CN107369809A - A kind of preparation method of lithium ion battery silicon-carbon cathode material - Google Patents
A kind of preparation method of lithium ion battery silicon-carbon cathode material Download PDFInfo
- Publication number
- CN107369809A CN107369809A CN201710369005.5A CN201710369005A CN107369809A CN 107369809 A CN107369809 A CN 107369809A CN 201710369005 A CN201710369005 A CN 201710369005A CN 107369809 A CN107369809 A CN 107369809A
- Authority
- CN
- China
- Prior art keywords
- silicon
- silica
- carbon
- preparation
- cathode
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
Abstract
The present invention relates to a kind of preparation method of lithium ion battery silicon-carbon cathode material, it is characterised in that its preparation technology, specific preparation process are as follows：Pre-processed by expanded graphite, configure presoma suspension, prepared by presoma, prepared by silica-rich material, silica-rich material and other cathode of lithium battery carbon materials are sufficiently mixed, silica-rich material accounts for the 10% ~ 30% of gross mass, other cathode of lithium battery carbon materials are Delanium, by ball milling, silicon-carbon cathode material is just obtained.This method, as silicon source, on the one hand reduces material cost, insertion of the silicon in expanded graphite interlayer is on the other hand ensure that, so as to ensure cushioning effect of the expanded graphite to silicon without using silica flour；And this method uses other cathode of lithium battery carbon materials to improve the flexibility of material as primary carbon source, and cost is reduced, easily realize mass, reach cost, the controllability of performance.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery silicon-carbon cathode material, belongs to lithium ion battery technology neck
Domain.
Background technology
Currently, energy-storage units of the lithium ion battery as maturation, each part of life is gradually incorporated.In life
Mobile phone, the electrical equipment such as notebook be all to use lithium ion battery as its energy-storage units.In recent years lithium ion battery gradually by with
In terms of power energy storage, electric automobile is exactly the important application of lithium ion battery, but current lithium ion battery energy
Density is still unable to reach requirement of the pure electric automobile to course continuation mileage.
For electrokinetic cell, it should be positive electrode and negative material to influence most factors to its energy density.
Positive electrode current material just develops towards high power capacity and high voltage both direction, the negative pole material that exploitation matches with positive electrode performance
Material, could effectively give play to the characteristic of positive electrode.
Silicon based cells negative material has very high volumetric properties, and the theoretical specific capacity of pure silicon is 4200mAh/g, is great
The lithium ion battery negative material of potentiality to be exploited.The subject matter that silicon based anode material faces at present is silicon in charge and discharge process
Volume Changes, cause the efflorescence of material, therefore use carbon material to buffer the volumetric expansion of silicon materials as cushioning frame
And diminution, silicon-carbon composite cathode material arise at the historic moment.The research to silicon-carbon cathode material is many at present, such as patent application
The preparation method and a kind of 201210283761.3 Gao Rong of a kind of number 201210387258.2 lithium ion battery silicon-carbon composites
Measure in the preparation method of lithium ion battery negative material using silica flour and expanded graphite mixed processing, obtain silicon-carbon cathode material
Material, but this method is limited by silica flour size and dispersing technology, it is difficult to really realize in silica flour insertion expanded graphite space
Purpose, nanoscale silica flour improve material cost, all carbon sources select expanded graphite in 201210387258.2 patents in addition,
Greatly increase material cost.
The content of the invention
It is an object of the invention to provide a kind of preparation method of lithium ion battery silicon-carbon cathode material, and this method is using expansion
Silica is reduced to obtain silica-rich material after insertion Si oxide in situ between graphite flake layer, afterwards with other cathode of lithium battery
Carbon material compound obtains silicon-carbon cathode material with its.This method, as silicon source, on the one hand reduces material cost, separately without using silica flour
On the one hand insertion of the silicon in expanded graphite interlayer is ensure that, so as to ensure cushioning effect of the expanded graphite to silicon；And this method
Using other cathode of lithium battery carbon materials as primary carbon source, the flexibility of material is improved, and reduces cost, is easily realized
Mass, reach cost, the controllability of performance.
The technical proposal of the invention is realized in this way：A kind of preparation method of lithium ion battery silicon-carbon cathode material, its
It is characterised by its preparation technology, specific preparation process is as follows：
Step 1: expanded graphite pre-processes：Organic solvent is added dropwise into expanded graphite, addition is the 8 ~ 15 of expanded graphite quality
Times, organic solvent is dimethylformamide, and expanded graphite is soaked, and is ultrasonically treated 30 ~ 120min, and obtained suspension is standby；
Step 2: configuration presoma suspension：Tetraethyl orthosilicate is dissolved in the suspension obtained in step 1, positive silicic acid second
Ester addition is 15 ~ 23 times of expanded graphite quality；Add catalyst and keep the PH of solution catalyst is within the specific limits
Nitric acid, control PH scopes obtain presoma suspension between 2 ~ 5；
Step 3: prepared by presoma：Deionized water is added drop-wise to dropwise in the presoma suspension obtained in step 2, addition is gone
The quality of ionized water is 1.2 ~ 1.8 times of tetraethyl orthosilicate quality, and is subject to strong agitation, and 25 DEG C stand 1 ~ 5 hour.Afterwards will
Suspension is dried at 60 ~ 80 DEG C, obtains presoma；
Step 4: prepared by silica-rich material：Presoma is mixed with magnesium powder, magnesium powder quality is the 20% ~ 30% of tetraethyl orthosilicate, in argon
High temperature sintering under gas shielded, sintering temperature is between 600 ~ 800 DEG C, and sintering time is between 2 ~ 5 hours, by silica also
Original, product are dried after overpickling, washing, after crushing, just obtain silica-rich material；
Step 5: silicon-carbon cathode is compound：Silica-rich material and other cathode of lithium battery carbon materials are sufficiently mixed, silica-rich material accounts for always
The 10% ~ 30% of quality, other cathode of lithium battery carbon materials are Delanium, by ball milling, just obtain silicon-carbon cathode material.
Organic solvent in described step one can replace with dimethylformamide dimethyl acetamide or N- methyl pyrroles
Pyrrolidone.
Catalyst in described step two can replace with nitric acid hydrochloric acid, and control PH scopes are between 2 ~ 5；Or replace
For ammoniacal liquor, solution pH range is controlled between 8 ~ 12.
Other cathode of lithium battery carbon materials in described step five can replace with Delanium native graphite or hard
Carbon.
Originally it is that new good effect is it without using silica flour as silicon source, on the one hand reduces material cost, on the other hand
Insertion of the silicon in expanded graphite interlayer is ensure that, so as to ensure cushioning effect of the expanded graphite to silicon；And this method uses it
His cathode of lithium battery carbon material is compound to adjust silicon-carbon cathode by adding the silica-rich material of different proportion as primary carbon source
The capacity of material and other performances, improve the flexibility of material, and reduce cost, reach cost, the controllability of performance.
Brief description of the drawings
Fig. 1 is material precursor stereoscan photograph in embodiment 1.
Fig. 2 is the first charge-discharge curve of Si-C composite material in embodiment 2.
Embodiment
The present invention will be further described with embodiment below in conjunction with the accompanying drawings：
Embodiment 1
500 g dimethylformamides will be added in 12g expanded graphites, 40 min is ultrasonically treated, 214.3g tetraethyl orthosilicates is added
Enter into expanded graphite suspension.The aqueous solution of nitric acid of configuration 5%, takes 17 g aqueous solution of nitric acid to be added in above-mentioned suspension, matches somebody with somebody
Make presoma suspension.285.7 g deionized waters are slowly dropped in presoma suspension, and are subject to strong stirring, it is quiet
After putting 1 hour, suspension is dried at 80 DEG C, obtains presoma.Presoma and 70g Mg powder are sufficiently mixed, insert gas
In atmosphere stove, heat treated under argon is incubated 3 hours to 700 DEG C.Reaction product is washed after overpickling, obtains Silicon-rich material
Material.By 10 g silica-rich materials and 90 g natural graphite material mixing and ball millings, silicon-carbon cathode material is made, its specific capacity can reach
372 mAh/g, cycle performance can reach 200 circulation volumes and keep more than 80%.
Embodiment 2
150 g dimethyl acetamides will be added in 3 g expanded graphites, 30min is ultrasonically treated, 60 g tetraethyl orthosilicates is added to
In expanded graphite suspension.The ammonia spirit of configuration 10%, takes 33 g ammonia spirits to be added in above-mentioned suspension, before making
Drive body suspension.85.7 g deionized waters are slowly dropped in presoma suspension, and are subject to strong stirring, stand 4 hours
Afterwards, suspension is dried at 80 DEG C, obtains presoma.Presoma and 30 g Mg powder are sufficiently mixed, inserted in atmosphere furnace,
Heat treated under argon is incubated 2.5 hours to 750 DEG C.Reaction product is washed after overpickling, obtains silica-rich material.Will
10g silica-rich materials and 90 g artificial graphite material mixing and ball millings, are made silicon-carbon cathode material, and its specific capacity can reach
431mAh/g, cycle performance are preferable.
Claims (4)
1. a kind of preparation method of lithium ion battery silicon-carbon cathode material, it is characterised in that its preparation technology, specific preparation process
It is as follows：
Step 1: expanded graphite pre-processes：Organic solvent is added dropwise into expanded graphite, addition is the 8 ~ 15 of expanded graphite quality
Times, organic solvent is dimethylformamide, and expanded graphite is soaked, and is ultrasonically treated 30 ~ 120min, and obtained suspension is standby；
Step 2: configuration presoma suspension：Tetraethyl orthosilicate is dissolved in the suspension obtained in step 1, positive silicic acid second
Ester addition is 15 ~ 23 times of expanded graphite quality；Add catalyst and keep the PH of solution catalyst is within the specific limits
Nitric acid, control PH scopes obtain presoma suspension between 2 ~ 5；
Step 3: prepared by presoma：Deionized water is added drop-wise to dropwise in the presoma suspension obtained in step 2, addition is gone
The quality of ionized water is 1.2 ~ 1.8 times of tetraethyl orthosilicate quality, and is subject to strong agitation, and 25 DEG C stand 1 ~ 5 hour;Afterwards will
Suspension is dried at 60 ~ 80 DEG C, obtains presoma；
Step 4: prepared by silica-rich material：Presoma is mixed with magnesium powder, magnesium powder quality is the 20% ~ 30% of tetraethyl orthosilicate, in argon
High temperature sintering under gas shielded, sintering temperature is between 600 ~ 800 DEG C, and sintering time is between 2 ~ 5 hours, by silica also
Original, product are dried after overpickling, washing, after crushing, just obtain silica-rich material；
Step 5: silicon-carbon cathode is compound：Silica-rich material and other cathode of lithium battery carbon materials are sufficiently mixed, silica-rich material accounts for always
The 10% ~ 30% of quality, other cathode of lithium battery carbon materials are Delanium, by ball milling, just obtain silicon-carbon cathode material.
2. according to a kind of preparation method of lithium ion battery silicon-carbon cathode material described in claim 1, it is characterised in that institute
Organic solvent in the step of stating one can replace with dimethylformamide dimethyl acetamide or 1-METHYLPYRROLIDONE.
3. according to a kind of preparation method of lithium ion battery silicon-carbon cathode material described in claim 1, it is characterised in that institute
Catalyst in the step of stating two can replace with nitric acid hydrochloric acid, and control PH scopes are between 2 ~ 5；Or ammoniacal liquor is replaced with, will
Solution pH range is controlled between 8 ~ 12.
4. according to a kind of preparation method of lithium ion battery silicon-carbon cathode material described in claim 1, it is characterised in that institute
Other cathode of lithium battery carbon materials in the step of stating five can replace with Delanium native graphite or hard carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710369005.5A CN107369809A (en) | 2017-05-23 | 2017-05-23 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710369005.5A CN107369809A (en) | 2017-05-23 | 2017-05-23 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107369809A true CN107369809A (en) | 2017-11-21 |
Family
ID=60305076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710369005.5A Pending CN107369809A (en) | 2017-05-23 | 2017-05-23 | A kind of preparation method of lithium ion battery silicon-carbon cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107369809A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196636A (en) * | 2022-09-15 | 2022-10-18 | 溧阳天目先导电池材料科技有限公司 | Metal-doped silicon-based negative electrode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394288A (en) * | 2011-11-24 | 2012-03-28 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon cathode material for lithium ion battery and manufacturing method thereof |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
-
2017
- 2017-05-23 CN CN201710369005.5A patent/CN107369809A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102394288A (en) * | 2011-11-24 | 2012-03-28 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon-carbon cathode material for lithium ion battery and manufacturing method thereof |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN103367726A (en) * | 2013-07-10 | 2013-10-23 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof as well as lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196636A (en) * | 2022-09-15 | 2022-10-18 | 溧阳天目先导电池材料科技有限公司 | Metal-doped silicon-based negative electrode material and preparation method and application thereof |
| CN115196636B (en) * | 2022-09-15 | 2022-11-22 | 溧阳天目先导电池材料科技有限公司 | Metal-doped silicon-based negative electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103247803B (en) | Graphene-cladding nano germanium composite material as well as preparation method and application thereof | |
| CN107342411B (en) | Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material | |
| CN103346324B (en) | Lithium ion battery cathode material and its preparation method | |
| CN102709536B (en) | Silicon-carbon composite material and preparation method thereof | |
| CN111146416B (en) | Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery | |
| CN105460917A (en) | Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method | |
| CN106856235A (en) | Lead carbon superbattery negative material and preparation method thereof | |
| CN107601490A (en) | A kind of fast charge graphite cathode material and preparation method thereof | |
| CN106410164A (en) | High-performance composite material and preparation method and application thereof | |
| CN107359317A (en) | Preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source | |
| CN108539173A (en) | A kind of preparation method of graphene coated silicon composite | |
| CN102832376A (en) | Preparation method for silicon carbon composite material for lithium ion battery negative electrode | |
| CN104659346A (en) | Germanium/carbon composite negative electrode material and preparation method thereof | |
| CN107394150A (en) | A kind of mesoporous silicon copper composition electrode material and its preparation method and application | |
| CN106848237A (en) | A kind of preparation method of the sodium ion positive electrode of height ratio capacity | |
| CN109216683A (en) | A kind of synthetic method of lithium ion battery high-capacity cathode material | |
| CN109037606A (en) | A kind of carbon coating porous silicon Antaciron composite negative pole material and its preparation, application | |
| CN108963237B (en) | Preparation method of sodium ion battery negative electrode material | |
| CN107316974B (en) | Preparation method of nano-silver composite lithium iron phosphate cathode material | |
| CN112216831B (en) | Method for synthesizing high-capacity negative electrode material of lithium ion power battery | |
| CN107369809A (en) | A kind of preparation method of lithium ion battery silicon-carbon cathode material | |
| CN112794310A (en) | Potassium ion battery negative electrode material and preparation method and application thereof | |
| CN108808005A (en) | A method of preparing lithium cell cathode material additive using calcining mixt | |
| CN107394122A (en) | A kind of preparation method of compound silicon-carbon cathode material | |
| CN108400396A (en) | A method of improving the first charge-discharge specific capacity of lithium ion battery and first effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171121 |