CN208722988U - A kind of sheet silicon grain for cathode of lithium battery - Google Patents
A kind of sheet silicon grain for cathode of lithium battery Download PDFInfo
- Publication number
- CN208722988U CN208722988U CN201821489679.5U CN201821489679U CN208722988U CN 208722988 U CN208722988 U CN 208722988U CN 201821489679 U CN201821489679 U CN 201821489679U CN 208722988 U CN208722988 U CN 208722988U
- Authority
- CN
- China
- Prior art keywords
- silicon
- sheet
- cathode
- lithium battery
- inner core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Silicon Compounds (AREA)
Abstract
The utility model discloses a kind of sheet silicon grains for cathode of lithium battery, belong to silicon materials preparation technical field；Including sheet elemental silicon inner core, the sheet elemental silicon inner core upper and lower surface has oxidation outer silicon, and multiple holes are distributed in perforation on the oxidation outer silicon；The silicon particle structure of the utility model, be conducive to be thoroughly mixed to form branch-like and network-like structure with graphite, be conducive to the bulk effect for alleviating silicon, meet the requirement in lithium battery silicon-carbon cathode to silicon materials, it realizes the recycling of diamond wire cutting waste material, and realizes huge economic benefit.
Description
Technical field
The utility model belongs to silicon materials preparation technical field, and in particular to a kind of sheet silicon for cathode of lithium battery
Grain.
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.
Utility model content
The utility model overcome the deficiencies in the prior art, waste material can not return after solving photovoltaic industry crystalline silicon diamond wire slice
The problem of utilizing is received, a kind of a kind of sheet silicon grain for cathode of lithium battery prepared using Buddha's warrior attendant wire cutting waste silicon powder is provided,
The phenomenon that silicium cathode structure caused by can solving because of silicium cathode embedding and removing collapses, dusting.
To achieve the above object, the technology employed by the present utility model is being prepared using Buddha's warrior attendant wire cutting waste silicon powder
The method of lithium cell cathode 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%,
The mixed solution of 20% ~ 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, 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.
By above method, a kind of sheet silicon grain for cathode of lithium battery described in the utility model is formd, is wrapped
Sheet elemental silicon inner core is included, the sheet elemental silicon inner core upper and lower surface has oxidation outer silicon, the oxidation outer silicon
Multiple holes are distributed in upper perforation.
Further, the sheet silicon grain with a thickness of 30 ~ 50nm.
Further, the thickness ratio of the elemental silicon inner core and the oxidation outer silicon is 2-3:1.
Further, multiple holes are uniformly distributed in the oxidation outer silicon.
Compared with prior art the utility model has the following beneficial effects:
The utility model is using chemical attack combination high-temperature calcination, the method for strong stirring, in diamond wire cutting waste liquor
Silicon materials surface be modified processing, form special lamella silicon grain structure, inner core is simple substance silicon wafer layer, and upper and lower surface is covered
One layer of silica of lid, and multiple holes through oxidation outer silicon are formed, the side of sheet silicon grain exposes elemental silicon inner core, this
The hole that is formed a bit on the one hand from the upper and lower surface of sheet silicon grain by internal layer elemental silicon partial denudation, another aspect surface it is this
Structure is conducive to be thoroughly mixed to form branch-like and network-like structure with graphite, and its is unique for the package oxide layer being prepared into
Thickness in laminated structure and axial direction is very beneficial for alleviating the bulk effect of silicon.In addition, lesser specific surface area also effectively subtracts
Side reaction between few silicon materials and electrolyte.By being recycled to the silicon materials in crystalline silicon diamond wire cutting waste liquor, it is pure
This silicon particle that the technical process such as change, surface modification, consistency treatment obtain can be used for preparing lithium battery silicon-based anode material
Material meets the requirement in lithium battery silicon-carbon cathode to silicon materials, realizes the recycling of diamond wire cutting waste material, and realizes huge
Economic benefit.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of sheet silicon grain.
Wherein, 1 is elemental silicon inner core, and 2 be oxidation outer silicon, and 3 be hole.
Specific embodiment
The technical solution of the utility model is described in detail below with reference to examples and drawings, but protection scope is not limited by this
System.
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) the crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder being collected into is removed remaining in crystalline silicon Buddha's warrior attendant wire cutting waste silicon powder
The impurity such as metal, 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.
As shown in Figure 1, the silicon particle in the consistency silicon powder B includes sheet elemental silicon inner core 1, in sheet elemental silicon
1 upper and lower surface of core has oxidation outer silicon 2, and multiple holes 3 are distributed in perforation on the oxidation outer silicon 2.Sheet silicon grain
With a thickness of 35nm.The thickness ratio of elemental silicon inner core 1 and oxidation outer silicon 2 is 3:1.Multiple holes 3 are uniformly distributed in outside silica
Layer 2.
Embodiment 2
The preparation method of the silicon particle is same as Example 1, and the silicon particle includes sheet elemental silicon inner core 1,
1 upper and lower surface of sheet elemental silicon inner core has oxidation outer silicon 2, and multiple holes are distributed in perforation on the oxidation outer silicon 2
3.Sheet silicon grain with a thickness of 50nm.The thickness ratio of elemental silicon inner core 1 and oxidation outer silicon 2 is 2.5:1.
