CN109250721A - A kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder and application - Google Patents
A kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder and application Download PDFInfo
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- CN109250721A CN109250721A CN201811063649.2A CN201811063649A CN109250721A CN 109250721 A CN109250721 A CN 109250721A CN 201811063649 A CN201811063649 A CN 201811063649A CN 109250721 A CN109250721 A CN 109250721A
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Abstract
The invention discloses a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder and applications, belong to silicon materials preparation technical field；It is calcined at high temperature again after Buddha's warrior attendant wire cutting waste silicon powder is impregnated using acid solution；Hydrofluoric acid dips are reused, and magnetic agitation is combined to obtain the modified silicon powder in surface；The carbon silicium cathode material that the present invention obtains is conducive to alleviate the bulk effect of silicon, effectively reduces the side reaction between silicon materials and electrolyte；Silicon materials in diamond wire cutting waste liquor are used to prepare lithium battery silicon based anode material in a manner of inexpensive, realize the recycling of diamond wire cutting waste material, and realize huge economic benefit.
Description
Technical field
The invention belongs to silicon materials preparation technical fields, and in particular to a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder and
Using.
Background technique
Lithium ion battery is most widely used energy storage battery core in current energy storage technology, and improving battery core energy storage density is
The target that the whole world is pursued, the raising of battery core energy density depend on the progress of its positive and negative electrode material.
People generally use negative electrode material of the carbon based negative electrodes material as lithium ion battery, but carbon based negative electrodes material energy is close
Spend low (theoretical specific capacity 372mAh/g, practical reversible specific capacity are 330mAh/g).Silicon is to be currently known specific capacity (theoretical specific volume
Measure 4200mAh/g) highest lithium ion battery negative material, but due to its huge bulk effect (> 300%), silicon electrode material
Dusting is understood in charge and discharge process and is peeled off from collector, so that active material and active material, active material and collector
Between lose electrical contact, while constantly forming new solid-phase electrolyte layer SEI, eventually lead to the deterioration of chemical property.
The material of crystalline silicon slice about 40% becomes powder by Buddha's warrior attendant wire cutting and is lost, by taking polycrystalline silicon rod as an example, 2018
About 105 yuan of August part per kilogram, upper half annual output about 50GW in 2018, about 200,000 tons of crystal bar is converted into, slice is lost 40%, converts into 10
Ten thousand tons, and the powder diameter is too small (particle diameter distribution 200nm ~ 2.5um), and conventional method can not be handled, and be formed to environmental protection
Biggish pressure.
Summary of the invention
Overcome the deficiencies in the prior art of the present invention, waste material can not recycle benefit after solving photovoltaic industry crystalline silicon diamond wire slice
With the problem of, a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder is provided, after modification, of Buddha's warrior attendant wire cutting waste silicon powder
Kernel structure changes, and this structure can be applied to the preparation of lithium cell cathode material, can solve because of silicium cathode embedding and removing
The phenomenon that caused silicium cathode structure collapses, dusting.
To achieve the above object, the technical scheme adopted by the invention is as follows: using Buddha's warrior attendant wire cutting waste silicon powder prepare lithium electricity
The method of pond negative electrode material, comprising the following steps:
A) by Buddha's warrior attendant wire cutting waste silicon powder using the hydrochloric acid of 0.1 ~ 0.5mol/L, the sulfuric acid that mass fraction is 30% ~ 50%, 20% ~
The mixed solution of 45% nitric acid impregnates 3 ~ 6h；It rinses later and dry.
B) under inert gas protection, the Buddha's warrior attendant wire cutting waste silicon powder after drying is small in 180 ~ 260 DEG C of high-temperature calcinations 2 ~ 5
When；The hydrofluoric acid dips of 0.03 ~ 0.08mol/L, and 30 ~ 100min of magnetic agitation are reused, the modified silicon powder A in surface is obtained.
C) silicon powder A modified to surface carries out partial size consistency treatment using the method for wet grinding and obtains consistency silicon powder B,
The consistency silicon powder B partial size is 30 ~ 50nm of D95 partial size, and D20 partial size < 10nm.
D) the sorting silicon powder C that partial size is 30 ~ 50nm is sub-elected from the consistency silicon powder B, by the sorting silicon
After powder C carries out carbonization treatment, lithium battery silicon carbon anode material is obtained.
Preferably, impurity remaining in Buddha's warrior attendant wire cutting waste silicon powder is first removed before the step a).
Preferably, rinsing described in step a) and drying are DI water, the alcohol mixeding liquid using resistivity >=10 ~ 15 megaohm
5 ~ 20 rinsings are carried out, 50 ~ 200 DEG C of the drying temperature, hold time 2 ~ 8h.
Preferably, the hydrochloric acid, sulfuric acid, nitric acid volume ratio are 1-2.5:0.8-1.5:1.
Preferably, which is characterized in that hydrochloric acid, sulfuric acid, nitric acid mixed solution temperature be 40-80 DEG C.
Preferably, the magnetic agitation of the step b) is superimposed forced vibration, and forms forced convection, and forced vibration includes
Any one of ultrasound, mechanical stirring, reactor shaking, electric and magnetic oscillation.
The partial size consistency treatment be by the modified silicon powder A in the surface according to the every increase 100-200nm of partial size into
Row stepping forms the modified silicon powder in surface of different-grain diameter rank, and mixed liquor H is added in the modified silicon powder in the surface of each rank, is carried out
It includes dispersing agent, surfactant, addition that dry mixed, which obtains consistency the silicon powder B, the mixed liquor H, after grinding
Agent, the additive are diethanol amine or triethanolamine.
Preferably, the surfactant is SDBS, and the dispersing agent is polyethylene glycol 200.
Preferably, 30 ~ 60wt% of dispersing agent, 5 ~ 20wt% of surfactant, 5 ~ 20wt% of additive.
Preferably, the temperature of the mixed liquor H is 60-90 DEG C, pH 7-9.
Preferably, which is characterized in that in the process of lapping, using 0.2 ~ 0.6mm zirconium oxide or corundum it is spherical
Or ellipticity abrasive media, milling apparatus stir 8 ~ 12m/s of axial velocity, milling time 2 ~ 8 hours.
Particle unit in the modified silicon powder A in the surface being prepared by the above method is spherical or laminated structure, described
Spherical or laminated structure there is elemental silicon inner core, the elemental silicon inner core of the chondritic is wrapped with oxidation outer silicon,
The elemental silicon inner core upper and lower surface of the laminated structure has oxidation outer silicon, and perforation distribution is more on the oxidation outer silicon
A hole.
Preferably, multiple holes are evenly distributed on oxidation outer silicon.
The graphite material for meeting cathode of lithium battery is chosen, by grinding, sorting, the partial size of the graphite material is adjusted
Extremely: D95 partial size 200 ~ 300nm, D10 partial size < 200nm obtains graphite D.
The sorting silicon powder C into after carbonization treatment excessively is mixed with graphite D by weight 0.8-1.2:1.
Conductive agent, binder are added in sorting silicon powder C and graphite D mixture, and sufficiently stirs evenly, reaches sorting silicon powder C
It is uniformly mixed with graphite D；Uniform intermixture is applied to copper foil again, through oversintering, is prepared into cathode.
After mixing, since the partial size of graphite D is greater than the partial size of sorting silicon powder C, there is spherical sorting silicon powder C particle
It is wrapped in the outer surface of graphite D particle.Sorting silicon powder C particle with laminated structure is incorporated in graphite D particle with branch-like
Surface.
Preferably, the partial size of the graphite material D: D95 partial size 30 ~ 50nm, D10 partial size < 30nm.At this time due to stone
The partial size of black D and the partial size of sorting silicon powder C are close, and graphite D particle and the particle of the sorting silicon powder C with chondritic are mutually handed over
Mistake forms uniform mixture；When mixing for the sorting silicon powder C with laminated structure with graphite D, formation is to sort silicon powder C
Network, graphite D are the structure of network node.
Compared with prior art the invention has the following advantages:
1) present invention by being recycled, being purified to the silicon materials in crystalline silicon diamond wire cutting waste liquor, surface is modified, consistency
The technical process such as processing, it is modified in a manner of inexpensive silicon materials in crystalline silicon diamond wire cutting waste liquor to be carried out surface, can be with
It is used to prepare lithium battery silicon based anode material.
2) present invention is modified place to silicon powder surface using chemical attack combination high-temperature calcination, the method for strong stirring
Reason, the hole of formation, on the one hand by internal layer elemental silicon partial denudation, this structure on another aspect surface is conducive to fill with graphite
Divide its unique laminated structure of package oxide layer for being mixed to form spherical or branch-like and network-like structure, and being prepared into and axis
Upward thickness is very beneficial for alleviating the bulk effect of silicon.In addition, lesser specific surface area also effectively reduces silicon materials and electricity
Solve the side reaction between liquid.
3) it is prepared into through the invention by becoming the techniques such as useless purifying, sorting, broken, corrosion to diamond wire cutting waste material
Meet the requirement in lithium battery silicon-carbon cathode to silicon materials, realize the recycling of diamond wire cutting waste material, and realizes huge warp
Ji benefit.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the modified silicon powder A particle in surface of chondritic.
Fig. 2 is the sectional view of the modified silicon powder A particle in surface of chondritic.
Fig. 3 is the structural schematic diagram of the modified silicon powder A particle in surface of laminated structure.
Fig. 4 is the graphite D complex space structure figure of the sorting silicon powder C and 200 ~ 300nm of D95 partial size of chondritic.
Fig. 5 is the graphite D complex space structure figure of the sorting silicon powder C and 200 ~ 300nm of D95 partial size of laminated structure.
Fig. 6 is the graphite D complex space structure figure of the sorting silicon powder C and 30 ~ 50nm of D95 partial size of chondritic.
Fig. 7 is the graphite D complex space structure figure of the sorting silicon powder C and 30 ~ 50nm of D95 partial size of laminated structure.
Wherein, 1 is elemental silicon inner core, and 2 be oxidation outer silicon, and 3 be hole, and 4 be carbon particle, and 5 be silicon particle.
Specific embodiment
Below with reference to the examples and drawings technical solution that the present invention will be described in detail, but the scope of protection is not limited by this.
Embodiment 1
The method for preparing lithium cell cathode material using Buddha's warrior attendant wire cutting waste silicon powder, comprising the following steps:
1) by the crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder being collected into remove remaining metal in crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder,
The impurity such as polyethylene glycol, glue, glass.
2) configure mixed solution: using the hydrochloric acid of 0.3mol/L, mass fraction be 40% sulfuric acid, 45% nitric acid is configured to
Mixed solution, wherein hydrochloric acid, sulfuric acid, nitric acid volume ratio are 1:0.8:1；The temperature of mixed solution is 80 DEG C.
3) by Buddha's warrior attendant wire cutting waste silicon powder be placed in mixed solution impregnate 6h and be stirred under vacuum, with remove metallic copper,
Buddha's warrior attendant wire cutting waste silicon powder particle surface is tentatively corroded while iron, nickel plasma, is not less than later using resistivity
10 ~ 15 megaohms of DI water, alcohol mixeding liquid progress 5 ~ 20 times rinsings, and the mode of heating in vacuum is taken to be dried, it heats
120 DEG C of temperature, hold time 6h.
4) under argon gas, helium protective atmosphere, the Buddha's warrior attendant wire cutting waste silicon powder after drying is small in 260 DEG C of high-temperature calcinations 3
When；The hydrofluoric acid dips of 0.05mol/L are reused, and combine magnetic agitation and ultrasonic vibration treatment 100min, surface is obtained and changes
Property silicon powder A.
5) will purifying silicon powder A by partial size carry out stepping, mono- grade of every 100 ~ 200nm, obtain purifying silicon powder A1(300nm ~
400nm), purify silicon powder A2(400nm ~ 600nm), purifying silicon powder A3(600nm ~ 800nm), purifying silicon powder A4(800nm ~
1000nm), purify silicon powder A5(1000nm ~ 1200nm), purifying silicon powder A6(1200nm ~ 1400nm), purifying silicon powder A7(1400nm
~ 1600nm), purifying silicon powder A8(1600nm ~ 1800nm), purifying silicon powder A9(1800nm ~ 2000nm).
6) configuration includes the mixed liquor H of dispersing agent, 20% surfactant, 15% additive that mass percent is 30%；Point
Powder uses polyethylene glycol 400, and surfactant SDBS, additive is diethanol amine；The temperature of mixed liquor H is 60 DEG C, pH
Value is 8.
