 1:2 ~ 10.
As further technical scheme of the present invention, described in step (3), the mass fraction of glue sample solution is 0.1 ~ 5g/L.
As further technical scheme of the present invention, mass ratio 1:5 ~ 10 of nano-silicon and graphene oxide in step (4).
As further technical scheme of the present invention, the mass percent adding electronics solution in step (4) is 0% ~ 5%, and the frequency of ultrasonic process is 40 ~ 80Hz.
As further technical scheme of the present invention, the gas flow rate in step (5) is 20 ~ 100mL/min, and sintering temperature is 500 DEG C ~ 800 DEG C, calcining 2 ~ 5h.
Compared to existing technology, beneficial effect of the present invention is:
1) silicon-carbon composite electrode material prepared of the present invention, after obtaining the more controlled nano-silicon particle of granularity by the mode of liquid-phase reduction, glue-line is formed while mode again by changing solvent precipitation colloid makes Graphene be reduced, be adsorbed on existing nanometer silica gel core, thus make the combination reaching molecule aspect between silicon-carbon, the Si-C composite material obtained by the method, its stable cycle performance, relative conventional graphite class and pure Graphene class material, there is the specific capacity of more than 1 times, and complete in reaction homophase, simple to operate, special equipment is not needed to complete.
2) silicon tetrachloride liquid-phase reduction is become nano-silicon by the present invention, again in liquid phase situ by graphene-supported for partial oxidation on nano-silicon, under reproducibility environment, partial oxidation Graphene is reduced to Graphene further, on molecular scale, Graphene and nano-silicon can be combined efficiently, thus a kind of performance better Graphene-nano-silicon negative material is provided.
3) silicon tetrachloride liquid-phase reduction is become nano-silicon by the liquid-phase reduction technology that the present invention adopts, and the nano-silicon obtained has better yardstick and structure.
4), while the present invention utilizes nano-silicon to have the highest theoretical specific capacity in material on year-on-year basis, using Graphene as carrier, load in addition, effectively can reduce the bulk effect of material, overall cycle performance is improved further on a molecular scale.
5) Graphene in composite material of the present invention effectively can suppress the volumetric expansion of silicium cathode, therefore the nanometer silicon/graphene lithium ion battery cathode material prepared has excellent electric conductivity, and corresponding lithium ion battery specific capacity is large, good cycle.
Embodiment
Embodiment 1:
Under argon shield, be that the lithium metal of 1% and the biphenyl of 1% are dissolved in the glycol dimethyl ether of 1kg by mass percent, magnetic agitation is dissolved, and after dissolving, solution is blackish green.In this solution, drip the silicon tetrachloride that mass ratio is 5% again, drip in 1h, simultaneously in addition magnetic agitation, maintain 100 revs/min, stop after 1h stirring.
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.5g/L, adding volume ratio is with ultrasonic process 0.5h after the nitric acid of 60% concentration of 1:2.After process, by the solution centrifuge washing repeatedly obtained, terminate when being washed till pH=7.Again with ultrasonic process 0.5h after vacuumize, make it be dissolved in cyclohexanol, be configured to the graphene oxide glue sample solution of 0.1g/L.
Nano-silicon suspension-turbid liquid is stirred with the rotating speed of 200 revs/min, and in whipping process, is nano-silicon in mass ratio: Graphene=1:8 drips the graphene oxide solution of above-mentioned 0.1g/L, dropwises in 1h.After 1h, then use the ultrasonic disperse 0.5h of 40Hz, after having disperseed, centrifugal rotational speed is 16000 revs/min, centrifugal 0.5h.Centrifugally complete final vacuum suction filtration, dry, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 20mL/min, at 500 DEG C, calcine 2h, by the product grinding and sieving obtained, obtain the combination electrode material of embodiment 1.
Embodiment 2:
Under argon shield, be the lithium metal of 3% and 5% 4 by mass percent, 4 '-dimethoxy-biphenyl is dissolved in the tripropyl amine (TPA) of 1kg, and magnetic agitation is dissolved, and after dissolving, solution is close to navy blue.In this solution, drip the silicon tetrachloride that mass ratio is 20% again, drip in 3h, simultaneously in addition magnetic agitation, maintain 150 revs/min, stop after 1h stirring.
Using water as dispersant, the graphite oxide aqueous solution of configuration 0.5g/L, adding volume ratio is after the nitric acid of 60% concentration of 1:5, with ultrasonic process 0.5h.After process, by the solution centrifuge washing repeatedly obtained, terminate when being washed till pH=7.Again with ultrasonic process 3h after vacuumize, make it be dissolved in ethanol, be configured to the graphene oxide glue sample solution of 5g/L.
Nano-silicon suspension-turbid liquid is stirred with the rotating speed of 150 revs/min, and in whipping process, is nano-silicon in mass ratio: Graphene=1:5 drips the graphene oxide solution of above-mentioned 5g/L, dropwises in 2h.After 2h, then use 40Hz ultrasonic disperse 1h, after having disperseed, centrifugal rotational speed is 16000 revs/min, centrifugal 0.5h.Centrifugally complete final vacuum suction filtration, dry, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 30mL/min, at 600 DEG C, calcine 5h, by the product grinding and sieving obtained, obtain the combination electrode material of embodiment 2.
Embodiment 3:
Under argon shield, be that the lithium metal of 5% and the anthracene of 5% are dissolved in the morpholine of 1kg by mass percent, magnetic agitation is dissolved, and after dissolving, solution is close to metal black.In this solution, drip the silicon tetrachloride that mass ratio is 20% again, drip in 3h, simultaneously in addition magnetic agitation, maintain 150 revs/min, stop after 1h stirring.
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.5g/L, adding volume ratio is after the nitric acid of 60% concentration of 1:10, with 60Hz ultrasonic process 0.5h.After process, by the solution centrifuge washing repeatedly obtained, terminate when being washed till pH=7.Again with ultrasonic process 3h after vacuumize, make it be dissolved in ethylene glycol, be configured to the graphene oxide glue sample solution of 1g/L.
Nano-silicon suspension-turbid liquid is stirred with the rotating speed of 200 revs/min, and in whipping process, is nano-silicon in mass ratio: Graphene=1:10 drips the graphene oxide solution of above-mentioned 1g/L, dropwises in 2h.After 2h, then use ultrasonic disperse 1h, after having disperseed, centrifugal rotational speed is 16000 revs/min, centrifugal 0.5h.Centrifugally complete final vacuum suction filtration, dry, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 50mL/min, at 800 DEG C, calcine 3h, by the product grinding and sieving obtained, obtain the combination electrode material of embodiment 3.
Embodiment 4:
Under argon shield, be the lithium metal of 5%, do not add cosolvent by mass percent, be directly dissolved in the ethylenediamine of 1kg, magnetic agitation is dissolved, and after dissolving, solution is navy blue.In this solution, drip the silicon tetrachloride that mass ratio is 15% again, drip in 2h, simultaneously in addition magnetic agitation, maintain 200 revs/min, stop after 1h stirring.
Using water as dispersant, the graphite oxide aqueous solution of configuration 0.5g/L, adding volume ratio is with ultrasonic process 0.5h after the nitric acid of 60% concentration of 1:2.After process, by the solution centrifuge washing repeatedly obtained, terminate when being washed till pH=7.Again with ultrasonic process 1h after vacuumize, make it be dissolved in ethanol, be configured to the graphene oxide glue sample solution of 2g/L.
Nano-silicon suspension-turbid liquid is stirred with the rotating speed of 300 revs/min, and in whipping process, is nano-silicon in mass ratio: Graphene=1:9 drips the graphene oxide solution of above-mentioned 2g/L, dropwises in 2h.After 2h, then use 60Hz ultrasonic disperse 1h, after having disperseed, centrifugal rotational speed is 30000 revs/min, centrifugal 1h.Centrifugally complete final vacuum suction filtration, dry, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 70mL/min, at 800 DEG C, calcine 2h, by the product grinding and sieving obtained, obtain the combination electrode material of embodiment 4.
Embodiment 5:
Under argon shield, be the lithium metal of 5%, do not add cosolvent by mass percent, be directly dissolved in the tripropyl amine (TPA) of 1kg, magnetic agitation is dissolved, and after dissolving, solution is metal black.In this solution, drip the silicon tetrachloride that mass ratio is 20% again, drip in 1h, simultaneously in addition magnetic agitation, maintain 300 revs/min, stop after 1h stirring.
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.5g/L, adding volume ratio is with ultrasonic process 0.5h after the nitric acid of 60% concentration of 1:2.After process, by the solution centrifuge washing repeatedly obtained, terminate when being washed till pH=7.Again with ultrasonic process 1h after vacuumize, make it be dissolved in cyclohexanol, be configured to the graphene oxide glue sample solution of 5g/L.
Nano-silicon suspension-turbid liquid is stirred with the rotating speed of 300 revs/min, and in whipping process, is nano-silicon in mass ratio: Graphene=1:9 drips the graphene oxide solution of above-mentioned 5g/L, drips in 2h.After 2h, then use 80Hz ultrasonic disperse 1h, after having disperseed, centrifugal rotational speed is 30000 revs/min, centrifugal 1h.Centrifugally complete final vacuum suction filtration, dry, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 100mL/min, at 500 DEG C, calcine 5h, by the product grinding and sieving obtained, obtain the combination electrode material of embodiment 5.
Comparative example:
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.4g/L, adding volume ratio is with ultrasonic process 0.5h after the nitric acid of 60% concentration of 1:2.After process, by the solution centrifuge washing repeatedly obtained, terminate when being washed till pH=7.Again with ultrasonic process 1h after vacuumize, make it be dissolved in the water, be configured to the graphene oxide glue sample solution of 0.4g/L.
Getting a certain amount of commercially available grain size is 20 ~ 50nm nano-silicon, be exposed to 16h in air, more above-mentioned nano-silicon is added to the water, after ultrasonic disperse 1h, be nano-silicon in mass ratio: Graphene=1:2 drips the graphene oxide solution of above-mentioned 0.4g/L, dropwises in 2h.After 2h; use 40Hz ultrasonic disperse 1.5h again; disperse final vacuum suction filtration; drying, then be positioned in quartz boat, is positioned in tube furnace that hydrogen-argon-mixed body (hydrogen: argon=6%:94%) protects; keep the gas flow rate of 70mL/min; at 800 DEG C, calcine 1h, by the product grinding and sieving obtained, obtain the combination electrode material of comparative example.
The electrical performance test method of above-described embodiment 1 ~ 5 and comparative example is: be placed on Copper Foil by the electrode material obtained and make cathode pole piece, and metal lithium sheet is assembled into 2016 type button cells, and electrolyte is the LiPF of 1mol/L
6be dissolved in DMC, in the voltage range of 0.02 ~ 1.5V, under room temperature, carry out charge and discharge cycles test with the electric current of 100mAh/g, circulate 100 times.
The results list of the electrical performance testing of above-described embodiment 1 ~ 5 and comparative example is as follows:
As seen from the above table, preparation method of the present invention, compared with comparative example, has the difference of conspicuousness, and negative material of the present invention can reserve capacity effectively.But, the first discharge specific capacity of current existing graphitic carbon negative electrode material is 350mAh/g, reserve capacity is 320 ~ 340mAh/g, and therefore, the specific capacity of negative material of the present invention is far superior to the performance of existing graphitic carbon negative electrode material and similar silicon-carbon cathode material.This is because new carrying method and method of reducing can control combining closely between nano-silicon and Graphene effectively, and Graphene, as buffer substance, prevents structural deterioration and the change in volume caused, thus eliminates the problem of cycle performance difference.
Above-mentioned execution mode is only the preferred embodiment of the present invention; can not limit the scope of protection of the invention with this, change and the replacement of any unsubstantiality that those skilled in the art does on basis of the present invention all belong to the present invention's scope required for protection.
Claims (9)
1. a nanometer silicon/graphene lithium ion battery cathode material, is characterized in that: it comprises nano-silicon and Graphene, and wherein, nano-silicon particle size is 10 ~ 100nm, mass ratio 1:5 ~ 10 of nano-silicon and Graphene;
The preparation method of described nanometer silicon/graphene lithium ion battery cathode material comprises the following steps:
(1) preparation of electronics solution: under argon shield, by the organic compound solubilization of lithium metal and multiring aromatic hydrocarbon in the first kind solvent anhydrated, magnetic agitation is dissolved, to be dissolved complete after, containing when measuring the electronics of ratio with lithium metal etc. in solution, stand-by under being kept at ar gas environment;
Described first kind solvent is ethers or amine organic compound;
(2) silicon tetrachloride liquid-phase reduction becomes nano-silicon: under argon shield, to in the reactor that the obtained electronics solution of step (1) is housed, dropwise add the silicon tetrachloride accounting for electronics total solution weight 5% ~ 20%, simultaneously with magnetic agitation or electric stirring, after silicon tetrachloride dropwises, obtain the suspension-turbid liquid that the granularity be in electronics solution is the nano-silicon particle of 10 ~ 100nm;
(3) preparation of graphene oxide glue sample solution: using water as dispersant, the configuration graphite oxide aqueous solution or Graphene suspension-turbid liquid, add nitric acid again, the graphite oxide aqueous solution or Graphene suspension-turbid liquid are mixed with nitric acid, after From Solution Under Ultrasound Treatment, centrifuge washing repeatedly, after system is washed pH=7, vacuumize, then by the desciccate that obtains and the process of Equations of The Second Kind solvent supersonic, be made into glue sample solution;
Described Equations of The Second Kind solvent is amine or alcohols solvent;
(4) graphene oxide glue sample solution loadings is in nano-silicon: by extremely even for the nano-silicon suspension-turbid liquid high-speed stirred be in step (2) in electronics solution, and add electronics solution and dilute as reducing agent, start again to be slowly added dropwise to the obtained graphene oxide glue sample solution of step (3), the addition of graphene oxide glue sample solution is determined by the mass ratio of nano-silicon and Graphene, stir, adjoint first kind solvent mixes indigenous graphite alkene gradually with Equations of The Second Kind solvent, after Graphene glue sample solution to be oxidized is added dropwise to complete, again through ultrasonic process, dispersing nanometer silicon and Graphene,
(5) the half-finished drying of combination electrode material and sintering: the mixed solution that step (4) obtains is through centrifugation; after vacuum filtration and drying; be placed in quartz boat; be positioned in the tube furnace of argon shield; control gas flow rate; calcining, by the product grinding and sieving obtained, obtains combination electrode material.