Embodiment 3
The preparation method of the silicon particle is same as Example 1, and the silicon particle includes sheet elemental silicon inner core 1,
1 upper and lower surface of sheet elemental silicon inner core has oxidation outer silicon 2, and multiple holes are distributed in perforation on the oxidation outer silicon 2
3.Sheet silicon grain with a thickness of 30nm.The thickness ratio of elemental silicon inner core 1 and oxidation outer silicon 2 is 2:1.Multiple holes 3 uniformly divide
It is distributed in oxidation outer silicon 2.
The above content is the further descriptions done in conjunction with specific preferred embodiment to the utility model, cannot
Assert that specific embodiment of the present utility model is only limitted to this, for the utility model person of an ordinary skill in the technical field
For, under the premise of not departing from the utility model, several simple deduction or replace can also be made, all shall be regarded as belonging to
The utility model determines scope of patent protection by the claims submitted.
Claims (4)
1. a kind of sheet silicon grain for cathode of lithium battery, which is characterized in that including sheet elemental silicon inner core (1), the piece
Shape elemental silicon inner core (1) upper and lower surface has oxidation outer silicon (2), and perforation is distributed with multiple on the oxidation outer silicon (2)
Hole (3).
2. a kind of sheet silicon grain for cathode of lithium battery according to claim 1, which is characterized in that the sheet silicon
Grain with a thickness of 30 ~ 50nm.
3. a kind of sheet silicon grain for cathode of lithium battery according to claim 1, which is characterized in that the elemental silicon
The thickness ratio of inner core (1) and the oxidation outer silicon (2) is 2-3:1.
4. a kind of sheet silicon grain for cathode of lithium battery according to claim 1, which is characterized in that multiple holes
Hole (3) is uniformly distributed in the oxidation outer silicon (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821489679.5U CN208722988U (en) | 2018-09-12 | 2018-09-12 | A kind of sheet silicon grain for cathode of lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821489679.5U CN208722988U (en) | 2018-09-12 | 2018-09-12 | A kind of sheet silicon grain for cathode of lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN208722988U true CN208722988U (en) | 2019-04-09 |
Family
ID=65981849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201821489679.5U Active CN208722988U (en) | 2018-09-12 | 2018-09-12 | A kind of sheet silicon grain for cathode of lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN208722988U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148868A (en) * | 2018-09-12 | 2019-01-04 | 山西中电科新能源技术有限公司 | Sheet silicon grain for cathode of lithium battery |
-
2018
- 2018-09-12 CN CN201821489679.5U patent/CN208722988U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148868A (en) * | 2018-09-12 | 2019-01-04 | 山西中电科新能源技术有限公司 | Sheet silicon grain for cathode of lithium battery |
| CN109148868B (en) * | 2018-09-12 | 2023-09-12 | 山西中电科新能源技术有限公司 | Flaky silicon particles for negative electrode of lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111326723B (en) | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN111362269A (en) | Preparation method of SEI (solid electrolyte interphase) film of lithium ion battery cathode, lithium ion battery cathode material and application of lithium ion battery cathode material | |
| CN112467067B (en) | Three-dimensional porous silicon-carbon material prepared by purifying photovoltaic silicon mud and preparation method thereof | |
| CN109148868A (en) | Sheet silicon grain for cathode of lithium battery | |
| CN104701491A (en) | Nano-porous silica lithium battery anode material and preparation method and application thereof | |
| CN109148867A (en) | Compound silicon carbide particles for cathode of lithium battery | |
| CN108987677A (en) | The method that silicon wafer cut by diamond wire waste recovery is used for lithium ion battery negative material preparation | |
| CN108448090A (en) | A kind of preparation method of lithium battery silicon-carbon composite material | |
| CN106450305A (en) | Preparation method of lithium ion battery cathode material CoP/C | |
| CN110474049A (en) | A kind of preparation method of lithium ion battery antimony sulfide nano rod cathode | |
| WO2023001213A1 (en) | Sio@mg/c composite material, and preparation method therefor and application thereof | |
| CN108400309B (en) | Method for preparing modified high-voltage single crystal ternary positive electrode material by composite coating | |
| CN208722989U (en) | A kind of silicon carbide particles for cathode of lithium battery | |
| CN109494399A (en) | A kind of silicon/solid electrolyte nanocomposite and its preparation method and application | |
| CN110492074B (en) | Method for preparing carbon fiber/antimony sulfide composite cathode of lithium ion battery | |
| CN109167046A (en) | Silicon carbide particles for cathode of lithium battery | |
| CN208722988U (en) | A kind of sheet silicon grain for cathode of lithium battery | |
| CN104733719A (en) | Method for preparing germanium-based cathode material for lithium ion battery by adopting carbothermic reduction method | |
| CN109250721A (en) | A kind of method of modifying of Buddha's warrior attendant wire cutting waste silicon powder and application | |
| CN109686941A (en) | A method of preparing lithium-ion-power cell silicon-carbon cathode material | |
| CN208722987U (en) | A kind of compound silicon carbide particles for cathode of lithium battery | |
| CN107749478A (en) | A kind of LiMn2O4 ternary power lithium ion battery | |
| CN109360942A (en) | A method of negative electrode of lithium ion battery is prepared based on recycling solar cell | |
| CN208722990U (en) | A kind of modified silicon particle in surface for cathode of lithium battery | |
| CN108832106A (en) | A kind of redox graphene-cobalt nickel oxide aluminium lithium composite positive pole, preparation method and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |