CN105206806A - Lithium ion battery negative electrode material and preparing method thereof - Google Patents
Lithium ion battery negative electrode material and preparing method thereof Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- 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
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Abstract
The invention relates to a lithium ion battery negative electrode material and a preparing method thereof. The negative electrode material comprises an organosilicone waste contact mass, a silicon-carbon composite material and a carbon material matrix. The preparing method of the lithium ion battery negative electrode material includes the steps that a carbonaceous organic material serves as a raw material and is subjected to splitting decomposition to obtain carbon particles; the silicon-carbon composite material is formed by the carbon particles and silicon through a modifying reaction; according to the modifying reaction, the carbon particles and the silicon are dissolved in solvent and subjected to electrolysis, and the silicon-carbon composite material is obtained through smashing and screening after ultrasonic treatment is carried out. The lithium ion battery negative electrode material is high in first-time discharge efficiency and good in conducting performance, IACS% reaches 60-70%, and the room-temperature diffusion rate of lithium ions in the electrode material is high; the negative electrode material is good in cycle performance, capable of preventing agglomeration of nano active bodies and beneficial for stabilization of an electrode structure and battery performance, and therefore the life of a battery is longer; the preparing method is easy to operate and low in cost and belongs to waste utilization, and mass production is easy to realize.
Description
Technical field
The present invention relates to battery material field, be specifically related to negative material of a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is with lithium metal for positive electrode, take carbon as the battery of main negative material; When charging to battery, positive pole there is lithium ion generate, and by electrolyte movement to negative pole; And negative material is layer structure, have a lot of micropore, the lithium ion therefore moving to negative pole just embeds in micropore, and the lithium ion of embedding is more, and charging capacity is higher; Similarly, when carrying out battery discharge, the lithium ion being embedded in negative pole is deviate to move back positive pole.At present, lithium ion battery because of its high-energy-density, high working voltage, excellent security performance, nuisanceless, have extended cycle life, charge fast, the advantage such as the little and memory-less effect of self discharge, just be widely used in various electrical equipment, such as mobile phone, digital camera, notebook computer and intercom etc.But the theoretical capacity of the lithium ion battery of market sale is at present only 400mAh/g, can not meet the demand of the large-capacity high-power equipment such as electric automobile for lithium ion battery.
Therefore, large quantifier elimination has turned to the Novel anode material that can substitute material with carbon element, and wherein, silicon becomes popular candidate material because it has fabulous theoretical capacity and low intercalation potential; But the cycle performance of the lower initial coulomb efficiency of silicon materials and extreme difference limits its practical application.CN102637920B discloses a kind of utilization and prepares the application as lithium ion battery negative material of the waste catalyst that produces in organic silicon monomer methylchlorosilane process, and this invention solves the problem of the high-valued comprehensive utilization of the solid residue waste catalyst of organosilicon compound probability; With low cost, modifying and decorating method is simple, is easy to large-scale production; Reduce bulk effect; Improve electric conductivity, specific capacity and cyclical stability.But, in silicon-carbon composite cathode material, although the volumetric expansion that the embedding of lithium produces is uniform, even if expand and shrink reversible, the change of volume can produce very large irreversible capacity, causes the efficiency of first charge-discharge on the low side, therefore the change in volume cushioning silicon is needed, the film as far as possible not allowing electrode surface produce is damaged, in cyclic process, do not cause new surface exposure as far as possible, reduces the loss of irreversible capacity; Secondly, silicon is typical semiconductor structure materials, in order to improve the room temperature diffusion rate of lithium ion in silicon electrode material, will improve the electric conductivity of silicon materials, and this point is also be badly in need of improving; Again, due to the problem of bulk effect, elemental silicon material does electrode and cycle performance can be caused poor, therefore in order to improve the stable circulation performance of elemental silicon material, most employing Si-C composite material, so both can prevent the reunion of nano active body, is beneficial to again the stable of electrode structure; Suitably can also reduce the embedding lithium capacity of composite material, thus improve the cycle performance of material.