7) will purifying silicon powder A1-A9 mixed respectively with mixed liquor H, respectively obtain AH1, AH2, AH3, AH4, AH5,
AH6、AH7、AH8、AH9。
8) in such a way that diaphragm is pumped into grinder, will AH9 grind 2h after mix with AH8 after grinding 3h after, then with AH7
After mixed grinding 4h, then with after AH6 mixed grinding 3h, then with after AH5 mixed grinding 4h, then with after AH4 mixed grinding 5h；Again with
After AH3 mixed grinding 5h；Again and after AH2 mixed grinding 4h；AH is obtained with after AH1 mixed grinding 8h again, AH is subjected to solid-liquid point
From obtaining consistency silicon powder B after dry.
9) consistency silicon powder B is sorted, by consistency silicon powder B partial size according to<30nm, 30 ~ 50nm,>50nm third gear
It is sorted and is packed, obtain the sorting silicon powder C1 of partial size<30nm, the sorting silicon powder C2 of 30 ~ 50nm of partial size, partial size>50nm point
Silicon powder C3 is selected, wherein can will sell after sorting silicon powder C1, sorting silicon powder C3 packaging.
10) carbonization treatment is carried out using the method for vapor deposition to sorting silicon powder C2, obtains lithium battery silicon carbon anode material.
Embodiment 2
The method for preparing lithium cell cathode material using Buddha's warrior attendant wire cutting waste silicon powder, comprising the following steps:
1) by the crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder being collected into remove remaining metal in crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder,
The impurity such as polyethylene glycol, glue, glass.
2) configure mixed solution: using the hydrochloric acid of 0.1mol/L, mass fraction be 50% sulfuric acid, 20% nitric acid is configured to
Mixed solution, wherein hydrochloric acid, sulfuric acid, nitric acid volume ratio are 2.5:1:1；The temperature of mixed solution is 40 DEG C.
3) by Buddha's warrior attendant wire cutting waste silicon powder be placed in mixed solution impregnate 4h and be stirred under vacuum, with remove metallic copper,
Buddha's warrior attendant wire cutting waste silicon powder particle surface is tentatively corroded while iron, nickel plasma, is not less than later using resistivity
10 ~ 15 megaohms of DI water, alcohol mixeding liquid progress 5 ~ 20 times rinsings, and the mode of heating in vacuum is taken to be dried, it heats
200 DEG C of temperature, hold time 8h.
4) under argon gas, helium protective atmosphere, the Buddha's warrior attendant wire cutting waste silicon powder after drying is small in 180 DEG C of high-temperature calcinations 5
When；The hydrofluoric acid dips of 0.08mol/L are reused, and magnetic agitation and mechanical oscillation is combined to handle 50min, it is modified to obtain surface
Silicon powder A.
5) will purifying silicon powder A by partial size carry out stepping, mono- grade of every 100 ~ 200nm, obtain purifying silicon powder A1(300nm ~
400nm), purify silicon powder A2(400nm ~ 600nm), purifying silicon powder A3(600nm ~ 800nm), purifying silicon powder A4(800nm ~
1000nm), purify silicon powder A5(1000nm ~ 1200nm), purifying silicon powder A6(1200nm ~ 1400nm), purifying silicon powder A7(1400nm
~ 1600nm), purifying silicon powder A8(1600nm ~ 1800nm), purifying silicon powder A9(1800nm ~ 2000nm).
6) configuration includes the mixed liquor H of dispersing agent, 10% surfactant, 5% additive that mass percent is 60%；Point
Powder uses polyethylene glycol-800, and surfactant SDBS, additive is triethanolamine；The temperature of mixed liquor H is 90 DEG C, pH
Value is 7.
7) will purifying silicon powder A1-A9 mixed respectively with mixed liquor H, respectively obtain AH1, AH2, AH3, AH4, AH5,
AH6、AH7、AH8、AH9。
8) in such a way that diaphragm is pumped into grinder, using the spherical abrasive media of the zirconium oxide of 0.5mm, equipment agitating shaft
Linear velocity 12m/s is ground.Will AH9 grind 3h after mix with AH8 after grinding 2h after, then with after AH7 mixed grinding 3h, then with
After AH6 mixed grinding 4h, then with after AH5 mixed grinding 4h, then with after AH4 mixed grinding 4h；Again and after AH3 mixed grinding 4h；
Again and after AH2 mixed grinding 5h；AH is obtained with after AH1 mixed grinding 8h again, AH is separated by solid-liquid separation, is obtained after dry consistent
Property silicon powder B.
