CN103400970A - 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 nano-silicon/graphene lithium ion battery negative material and preparation method thereof.
Background technology
Since Japanese Sony Corporation in 1991 released commercial lithium ion battery product first, lithium ion battery developed so far, went through more than 20 years.Lithium ion battery has unique embedding/deviate from the Mechanism of electrochemical behaviors of anhydrous of lithium ion, thereby more similar battery product, and it has the advantages such as specific capacity is large, operating voltage is high, safe, environmental pollution is little.As the exploitation of the negative material of lithium ion battery storage lithium main body, just become and improved the total specific capacity of lithium ion battery, discharged and recharged and the key point of cycle performance.
In early days, the negative material of lithium ion battery is take lithium alloy as main, and main problem is that cycle performance is poor and irreversible capacity is large first.Its basic reason is that there is the restructuring of crystal structure in negative material in charge and discharge process, cause larger volumetric expansion; In addition, also there is alternate change in volume to cause the loss of embedding lithium material.So, in the commercial batteries after industrialization, abandoned the high alloy material of theoretical specific capacity and used the graphite-like material with carbon element that forms the slotting compound of layer with lithium ion instead.Because the graphite-like material with carbon element can hold lithium ion by its graphite gaps, thereby solved the problem of volumetric expansion.And the good graphite-like material with carbon element of this class chemical property has also just become modal negative material in present commodity lithium ion battery.
Yet 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 in practical application, has reached 370mAh/g, substantially near theoretical level.Even the graphite-like material with carbon element of modification, its capacity be 450mAh/g just also.Therefore, although graphite has guaranteed the cycle performance of lithium ion battery, greatly limited its total specific capacity, and this does not catch up with present functional requirement for lithium ion battery far away yet.So, have exploitation high power capacity, graphite-like material with carbon element lithium ion battery negative material in addition, become the task of top priority.
Under comparing, silicon based anode material is in non-carbon class negative material, and its performance seems and more has superiority.It has the highest theoretical capacity than (forming Li4.4Si, theoretical capacity is up to 4200mAh/g) and relatively low embedding lithium current potential, than other metal materials, better stability and fail safe also being arranged, 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 exists the bulk effect (cubical expansivity>300%) in charge and discharge process, and cause that the own recurring structure of material in charge and discharge process collapses, the forfeiture that electrically contacts forfeiture, conductivity ability of efflorescence gradually, active material and collector, finally caused the loss of reversible capacity.
But, the technical problem that exists for silica-base material has at present also had certain solution.By silicon is processed to nanoscale, its absolute volume is changed greatly to descend, or adopt surface modification, doping, the method such as compound to form to coat or the system of high degree of dispersion, thereby improve the mechanical property of material, to alleviate internal stress that in the removal lithium embedded process, volumetric expansion the produces destruction to material structure, this just can eliminate the impact of bulk effect, thereby reaches the purpose that improves its electrochemistry cyclical stability.But then, pure nano-silicon is easily reunited again, and utilizes the silica-base material of existing surface modification and doping techniques modified, exists again expensive or doped level is bad, the inhomogenous new problem of product.Therefore, the lithium ion battery take the silica-base material of pure nano-silicon or modified as negative material, can only lie in laboratory all the time, and industrialization that can not be successful.
In addition, the chemical property research and development of carbon class material preferably also have breakthrough.After using the negative material of single-layer graphene as lithium ion battery instead, its theoretical capacity ratio can reach 744mAh/g, and the Graphene negative material of report is arranged, its first discharge capacity can reach 650mAh/g, after 100 circulations, its capacity still remains on the level of 460mAh/g.Therefore, although the Graphene theoretical capacity relatively some metals and silica-base material more weak, if the high power capacity of it and silica-base material closely can be combined, just can improve the cycle performance of silica-base material.In the research report, by silica flour (～40nm) with Graphene, according to the ratio mechanical mixture of mass ratio 1:1, grind, 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, nano-silicon and the Graphene of high theoretical capacity ratio being combined, is exactly the emphasis of studying for non-carbon negative pole material now.Now main combination is all the time still on mechanical yardstick, mainly with ball-milling method, Graphene and nano-silicon to be combined, although can play certain effect, because mechanical yardstick mixing is inhomogeneous, can't allow all the time the performance of Graphene give full play to.And the heat treating process energy consumption that can reach the molecular scale combination is high, and the COD chemical vapour deposition technique involves great expense again, is not suitable for commercial development.Therefore, the combination technology of carrying out a kind of Graphene effectively and nano-silicon is 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 are 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 that a kind of electric conductivity is excellent, the nano-silicon of stable cycle performance/graphene lithium ion battery negative material.
Another object of the present invention is to provide the preparation method of a kind of nano-silicon/graphene lithium ion battery negative material.
For addressing the above problem, the technical solution adopted in the present invention is as follows:
A kind of nano-silicon/graphene lithium ion battery negative material, it comprises nano-silicon and Graphene, wherein, the nano-silicon particle size is 10～100nm, the mass ratio 1:5 of nano-silicon and Graphene～10.
Due to the theoretical specific capacity of Graphene (～700mAh/g) to compare nano-silicon less, excessive Graphene can cause the average specific capacity loss of material monolithic, therefore, during greater than 1:10, the specific capacity of material monolithic just starts to have occurred decay when the ratio of nano-silicon and Graphene.In addition, if nano-silicon and Graphene contain quantity not sufficient 1:5, can cause Graphene to cover nano-silicon fully, make still to exist and reunite and lose the possibility that electrically contacts between the nano-silicon particle, thereby further cause the cycle performance of material to be affected.
The preparation method of a kind of nano-silicon/graphene lithium ion battery negative material, comprise the following steps:
(1) preparation of electronics solution: under argon shield, lithium metal and cosolvent are dissolved in the first kind solvent that anhydrates, magnetic agitation is dissolved, and after to be dissolved completing, while in solution, containing the electronics with the metering ratio such as lithium metal, is kept under ar gas environment stand-by;
(2) the silicon tetrachloride liquid-phase reduction becomes nano-silicon: under argon shield, in the reactor that the electronics solution that step (1) makes is housed, add dropwise that to account for the electronics total solution weight be 5%～20% silicon tetrachloride, follow simultaneously magnetic agitation or electric stirring, after silicon tetrachloride dropwises, the granularity that acquisition is in electronics solution is the suspension-turbid liquid of the nano-silicon particle of 10～100nm, and preferred, the rotating speed of stirring maintains 100～300 rev/mins;
(3) preparation of graphene oxide glue sample solution: using water as dispersant, the configuration graphite oxide aqueous solution or Graphene suspension-turbid liquid, add again nitric acid, the graphite oxide aqueous solution or Graphene suspension-turbid liquid are mixed with nitric acid, after From Solution Under Ultrasound Treatment, centrifuge washing repeatedly, by system wash pH near neutrality after, vacuumize, then the desciccate that will obtain and the processing of Equations of The Second Kind solvent supersonic, be made into glue sample solution;
(4) graphene oxide glue sample solution is carried on nano-silicon: the nano-silicon suspension-turbid liquid high-speed stirred that is in step (2) in electronics solution is extremely even, and add electronics solution and dilute as reducing agent, start again slowly to be added dropwise to the graphene oxide glue sample solution that step (3) makes, the mass ratio of pressing nano-silicon and Graphene determines the addition of graphene solution, stir, follow the indigenous graphite alkene gradually that mixes of first kind solvent and Equations of The Second Kind solvent, after graphene solution is added dropwise to complete, pass through again ultrasonic processing, dispersing nanometer silicon and Graphene, preferably, the rotating speed that stirs is 150～300 rev/mins,
(5) the half-finished drying of combination electrode material and sintering: the mixed solution that step (4) obtains separates 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, the product grinding and sieving by obtaining, obtain combination electrode material.
As further technical scheme of the present invention, the described cosolvent of step (1) is the organic compound of multiring aromatic hydrocarbon, and described first kind solvent is ethers or amine organic compound, and the described Equations of The Second Kind solvent of step (3) is amine or alcohols solvent.
Polycyclic aromatic hydrocarbon can make lithium metal in the lithium ion that dissolving forms afterwards is embedded into the fragrance layer as cosolvent, thereby dissolution equilibrium is moved, and further promotes the formation of solvated electron in solvent.Because there are not active hydrogen in amine and ethers, 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 partial oxidation on graphite and Graphene, thereby can effectively assist the dissolving of graphite and Graphene, therefore select alcohols or amine as the Equations of The Second Kind solvent.
Preferably, the described cosolvent of step (1) is biphenyl, 4,4 '-benzidine, 4,4 '-dimethoxy-biphenyl and analog, a kind of or two or more in anthracene, naphthalene, phenanthrene and Graphene.
Preferably, described first kind solvent is a kind of or two or more in ethylenediamine, tripropyl amine (TPA), morpholine, dicyclohexyl ether, glycol dimethyl ether and ether.
Preferably, the described Equations of The Second Kind solvent of step (3) is a kind of or two or more in ethanol, ethylenediamine, tripropyl amine (TPA), cyclohexanol and ethylene glycol.
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 cosolvent also can cause the formation of solvated electron, just reaction is carried out slowlyer.
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, the mass ratio 1:5 of nano-silicon and graphene oxide～10 in step (4).
As further technical scheme of the present invention, the mass percent of adding electronics solution in step (4) is 0%～5%, and the frequency of ultrasonic processing 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 ℃～800 ℃, calcining 2～5h.
Compared to existing technology, beneficial effect of the present invention is:
1) the silicon-carbon combination electrode material for preparing of the present invention, after mode by liquid-phase reduction obtains the more controlled nano-silicon particle of granularity, the mode of separating out again colloid by changing solvent forms glue-line when Graphene is reduced, be adsorbed on existing nanometer silica gel core, thereby make between silicon-carbon to reach the combination of molecule aspect, the Si-C composite material that is obtained by the method, its stable cycle performance, relative conventional graphite class and pure Graphene class material, has the specific capacity more than 1 times, and complete in the reaction homophase, simple to operate, do not need special equipment to complete.
2) the present invention becomes nano-silicon by the silicon tetrachloride liquid-phase reduction, in the liquid phase situ, that partial oxidation is graphene-supported on nano-silicon again, further under the reproducibility environment, the partial oxidation Graphene is reduced to Graphene, can be efficiently on molecular scale by Graphene and nano-silicon combination, thereby the better Graphene of a kind of performance-nano-silicon negative material is provided.
3) the liquid-phase reduction technology of the present invention's employing becomes nano-silicon by the silicon tetrachloride liquid-phase reduction, and the nano-silicon that obtains has better yardstick and structure.
4) when 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 on molecular level, can reduce the bulk effect of material effectively, and whole cycle performance is further improved.
5) Graphene in composite material of the present invention can effectively suppress the volumetric expansion of silicium cathode, and the nano-silicon that therefore prepares/graphene lithium ion battery negative material has excellent electric conductivity, and corresponding lithium ion battery specific capacity is large, good cycle.
Embodiment
Embodiment 1:
Under argon shield, by mass percent, be that 1% lithium metal and 1% biphenyl are dissolved in the glycol dimethyl ether of 1kg, magnetic agitation is dissolved, and after dissolving, solution is blackish green.To dripping mass ratio in this solution, be 5% silicon tetrachloride again, in 1h, drip, magnetic agitation in addition, maintain 100 rev/mins simultaneously, after 1h, stops stirring.
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.5g/L, adding volume ratio is with ultrasonic processing 0.5h after the nitric acid of 60% concentration of 1:2.After processing, by the solution that obtains centrifuge washing repeatedly, while being washed till pH=7, finish.After vacuumize, again with ultrasonic processing 0.5h, it is dissolved in cyclohexanol, is configured to the graphene oxide glue sample solution of 0.1g/L.
The rotating speed of nano-silicon suspension-turbid liquid with 200 rev/mins stirred, and, in whipping process, be nano-silicon in mass ratio: Graphene=1:8 drips the graphene oxide solution of above-mentioned 1g/L, in 1h, dropwises.After 1h, then with the ultrasonic dispersion 0.5h of 40Hz, after disperseing to complete, centrifugal rotational speed is 16000 rev/mins, centrifugal 0.5h.The centrifugal final vacuum suction filtration that completes, drying, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 20mL/min, under 500 ℃, calcine 2h, by the product grinding and sieving that obtains, obtain the combination electrode material of embodiment 1.
Embodiment 2:
Under argon shield, by mass percent, be 4 of 3% lithium metal and 5%, 4 '-dimethoxy-biphenyl is dissolved in the tripropyl amine (TPA) of 1kg, and magnetic agitation is dissolved, and after dissolving, solution is near navy blue.To dripping mass ratio in this solution, be 20% silicon tetrachloride again, in 3h, drip, magnetic agitation in addition, maintain 150 rev/mins simultaneously, after 1h, stops stirring.
Using water as dispersant, and the graphite oxide aqueous solution of configuration 0.5g/L, after adding volume ratio to be the nitric acid of 60% concentration of 1:5, with ultrasonic processing 0.5h.After processing, by the solution that obtains centrifuge washing repeatedly, while being washed till pH=7, finish.After vacuumize, again with ultrasonic processing 3h, it is dissolved in ethanol, is configured to the graphene oxide glue sample solution of 5g/L.
The rotating speed of nano-silicon suspension-turbid liquid with 150 rev/mins stirred, and, in whipping process, be nano-silicon in mass ratio: Graphene=1:5 drips the graphene oxide solution of above-mentioned 5g/L, in 2h, dropwises.After 2h, then with the ultrasonic dispersion of 40Hz 1h, after disperseing to complete, centrifugal rotational speed is 16000 rev/mins, centrifugal 0.5h.The centrifugal final vacuum suction filtration that completes, drying, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 30mL/min, under 600 ℃, calcine 5h, by the product grinding and sieving that obtains, obtain the combination electrode material of embodiment 2.
Embodiment 3:
Under argon shield, by mass percent, be that 5% lithium metal and 5% anthracene are dissolved in the morpholine of 1kg, magnetic agitation is dissolved, and after dissolving, solution is near metal black.To dripping mass ratio in this solution, be 20% silicon tetrachloride again, in 3h, drip, magnetic agitation in addition, maintain 150 rev/mins simultaneously, after 1h, stops stirring.
Using water as dispersant, and the Graphene suspension-turbid liquid of configuration 0.5g/L, after adding volume ratio to be the nitric acid of 60% concentration of 1:10, with the ultrasonic processing of 60Hz 0.5h.After processing, by the solution that obtains centrifuge washing repeatedly, while being washed till pH=7, finish.After vacuumize, again with ultrasonic processing 3h, it is dissolved in ethylene glycol, is configured to the graphene oxide glue sample solution of 1g/L.
The rotating speed of nano-silicon suspension-turbid liquid with 200 rev/mins stirred, and, in whipping process, be nano-silicon in mass ratio: Graphene=1:10 drips the graphene oxide solution of above-mentioned 5g/L, in 2h, dropwises.After 2h, then with ultrasonic dispersion 1h, after disperseing to complete, centrifugal rotational speed is 16000 rev/mins, centrifugal 0.5h.The centrifugal final vacuum suction filtration that completes, drying, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 50mL/min, under 800 ℃, calcine 3h, by the product grinding and sieving that obtains, obtain the combination electrode material of embodiment 3.
Embodiment 4:
Under argon shield, by mass percent, be 5% lithium metal, do not add cosolvent, directly be dissolved in the ethylenediamine of 1kg, magnetic agitation is dissolved, and after dissolving, solution is navy blue.To dripping mass ratio in this solution, be 15% silicon tetrachloride again, in 2h, drip, magnetic agitation in addition, maintain 200 rev/mins simultaneously, after 1h, stops stirring.