Summary of the invention
The object of the present invention is to provide a kind of discharging efficiency first high, conduct electricity very well and negative material of the strong lithium ion battery of cycle performance and preparation method thereof.
First aspect, the invention provides a kind of negative material of lithium ion battery, it is characterized in that, described negative material comprises abandoned catalyst in direct synthesis methylchlorosilane, Si-C composite material and material with carbon element matrix.For the addition of abandoned catalyst in direct synthesis methylchlorosilane, Si-C composite material and material with carbon element matrix, the present invention does not do concrete restriction, those skilled in the art can rule of thumb suitably add, and the present invention is typical but the addition of unrestriced abandoned catalyst in direct synthesis methylchlorosilane is 20g, 21g, 22g, 23g, 24g, 25g, 26g, 27g, 28g, 29g, 30g, 40g, 50g, 60g, 70g, 80g, 90g or 100g; The present invention is typical but the addition of unrestriced Si-C composite material is 20g, 21g, 22g, 23g, 24g, 25g, 26g, 27g, 28g, 29g, 30g, 40g, 50g, 60g, 70g, 80g, 90g or 100g; The present invention is typical but the addition of unrestriced material with carbon element matrix is 20g, 21g, 22g, 23g, 24g, 25g, 26g, 27g, 28g, 29g, 30g, 40g, 50g, 60g, 70g, 80g, 90g or 100g.
Preferably, the particle diameter of described abandoned catalyst in direct synthesis methylchlorosilane is 30nm ~ 40 μm, can be such as 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 500nm, 1 μm, 5 μm or 10 μm, more preferably 60nm ~ 10 μm;
Preferably, the aperture of described abandoned catalyst in direct synthesis methylchlorosilane is 3nm ~ 20 μm, can be such as 3nm, 10nm, 30nm, 50nm, 100nm, 300nm, 500nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, more preferably 10nm ~ 3 μm;
Preferably, described abandoned catalyst in direct synthesis methylchlorosilane comprises the mixture of carbon and/or copper and porous silicon.
Preferably, described material with carbon element matrix is the mixture of a kind of in carbon nano-tube, carbon fiber, graphite nodule, Graphene or native graphite or at least two kinds, it can be such as carbon nano-tube, carbon fiber, the mixture of graphite nodule and Graphene, the mixture of the mixture of native graphite, Graphene and graphite nodule or carbon nano-tube, carbon fiber, graphite nodule and native graphite.
Second aspect, the invention provides the preparation method of lithium ion battery negative material as described in relation to the first aspect, comprise with carbonaceous organic material is raw material, carbon granule is obtained by cracking, then carbon granule and silicon are dissolved in electrolysis in solvent, through ultrasonic wave process, pulverize and sieve and obtain Si-C composite material.
Preferably, described carbonaceous organic material is alkane and/or alkene;
Preferably, described alkane is the mixture of a kind of in C1 ~ C6 alkane or at least two kinds, such as, can be methane, ethane, the mixture of the mixture of methane and ethane or methane, ethane and propane, the mixture of a kind of more preferably in methane, ethane or propane or at least two kinds;
Preferably, described alkene is the mixture of a kind of in C2 ~ C8 alkene or at least two kinds, can be such as ethene, propylene, the mixture of ethene and propylene, the mixture of the mixture of ethene, propylene and butylene or ethene, propylene, butylene and divinyl, the mixture of a kind of more preferably in ethene, propylene or divinyl or at least two kinds;
Preferably, described carbonaceous organic material is the mixture of a kind of in methane, ethane, propane, ethene or propylene or at least two kinds, can be such as methane, ethane, propane, the mixture of methane and ethene, the mixture of the mixture of ethane, propane and propylene or methane, ethane, propane, ethene and propylene.
Preferably, the temperature of described cracking is 300 ~ 2000 DEG C, it can be such as 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, 1300 DEG C, 1400 DEG C, 1500 DEG C, 1600 DEG C, 1700 DEG C, 1800 DEG C, 1900 DEG C or 2000 DEG C, more preferably 600 ~ 1600 DEG C, be further preferably 800 ~ 1500 DEG C;
Preferably, the pressure of described cracking is 1 ~ 3MPa, can be such as 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2.0MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa, 2.5MPa, 2.6MPa, 2.7MPa, 2.8MPa, 2.9MPa or 3MPa, more preferably 1.5 ~ 2MPa;
Preferably, the time of described cracking is 1.5 ~ 24h, can be such as 1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, more preferably 3 ~ 12h.
Preferably, described composite modified reaction solvent used is the mixture of a kind of in ether, ethyl methyl ether, dimethylbenzene, toluene, water, chloroform or acetone or at least two kinds, it can be such as ether, ethyl methyl ether, the mixture of ether and dimethylbenzene, the mixture of the mixture of ethyl methyl ether, toluene and water or acetone, chloroform, water, toluene and ether;
Preferably, the bath raio of described modified-reaction is 1:(15 ~ 60), can be such as 1:15,1:20,1:25,1:30,1:35,1:40,1:45,1:50,1:55 or 1:60, more preferably 1:(30 ~ 40).
Preferably, the voltage of described electrolysis is 100 ~ 300V, such as, can be 100V, 110V, 120V, 130V, 140V, 150V, 160V, 170V, 180V, 190V, 200V, 210V, 220V, 230V, 240V, 250V, 260V, 270V, 280V, 290V or 300V; The time of described electrolysis is 15 ~ 25h, such as, can be 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h or 25h.
Preferably, described preparation method comprises by described Si-C composite material and waste catalyst vapour deposition on material with carbon element matrix, obtains the step of lithium ion battery negative material.
Preferably, described vapour deposition for carry out under protective atmosphere;
Preferably; described protective atmosphere is the mixture of a kind of in nitrogen, helium, argon gas or neon or at least two kinds, such as, can be nitrogen, helium; the mixture of argon gas and neon, the mixture of the mixture of nitrogen, helium and argon gas or nitrogen, helium, argon gas and neon.
Preferably, the time of described vapour deposition is more than 0.5h, such as, can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 15h, 13h, 14h or 15h, is preferably 1.5 ~ 48h, more preferably 3 ~ 36h;
Preferably, the temperature of described vapour deposition is 500 ~ 1000 DEG C, such as, can be 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C, more preferably 700 ~ 900 DEG C;
Preferably, the air pressure of described vapour deposition is below 3MPa, can be such as 2.9MPa, 2.8MPa, 2.7MPa, 2.6MPa, 2.5MPa, 2.4MPa, 2.3MPa, 2.2MPa, 2.1MPa, 2.0MPa, 1.9MPa, 1.8MPa, 1.7MPa, 1.6MPa, 1.5MPa, 1.4MPa, 1.3MPa, 1.2MPa, 1.1MPa or 1MPa, more preferably 1 ~ 2MPa;
Preferably, the equipment that described vapour deposition is used is fixed bed or fluid bed.Abandoned catalyst in direct synthesis methylchlorosilane the present invention at least possesses following advantage:
Lithium ion battery negative material of the present invention first discharging efficiency is high, reaches more than 60%, thus without the need to worrying that electrode surface is produced film area that is whether impaired and exposed surface in cyclic process and whether changed; Conduct electricity very well, IACS% reaches 60 ~ 70%, and the room temperature diffusion rate of lithium ion in electrode material is high; Good cycle, can prevent the reunion of nano active body, is conducive to stablizing of electrode structure and stablizing of battery performance, makes the life-span of battery longer.
In addition, method of the present invention is simple to operate, and low raw-material cost is easy to large-scale production, and belongs to refuse reclamation, reaches the effect of waste catalyst residue high-efficiency comprehensive utilization.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
The each component of table 1 embodiment 1 ~ 5 and proportioning thereof
| Abandoned catalyst in direct synthesis methylchlorosilane | Si-C composite material | Material with carbon element matrix | |
| Embodiment 1 | 23g | 15g | 30g |
| Embodiment 2 | 20g | 19g | 20g |
| Embodiment 3 | 24g | 24g | 23g |
| Embodiment 4 | 35g | 30g | 35g |
| Embodiment 5 | 38g | 19g | 30g |
The abandoned catalyst in direct synthesis methylchlorosilane of embodiment 1 the present embodiment comprises porous silicon, carbon and copper; Material with carbon element matrix comprises carbon fiber, graphite nodule and Graphene; The preparation of Si-C composite material is for raw material with methane and propylene, at 2000 DEG C, under 1MPa condition, cracking 10h obtains carbon granule, then obtains through composite modified with silicon, composite modified solvent for use is the mixed solvent of ethyl methyl ether, dimethylbenzene and water, and the bath raio of modified-reaction is 1:15; Finally by Si-C composite material and abandoned catalyst in direct synthesis methylchlorosilane vapour deposition on material with carbon element matrix, the protective atmosphere of vapour deposition is nitrogen, and vapor deposition times is 4h, and temperature is 1000 DEG C, and air pressure is 2MPa.
Embodiment 2
The abandoned catalyst in direct synthesis methylchlorosilane of the present embodiment comprises porous silicon and copper; Material with carbon element matrix comprises carbon fiber, carbon nano-tube, graphite nodule and native graphite; The preparation of Si-C composite material is for raw material with methane and propylene, at 300 DEG C, under 3MPa condition, cracking 24h obtains carbon granule, then obtains through composite modified with silicon, composite modified solvent for use is the mixed solvent of chloroform and water, and the bath raio of modified-reaction is 1:60; Finally by Si-C composite material and abandoned catalyst in direct synthesis methylchlorosilane vapour deposition on material with carbon element matrix, the protective atmosphere of vapour deposition is nitrogen, helium and neon, and vapor deposition times is 0.5h, and temperature is 900 DEG C, and air pressure is 1MPa.
Embodiment 3
The abandoned catalyst in direct synthesis methylchlorosilane of the present embodiment comprises porous silicon and carbon; Material with carbon element matrix comprises carbon fiber, carbon fiber and Graphene; The preparation of Si-C composite material is for raw material with propane and ethene, at 1150 DEG C, under 1.5MPa condition, cracking 1.5h obtains carbon granule, then obtains through composite modified with silicon, composite modified solvent for use is the mixed solvent of ethyl methyl ether, toluene and acetone, and the bath raio of modified-reaction is 1:37; Finally by Si-C composite material and abandoned catalyst in direct synthesis methylchlorosilane vapour deposition on material with carbon element matrix, the protective atmosphere of vapour deposition is nitrogen and argon gas, and vapor deposition times is 3h, and temperature is 750 DEG C, and air pressure is 1.2MPa.
Embodiment 4
The abandoned catalyst in direct synthesis methylchlorosilane of the present embodiment comprises porous silicon, carbon and copper; Material with carbon element matrix comprises carbon nano-tube and carbon fiber; The preparation of Si-C composite material is with methane, ethane and propylene for raw material, and at 1000 DEG C, under 2MPa condition, cracking 13h obtains carbon granule, then obtains through composite modified with silicon, and composite modified solvent for use is ether, and the bath raio of modified-reaction is 1:25; Finally by Si-C composite material and abandoned catalyst in direct synthesis methylchlorosilane vapour deposition on material with carbon element matrix, the protective atmosphere of vapour deposition is neon, and vapor deposition times is 25h, and temperature is 700 DEG C, and air pressure is 1.8MPa.