9) consistency silicon powder B is sorted, by consistency silicon powder B partial size according to<30nm, 30 ~ 50nm,>50nm third gear
It is sorted and is packed, obtain the sorting silicon powder C1 of partial size<30nm, the sorting silicon powder C2 of 30 ~ 50nm of partial size, partial size>50nm point
Silicon powder C3 is selected, wherein can will sell after sorting silicon powder C1, sorting silicon powder C3 packaging.
10) carbonization treatment is carried out using the method for vapor deposition to sorting silicon powder C2, obtains lithium battery silicon carbon anode material.
Embodiment 3
The method for preparing lithium cell cathode material using Buddha's warrior attendant wire cutting waste silicon powder, comprising the following steps:
1) by the crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder being collected into remove remaining metal in crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder,
The impurity such as polyethylene glycol, glue, glass.
2) configure mixed solution: using the hydrochloric acid of 0.5mol/L, mass fraction be 30% sulfuric acid, 45% nitric acid is configured to
Mixed solution, wherein hydrochloric acid, sulfuric acid, nitric acid volume ratio are 2:1.5:1；The temperature of mixed solution is 60 DEG C.
3) Buddha's warrior attendant wire cutting waste silicon powder is placed in mixed solution to the reactor shaking for impregnating 3h and accompanied by intense, with removal
Buddha's warrior attendant wire cutting waste silicon powder particle surface is tentatively corroded while metallic copper, iron, nickel plasma, uses resistivity later
DI water, alcohol mixeding liquid not less than 10 ~ 15 megaohms carry out 5 ~ 20 rinsings, and the mode of heating in vacuum is taken to be done
Dry, 50 DEG C of heating temperature, hold time 2h.
4) under argon gas, helium protective atmosphere, the Buddha's warrior attendant wire cutting waste silicon powder after drying is small in 200 DEG C of high-temperature calcinations 2
When；The hydrofluoric acid dips of 0.03mol/L are reused, and magnetic agitation stacking reaction device is combined to shake processing 30min, obtain surface
Modified silicon powder A.
5) will purifying silicon powder A by partial size carry out stepping, mono- grade of every 100 ~ 200nm, obtain purifying silicon powder A1(300nm ~
400nm), purify silicon powder A2(400nm ~ 600nm), purifying silicon powder A3(600nm ~ 800nm), purifying silicon powder A4(800nm ~
1000nm), purify silicon powder A5(1000nm ~ 1200nm), purifying silicon powder A6(1200nm ~ 1400nm), purifying silicon powder A7(1400nm
~ 1600nm), purifying silicon powder A8(1600nm ~ 1800nm), purifying silicon powder A9(1800nm ~ 2000nm).
6) configuration includes the mixed liquor H of dispersing agent, 10% surfactant, 5% additive that mass percent is 60%；Point
Powder uses Macrogol 600, and surfactant SDBS, additive is triethanolamine；The temperature of mixed liquor H is 70 DEG C, pH
Value is 9.
7) will purifying silicon powder A1-A9 mixed respectively with mixed liquor H, respectively obtain AH1, AH2, AH3, AH4, AH5,
AH6、AH7、AH8、AH9。
8) in such a way that diaphragm is pumped into grinder, using the corundum ellipticity abrasive media of 0.6mm, equipment agitating shaft
Linear velocity 8m/s is ground.Will AH9 grind 3h after mix with AH8 after grinding 2h after, then with after AH7 mixed grinding 3h, then with
After AH6 mixed grinding 4h, then with after AH5 mixed grinding 4h, then with after AH4 mixed grinding 4h；Again and after AH3 mixed grinding 4h；
Again and after AH2 mixed grinding 5h；AH is obtained with after AH1 mixed grinding 8h again, AH is separated by solid-liquid separation, is obtained after dry consistent
Property silicon powder B.
9) consistency silicon powder B is sorted, by consistency silicon powder B partial size according to<30nm, 30 ~ 50nm,>50nm third gear
It is sorted and is packed, obtain the sorting silicon powder C1 of partial size<30nm, the sorting silicon powder C2 of 30 ~ 50nm of partial size, partial size>50nm point
Silicon powder C3 is selected, wherein can will sell after sorting silicon powder C1, sorting silicon powder C3 packaging.
10) carbonization treatment is carried out using the method for vapor deposition to sorting silicon powder C2, obtains lithium battery silicon carbon anode material.
The above content is combine specific preferred embodiment to the further description done of the present invention, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from the present invention, several simple deduction or replace can also be made, all shall be regarded as belonging to the present invention by being submitted
Claims determine scope of patent protection.
Claims (7)
1. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder, which comprises the following steps:
A) by Buddha's warrior attendant wire cutting waste silicon powder using the hydrochloric acid of 0.1 ~ 0.5mol/L, the sulfuric acid that mass fraction is 30% ~ 50%, 20% ~
The mixed solution of 45% nitric acid impregnates 3 ~ 6h；It rinses later and dry；
B) under inert gas protection, by the Buddha's warrior attendant wire cutting waste silicon powder after drying 180 ~ 260 DEG C high-temperature calcination 2 ~ 5 hours；
The hydrofluoric acid dips of 0.03 ~ 0.08mol/L, and 30 ~ 100min of magnetic agitation are reused, the modified silicon powder in surface is obtained.
2. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder according to claim 1, which is characterized in that in the step
It is rapid a) preceding first to remove impurity remaining in Buddha's warrior attendant wire cutting waste silicon powder.
3. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder according to claim 1, which is characterized in that the salt
Acid, sulfuric acid, nitric acid volume ratio are 1-2.5:0.8-1.5:1.
4. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder according to claim 1 or 3, which is characterized in that hydrochloric acid, sulphur
The temperature of sour, nitric acid mixed solution is 40-80 DEG C.
5. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder according to claim 1, which is characterized in that described in step a)
Rinsing and drying be the rinsing that 5 ~ 20 times are carried out using the DI water of resistivity >=10 ~ 15 megaohm, alcohol mixeding liquid, described is dry
50 ~ 200 DEG C of dry temperature, hold time 2 ~ 8h.
6. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder according to claim 1, which is characterized in that the step
B) magnetic agitation is superimposed forced vibration, and forms forced convection, forced vibration include ultrasound, mechanical stirring, reactor shaking,
Any one of electric and magnetic oscillation.
7. a kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder as described in claim 1 is in lithium cell cathode material preparation
Using.
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| CN111082033A (en) * | 2019-11-28 | 2020-04-28 | 中南大学 | Lithium ion battery nano silicon negative electrode material, and preparation method and application thereof by utilizing silicon cutting scraps |
| US11233230B2 (en) * | 2020-06-09 | 2022-01-25 | Enevate Corporation | Method and system for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes |
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| CN104701491A (en) * | 2015-03-31 | 2015-06-10 | 吕铁铮 | Nano-porous silica lithium battery anode material and preparation method and application thereof |
| CN107416839A (en) * | 2017-09-11 | 2017-12-01 | 商永辉 | A kind of method for preparing lithium ion battery negative material using the discarded silica flour slurry of Buddha's warrior attendant wire cutting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104701491A (en) * | 2015-03-31 | 2015-06-10 | 吕铁铮 | Nano-porous silica lithium battery anode material and preparation method and application thereof |
| CN107416839A (en) * | 2017-09-11 | 2017-12-01 | 商永辉 | A kind of method for preparing lithium ion battery negative material using the discarded silica flour slurry of Buddha's warrior attendant wire cutting |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082033A (en) * | 2019-11-28 | 2020-04-28 | 中南大学 | Lithium ion battery nano silicon negative electrode material, and preparation method and application thereof by utilizing silicon cutting scraps |
| US11233230B2 (en) * | 2020-06-09 | 2022-01-25 | Enevate Corporation | Method and system for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes |
| US11923531B2 (en) | 2020-06-09 | 2024-03-05 | Enevate Corporation | Method and system for water soluble weak acidic resins as carbon precursors for silicon-dominant anodes |
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