Using water as dispersant, the graphite oxide aqueous solution of configuration 0.5g/L, adding volume ratio is with ultrasonic processing 0.5h after the nitric acid of 60% concentration of 1:2.After processing, by the solution that obtains centrifuge washing repeatedly, while being washed till pH=7, finish.After vacuumize, again with ultrasonic processing 1h, it is dissolved in ethanol, is configured to the graphene oxide glue sample solution of 2g/L.
The rotating speed of nano-silicon suspension-turbid liquid with 300 rev/mins stirred, and, in whipping process, be nano-silicon in mass ratio: Graphene=1:9 drips the graphene oxide solution of above-mentioned 2g/L, in 2h, dropwises.After 2h, then with the ultrasonic dispersion of 60Hz 1h, after disperseing to complete, centrifugal rotational speed is 30000 rev/mins, centrifugal 1h.The centrifugal final vacuum suction filtration that completes, drying, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 70mL/min, under 800 ℃, calcine 2h, by the product grinding and sieving that obtains, obtain the combination electrode material of embodiment 4.
Embodiment 5:
Under argon shield, by mass percent, be 5% lithium metal, do not add cosolvent, directly be dissolved in the tripropyl amine (TPA) of 1kg, magnetic agitation is dissolved, and after dissolving, solution is metal black.To dripping mass ratio in this solution, be 20% silicon tetrachloride again, in 1h, drip, magnetic agitation in addition, maintain 300 rev/mins simultaneously, after 1h, stops stirring.
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.5g/L, adding volume ratio is with ultrasonic processing 0.5h after the nitric acid of 60% concentration of 1:2.After processing, by the solution that obtains centrifuge washing repeatedly, while being washed till pH=7, finish.After vacuumize, again with ultrasonic processing 1h, it is dissolved in cyclohexanol, is configured to the graphene oxide glue sample solution of 5g/L.
The rotating speed of nano-silicon suspension-turbid liquid with 300 rev/mins stirred, and, in whipping process, be nano-silicon in mass ratio: Graphene=1:9 drips the graphene oxide solution of above-mentioned 5g/L, in 2h, drips.After 2h, then with the ultrasonic dispersion of 80Hz 1h, after disperseing to complete, centrifugal rotational speed is 30000 rev/mins, centrifugal 1h.The centrifugal final vacuum suction filtration that completes, drying, then be positioned in quartz boat, be positioned in the tube furnace of argon shield, keep the gas flow rate of 100mL/min, under 500 ℃, calcine 5h, by the product grinding and sieving that obtains, obtain the combination electrode material of embodiment 5.
The comparative example:
Using water as dispersant, the Graphene suspension-turbid liquid of configuration 0.4g/L, adding volume ratio is with ultrasonic processing 0.5h after the nitric acid of 60% concentration of 1:2.After processing, by the solution that obtains centrifuge washing repeatedly, while being washed till pH=7, finish.After vacuumize, again with ultrasonic processing 1h, it is dissolved in the water, is 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 dispersion 1h, be nano-silicon in mass ratio: Graphene=1:2 drips the graphene oxide solution of above-mentioned 0.4g/L, in 2h, dropwises.After 2h; again with the ultrasonic dispersion of 40Hz 1.5h; disperse to complete the final vacuum suction filtration; drying, then be positioned in quartz boat, be positioned over hydrogen-argon-mixed body (hydrogen: in the tube furnace of the protection of argon=6%:94%); the gas flow rate that keeps 70mL/min; under 800 ℃, calcine 1h, by the product grinding and sieving that obtains, obtain the combination electrode material of comparative example.
Above-described embodiment 1～5 and comparative example's electrical performance test method is: the electrode material that will obtain is placed on Copper Foil makes 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, with the electric current of 100mAh/g, carry out the charge and discharge cycles test, circulate 100 times.