2. a preparation method for nanometer silicon/graphene lithium ion battery cathode material as claimed in claim 1, is characterized in that comprising the following steps:
(1) preparation of electronics solution: under argon shield, by the organic compound solubilization of lithium metal and multiring aromatic hydrocarbon in the first kind solvent anhydrated, magnetic agitation is dissolved, to be dissolved complete after, containing when measuring the electronics of ratio with lithium metal etc. in solution, stand-by under being kept at ar gas environment;
Described first kind solvent is ethers or amine organic compound;
(2) silicon tetrachloride liquid-phase reduction becomes nano-silicon: under argon shield, to in the reactor that the obtained electronics solution of step (1) is housed, dropwise add the silicon tetrachloride accounting for electronics total solution weight 5% ~ 20%, simultaneously with magnetic agitation or electric stirring, after silicon tetrachloride dropwises, obtain the suspension-turbid liquid that the granularity be in electronics solution is the nano-silicon particle of 10 ~ 100nm;
(3) preparation of graphene oxide glue sample solution: using water as dispersant, the configuration graphite oxide aqueous solution or Graphene suspension-turbid liquid, add nitric acid again, the graphite oxide aqueous solution or Graphene suspension-turbid liquid are mixed with nitric acid, after From Solution Under Ultrasound Treatment, centrifuge washing repeatedly, after system is washed pH=7, vacuumize, then by the desciccate that obtains and the process of Equations of The Second Kind solvent supersonic, be made into glue sample solution;
Described Equations of The Second Kind solvent is amine or alcohols solvent;
(4) graphene oxide glue sample solution loadings is in nano-silicon: by extremely even for the nano-silicon suspension-turbid liquid high-speed stirred be in step (2) in electronics solution, and add electronics solution and dilute as reducing agent, start again to be slowly added dropwise to the obtained graphene oxide glue sample solution of step (3), the addition of graphene oxide glue sample solution is determined by the mass ratio of nano-silicon and Graphene, stir, adjoint first kind solvent mixes indigenous graphite alkene gradually with Equations of The Second Kind solvent, after Graphene glue sample solution to be oxidized is added dropwise to complete, again through ultrasonic process, dispersing nanometer silicon and Graphene,
(5) the half-finished drying of combination electrode material and sintering: the mixed solution that step (4) obtains is through centrifugation; after vacuum filtration and drying; be placed in quartz boat; be positioned in the tube furnace of argon shield; control gas flow rate; calcining, by the product grinding and sieving obtained, obtains combination electrode material.
3. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, it is characterized in that: the organic compound of the multiring aromatic hydrocarbon described in step (1) is biphenyl, 4, 4 '-benzidine, 4, 4 '-dimethoxy-biphenyl, anthracene, naphthalene, one in luxuriant and rich with fragrance and Graphene or two or more, ethers organic compound described in step (1) is dicyclohexyl ether, one in glycol dimethyl ether and ether or two or more, the described amine organic compound of step (1) is ethylenediamine, tripropyl amine (TPA), morpholine, amine solvent described in step (3) be ethylenediamine and tripropyl amine (TPA) one or both, step (3) described alcohols solvent is ethanol, one in cyclohexanol and ethylene glycol or two or more.
4. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, it is characterized in that: described in step (1), the consumption of lithium metal is 1% ~ 5% of electronics total solution weight, the consumption of the organic compound of multiring aromatic hydrocarbon is 0% ~ 5% of electronics total solution weight.
5. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, it is characterized in that: described in step (3), the mass fraction of the graphite oxide aqueous solution or Graphene suspension-turbid liquid is 0.5 ~ 1.5g/L, the mass concentration of described nitric acid is 60% ~ 70%, and the volume ratio of the graphite oxide aqueous solution or Graphene suspension-turbid liquid and nitric acid is 1:2 ~ 10.
6. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, is characterized in that: in glue sample solution described in step (3), the mass fraction of graphene oxide is 0.1 ~ 5g/L.
7. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, is characterized in that: mass ratio 1:5 ~ 10 of nano-silicon and Graphene in step (4).
8. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, is characterized in that: the mass percent adding electronics solution in step (4) is 0% ~ 5%, and the frequency of ultrasonic process is 40 ~ 80Hz.
9. the preparation method of nanometer silicon/graphene lithium ion battery cathode material according to claim 2, is characterized in that: the gas flow rate 20 ~ 100mL/min in step (5), and sintering temperature is 500 DEG C ~ 800 DEG C, calcining 2 ~ 5h.
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