Embodiment 5
The abandoned catalyst in direct synthesis methylchlorosilane of the present embodiment comprises porous silicon, carbon and copper; Material with carbon element matrix is native graphite; The preparation of Si-C composite material is for raw material with propane, ethene and propylene, at 1500 DEG C, under 2.5MPa condition, cracking 15h obtains carbon granule, then obtain through composite modified with silicon, composite modified solvent for use is the mixed solvent of ether, toluene and chloroform, and the bath raio of modified-reaction is 1:52; Finally by Si-C composite material and abandoned catalyst in direct synthesis methylchlorosilane vapour deposition on material with carbon element matrix, the protective atmosphere of vapour deposition is helium and argon gas, and vapor deposition times is 40h, and temperature is 500 DEG C, and air pressure is 2.9MPa.
Comparative example 1
Identical with embodiment 1, just do not add abandoned catalyst in direct synthesis methylchlorosilane.Through performance test, discharging efficiency is 38% first, and conductivity is 40%, and after discharge and recharge 50 times, battery capacity conservation rate is 42%.
Comparative example 2
Identical with embodiment 2, just do not add Si-C composite material.Through performance test, discharging efficiency is 36.9% first, and conductivity is 38.7%, and after discharge and recharge 50 times, battery capacity conservation rate is 40%.
Comparative example 3
Identical with embodiment 3, just adopt commercially available Si-C composite material.Through performance test, discharging efficiency is 28.4% first, and conductivity is 32.6%, and after discharge and recharge 50 times, battery capacity conservation rate is 33%.The performance test results of embodiment 1 ~ 5 is as shown in table 2, can find out, the discharging efficiency first of lithium ion battery negative material of the present invention is high, all reach more than 60%, illustrate only have the positive pole lithium ion of less than 40% become after first time discharge and recharge negative pole SEI film component or consume cannot get back to positive pole in other respects, namely battery actual capacity than theoretical capacity reduce less than 40%.Existing Novel anode material, as carbon nano-tube and Graphene etc., first charge-discharge efficiency is generally lower, and how about 30%, therefore the first charge-discharge efficiency of negative material of the present invention at least improves 30 percentage points by comparison.Conductivity of the present invention is higher, and resistivity is little, and the electric current release efficiency of battery is higher; Simultaneously, battery capacity conservation rate after discharge and recharge 50 times is more than 90%, illustrate that negative material of the present invention has excellent cycle performance, this not only can prevent the reunion of nano active body, also help the stable of electrode structure, and battery performance is stable, make lithium ion battery more durable, the life-span is longer.
Table 2 the performance test results
Applicant states, the present invention illustrates process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned processing step, does not namely mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a negative material for lithium ion battery, is characterized in that, described negative material is abandoned catalyst in direct synthesis methylchlorosilane, Si-C composite material and material with carbon element matrix.
2. negative material according to claim 1, is characterized in that, the particle diameter of described abandoned catalyst in direct synthesis methylchlorosilane is 30nm ~ 40 μm, is preferably 60nm ~ 10 μm;
Preferably, the aperture of described abandoned catalyst in direct synthesis methylchlorosilane is 3nm ~ 20 μm, is preferably 10nm ~ 3 μm;
Preferably, described abandoned catalyst in direct synthesis methylchlorosilane comprises the mixture of carbon and/or copper and porous silicon.
3. negative material according to claim 1 and 2, is characterized in that, described material with carbon element matrix is the mixture of a kind of in carbon nano-tube, carbon fiber, graphite nodule, Graphene or native graphite or at least two kinds.
4. the preparation method of the lithium ion battery negative material as described in one of claims 1 to 3, it is characterized in that, comprise with carbonaceous organic material is raw material, carbon granule is obtained by cracking, then carbon granule and silicon are dissolved in electrolysis in solvent, through ultrasonic wave process, pulverize and sieve and obtain the step of Si-C composite material.
5. preparation method according to claim 4, is characterized in that, described carbonaceous organic material is alkane and/or alkene;
Preferably, described alkane is the mixture of a kind of in C1 ~ C6 alkane or at least two kinds, the mixture of a kind of more preferably in methane, ethane or propane or at least two kinds;
Preferably, described alkene is the mixture of a kind of in C2 ~ C8 alkene or at least two kinds, the mixture of a kind of more preferably in ethene, propylene or divinyl or at least two kinds;
Preferably, described carbonaceous organic material is the mixture of a kind of in methane, ethane, propane, ethene or propylene or at least two kinds.
6. the preparation method according to claim 4 or 5, is characterized in that, the temperature of described cracking is 300 ~ 2000 DEG C, is preferably 600 ~ 1600 DEG C, more preferably 800 ~ 1500 DEG C;
Preferably, the pressure of described cracking is 1 ~ 3MPa, more preferably 1.5 ~ 2MPa;
Preferably, the time of described cracking is 1.5 ~ 24h, more preferably 3 ~ 12h.
7. according to the preparation method one of claim 4 ~ 6 Suo Shu, it is characterized in that, described modified-reaction solvent used is the mixture of a kind of in ether, ethyl methyl ether, dimethylbenzene, toluene, water, chloroform or acetone or at least two kinds;
Preferably, the bath raio of described modified-reaction is 1:(15 ~ 60), more preferably 1:(30 ~ 40);
Preferably, the voltage of described electrolysis is 100 ~ 300V; The time of described electrolysis is 15 ~ 25h.
8. according to the preparation method one of claim 4 ~ 7 Suo Shu, it is characterized in that, comprise by described Si-C composite material and abandoned catalyst in direct synthesis methylchlorosilane vapour deposition on material with carbon element matrix, obtain the step of lithium ion battery negative material.
9. preparation method according to claim 8, is characterized in that, described vapour deposition for carry out under protective atmosphere;
Preferably, described protective atmosphere is the mixture of a kind of in nitrogen, helium, argon gas or neon or at least two kinds.
10. preparation method according to claim 8 or claim 9, it is characterized in that, the time of described vapour deposition is more than 0.5h, is preferably 1.5 ~ 48h, more preferably 3 ~ 36h;
Preferably, the temperature of described vapour deposition is 500 ~ 1000 DEG C, more preferably 700 ~ 900 DEG C;
Preferably, the air pressure of described vapour deposition is below 3MPa, more preferably 1 ~ 2MPa;
Preferably, the equipment that described vapour deposition is used is fixed bed or fluid bed.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637920A (en) * | 2012-04-09 | 2012-08-15 | 中国科学院过程工程研究所 | Application of waste contact as lithium ion battery negative material |
| CN102637874A (en) * | 2012-04-11 | 2012-08-15 | 中国科学院过程工程研究所 | Lithium ion battery silicon-carbon composite negative-electrode material and preparation method thereof |
| KR101396846B1 (en) * | 2013-07-09 | 2014-05-19 | 한국에너지기술연구원 | Method of manufacturing anode materials for lithium secondary battery using waste silicon |
| CN103911627A (en) * | 2012-12-31 | 2014-07-09 | 北京有色金属研究总院 | Molten salt electrolytic additive and method for preparing silicon composite material from the same |
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- 2015-08-31 CN CN201510549453.4A patent/CN105206806A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102637920A (en) * | 2012-04-09 | 2012-08-15 | 中国科学院过程工程研究所 | Application of waste contact as lithium ion battery negative material |
| CN102637874A (en) * | 2012-04-11 | 2012-08-15 | 中国科学院过程工程研究所 | Lithium ion battery silicon-carbon composite negative-electrode material and preparation method thereof |
| CN103911627A (en) * | 2012-12-31 | 2014-07-09 | 北京有色金属研究总院 | Molten salt electrolytic additive and method for preparing silicon composite material from the same |
| KR101396846B1 (en) * | 2013-07-09 | 2014-05-19 | 한국에너지기술연구원 | Method of manufacturing anode materials for lithium secondary battery using waste silicon |
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