The results list of above-described embodiment 1～5 and comparative example's electrical performance testing is as follows:
As seen from the above table, preparation method of the present invention compares with the comparative example, has the difference of conspicuousness, and negative material of the present invention is reserve capacity effectively.Yet, the first discharge specific capacity of present existing graphitic carbon negative 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 material and similar silicon-carbon cathode material.This is can effectively control combining closely between nano-silicon and Graphene due to new carrying method and method of reducing, and Graphene is as buffer substance, prevents structural deterioration and the change in volume that causes, thereby has eliminated the poor problem of cycle performance.
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, the variation of those skilled in the art does on basis of the present invention any unsubstantiality and replacement all belong to the present invention's scope required for protection.
Claims (10)
1. nano-silicon/graphene lithium ion battery negative material, it is characterized in that: it comprises nano-silicon and Graphene, wherein, the nano-silicon particle size is 10～100 nm, the mass ratio 1:5 of nano-silicon and Graphene～10.
2. the preparation method of nano-silicon as claimed in claim 1/graphene lithium ion battery negative material, is characterized in that comprising the following steps:
(1) preparation of electronics solution: under argon shield, lithium metal and cosolvent are dissolved in the first kind solvent that anhydrates, magnetic agitation is dissolved, and after to be dissolved completing, while in solution, containing the electronics with the metering ratio such as lithium metal, is kept under ar gas environment stand-by;
(2) the silicon tetrachloride liquid-phase reduction becomes nano-silicon: under argon shield, in the reactor that the electronics solution that step (1) makes is housed, dropwise add the silicon tetrachloride that accounts for electronics total solution weight 5%～20%, follow simultaneously magnetic agitation or electric stirring, after silicon tetrachloride dropwised, the granularity that obtains to be in electronics solution was the suspension-turbid liquid of the nano-silicon particle of 10～100 nm;
(3) preparation of graphene oxide glue sample solution: using water as dispersant, the configuration graphite oxide aqueous solution or Graphene suspension-turbid liquid, add again nitric acid, the graphite oxide aqueous solution or Graphene suspension-turbid liquid are mixed with nitric acid, after From Solution Under Ultrasound Treatment, centrifuge washing repeatedly, by system wash pH near neutrality after, vacuumize, then the desciccate that will obtain and the processing of Equations of The Second Kind solvent supersonic, be made into glue sample solution;
(4) graphene oxide glue sample solution is carried on nano-silicon: the nano-silicon suspension-turbid liquid high-speed stirred that is in step (2) in electronics solution is extremely even, and add electronics solution and dilute as reducing agent, start again slowly to be added dropwise to the graphene oxide glue sample solution that step (3) makes, the mass ratio of pressing nano-silicon and Graphene determines the addition of graphene solution, stir, follow the indigenous graphite alkene gradually that mixes of first kind solvent and Equations of The Second Kind solvent, after graphene solution is added dropwise to complete, pass through again ultrasonic processing, dispersing nanometer silicon and Graphene;
(5) the half-finished drying of combination electrode material and sintering: the mixed solution that step (4) obtains separates 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, the product grinding and sieving by obtaining, obtain combination electrode material.
3. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material, it is characterized in that: the described cosolvent of step (1) is the organic compound of multiring aromatic hydrocarbon, described first kind solvent is ethers or amine organic compound, and the described Equations of The Second Kind solvent of step (3) is amine or alcohols solvent.
4. the preparation method of nano-silicon according to claim 3/graphene lithium ion battery negative material, it is characterized in that: the described cosolvent of step (1) is biphenyl, 4, 4 '-benzidine, 4, 4 '-dimethoxy-biphenyl and analog, anthracene, naphthalene, a kind of or two or more in luxuriant and rich with fragrance and Graphene, described first kind solvent is ethylenediamine, tripropyl amine (TPA), morpholine, dicyclohexyl ether, a kind of or two or more in glycol dimethyl ether and ether, the described Equations of The Second Kind solvent of step (3) is ethanol, ethylenediamine, tripropyl amine (TPA), a kind of or two or more in cyclohexanol and ethylene glycol.
5. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material, it is characterized in that: 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.
6. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material, it is characterized in that: described in step (3), the mass fraction of the graphite oxide aqueous solution or Graphene suspension-turbid liquid is 0.5～1.5 g/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.
7. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material, it is characterized in that: described in step (3), the mass fraction of glue sample solution is 0.1～5 g/L.
8. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material, is characterized in that: the mass ratio 1:5 of nano-silicon and graphene oxide～10 in step (4).
9. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material, it is characterized in that: the mass percent of adding electronics solution in step (4) is 0%～5%, the frequency of ultrasonic processing is 40～80 Hz.
10. the preparation method of nano-silicon according to claim 2/graphene lithium ion battery negative material is characterized in that: gas flow rate 20～100 mL/min in step (5), sintering temperature is 500 ℃～800 ℃, calcining 2～5 h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015010437A1 (en) * | 2013-07-20 | 2015-01-29 | 深圳粤网节能技术服务有限公司 | A nano silicon/graphene lithium ion battery cathode material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522534A (en) * | 2012-01-09 | 2012-06-27 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery |
| CN102544445A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Preparation method for graphene composite material supporting silicon nanoparticles |
| US20120288750A1 (en) * | 2011-05-12 | 2012-11-15 | Northwestern University | Graphene materials having randomly distributed two-dimensional structural defects |
| CN103035890A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Silicon and graphene composite electrode material and preparation method thereof |
| WO2013056074A1 (en) * | 2011-10-14 | 2013-04-18 | Wayne State University | Composite anode for lithium ion batteries |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306757B (en) * | 2011-08-26 | 2014-07-02 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN103022436B (en) * | 2011-09-21 | 2015-04-01 | 海洋王照明科技股份有限公司 | Electrode composite material preparation method |
| CN103400970B (en) * | 2013-07-20 | 2015-07-08 | 深圳粤网节能技术服务有限公司 | Nanometer silicon/graphene lithium ion battery cathode material and preparation method thereof |
-
2013
- 2013-07-20 CN CN201310307450.0A patent/CN103400970B/en active Active
- 2013-12-31 WO PCT/CN2013/091124 patent/WO2015010437A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544445A (en) * | 2010-12-29 | 2012-07-04 | 海洋王照明科技股份有限公司 | Preparation method for graphene composite material supporting silicon nanoparticles |
| US20120288750A1 (en) * | 2011-05-12 | 2012-11-15 | Northwestern University | Graphene materials having randomly distributed two-dimensional structural defects |
| CN103035890A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Silicon and graphene composite electrode material and preparation method thereof |
| WO2013056074A1 (en) * | 2011-10-14 | 2013-04-18 | Wayne State University | Composite anode for lithium ion batteries |
| CN102522534A (en) * | 2012-01-09 | 2012-06-27 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015010437A1 (en) * | 2013-07-20 | 2015-01-29 | 深圳粤网节能技术服务有限公司 | A nano silicon/graphene lithium ion battery cathode material and preparation method thereof |
| CN104577113A (en) * | 2014-12-17 | 2015-04-29 | 李震祺 | Graphene-coated lithium ferric manganese phosphate cathode material and preparation method thereof |
| EP3133690A1 (en) | 2015-07-20 | 2017-02-22 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Silicon-carbon composite particulate material |
| TWI692901B (en) * | 2015-08-04 | 2020-05-01 | 日商三井化學股份有限公司 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery containing the same, and method for manufacturing negative electrode for lithium ion secondary battery |
| CN108232139A (en) * | 2017-12-20 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of graphene composite material and preparation method thereof |
| CN108232139B (en) * | 2017-12-20 | 2020-08-28 | 中国科学院福建物质结构研究所 | Graphene composite material and preparation method thereof |
| CN108807940A (en) * | 2018-07-18 | 2018-11-13 | 绍兴文理学院 | A kind of preparation method of graphene enhancing carbon-silicon composite material |
| CN113122749A (en) * | 2019-12-31 | 2021-07-16 | 山西沃特海默新材料科技股份有限公司 | Carbon source reinforcing agent, carbon source reinforcing alloy and preparation method thereof |
| CN115215342A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | In-situ symbiotic nano silicide and preparation method thereof |
| CN115215341A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Preparation method of nano silicon |
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