CN1251341C - Method for processing surface of natural griaphite for lithium ion battery - Google Patents
Method for processing surface of natural griaphite for lithium ion battery Download PDFInfo
- Publication number
- CN1251341C CN1251341C CNB031442781A CN03144278A CN1251341C CN 1251341 C CN1251341 C CN 1251341C CN B031442781 A CNB031442781 A CN B031442781A CN 03144278 A CN03144278 A CN 03144278A CN 1251341 C CN1251341 C CN 1251341C
- Authority
- CN
- China
- Prior art keywords
- graphite
- lithium ion
- natural graphite
- ion battery
- mixed solution
- 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.)
- Expired - Fee Related
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
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention belongs to the technical field of a material application of lithium ion batteries. A surface treatment method of natural graphite for the lithium ion batteries comprises the following technological processes: (1) a surface active agent is firstly obtained to coat the natural graphite; (2) then acetylene black is obtained to coat the natural graphite; (3) an organic polymer is obtained to coat the natural graphite; (4) finally, silicane is obtained to coat the natural graphite, natural graphite for lithium ion batteries with high performance and low cost by processing at high temperature is obtained, and the surface of the natural graphite is processed. The present invention solves the problems that a precursor of an organic substance is difficult to uniformly coat on every graphite particle surface, and after carbonization is carried out at high temperature, graphite particles are mutually connected; after graphite material is coated with hard carbon, the specific surface area of the graphite material is higher than that of graphite material which is not coated with the hard carbon, the first irreversible capacity loss is increased, etc. The natural graphite has the advantages of low cost and reliable product quality, and can be used for various kinds of negative electrode material of lithium ion batteries.
Description
Technical field
The invention belongs to the lithium ion battery material applied technical field, particularly relate to the surface treatment method of a kind of lithium ion battery with native graphite.
Background technology
The present widely used negative material of lithium ion battery is an electrographite, because electrographite class material price costliness, countries in the world just adopt native graphite to replace electrographite in active research.Much studies show that, replace electrographite to have a series of problems with native graphite, as: cycle efficieny is on the low side first, tap density is on the low side, cyclical stability is relatively poor, capacity under the high current charge-discharge condition is on the low side and to the requirement of solvent very strictness etc.Overcome at present that above problem is normal to adopt following several method: (1) by chemical oxidation or in oxygen or carbon dioxide high-temperature oxydation graphite, make surface generation oxygen-containing functional group, use alkali treatment again, to reach the purpose of passivation graphite surface.This method is more loaded down with trivial details, and reappearance is relatively poor, is difficult to suitability for industrialized production.(2) with certain SiO (SiO
2), ZrO
2Deng oxide graphite surface is coated processing.Difference is very big as a result to the graphite of separate sources for this method.(3) with hard carbon graphite is coated processing.Promptly earlier graphite is coated processing, under inert atmosphere, pass through high-temperature process again, make graphite surface coat the hard raw material of wood-charcoal material of one deck with specific organic polymer precursor.The main difficult point of this method is: be difficult to the organic substance precursor evenly is coated on each graphite granule surface, and through interconnecting between the graphite granule behind the high temperature sintering, and often than also high before not coating, making first, irreversible capacity loss increases the specific area of the graphite material after hard charcoal coats.
Summary of the invention
The present invention is the solution problems of the prior art, and the surface treatment method of a kind of lithium ion battery with native graphite is provided.
The purpose of this invention is to provide a kind of organic polymer that makes and evenly coat each graphite granule surface, and adhesion between the particle, reduce hard carbon coated graphite specific area and reduce the surface treatment method of a kind of lithium ion battery of irreversible capacity loss first with native graphite.
The present invention takes following technical scheme:
The lithium ion battery surface treatment method of native graphite, it is characterized in that: its surface treatment method comprises following technical process:
(1) the dose volume ratio is 9: 1, contains the de-ionate of 0.2wt% surfactant and the mixed solution of ethanol, puts into graphite in the whipping process, filters out graphite after continuing to stir;
(2) prepare the de-ionate that do not contain surfactant and the mixed solution of ethanol again according to aforementioned proportion, put into the graphite after the above-mentioned filtration in the whipping process, be that 3: 100 ratio adds acetylene black in acetylene black and graphite weight ratio when stirring, continue to filter out graphite after the stirring;
(3) graphite that filters out in (2) step is placed vacuum drying chamber dry, then graphite is pulverized; To pulverize in the mixed solution that graphite joins the oxolane that is dissolved with organic polymer and acetone, described graphite and described organic polymer weight ratio are 5: 1, the volume ratio of oxolane and acetone is 1: 1 in the described mixed solution, be heated to 50-100 ℃ in the whipping process, after evaporating oxolane and acetone, again graphite is pulverized;
(4) graphite of pulverizing in (3) step is placed the heating furnace of mobile dry oxygen or air, kept 2-4 hour, take out behind the cool to room temperature in 300-400 ℃ of constant temperature;
(5) graphite under the above-mentioned room temperature being put into weight ratio is 1: 10 the vinyltriethoxysilane and the mixed solution of ethanol, be heated to 70-100 ℃ under stirring, evaporated fully until ethanol, again graphite is placed the heating furnace of logical pure argon or nitrogen, when temperature is elevated to 500-600 ℃, be incubated 2-4 hour, and then furnace temp is elevated to 1000-1300 ℃, be incubated 1-2 hour again, be cooled to normal temperature, promptly get surface treated lithium ion battery native graphite with stove.
The present invention can also adopt following technical measures to realize:
The described lithium ion battery surface treatment method of native graphite, be characterized in: described surfactant is a polyvinyl alcohol; Described organic substance is pitch or resin.
Advantage and good effect that the present invention has are: can reach the purpose of the even coated graphite particle surface of organic polymer, make more than the reversible capacity increase 30mAh/g after native graphite coats hard charcoal; After adding silane crosslinker, can increase the pyrolysis yield of organic polymer and the tap density of hard charcoal coated natural graphite.When the silicon/charcoal atomic ratio on hard charcoal coated natural graphite surface within the specific limits the time, specific area is significantly reduced, thereby significantly reduce the irreversible capacity loss of circulation first.
Description of drawings
Fig. 1 is the process chart of lithium ion battery of the present invention with the surface treatment method of native graphite.
Embodiment
For further understanding content of the present invention, characteristics and effect, enumerate following example now and be described in detail as follows:
Embodiment 1
With reference to Fig. 1,10g graphite is joined in the mixed solution of de-ionate, ethanol and polyvinyl alcohol of 100ml, wherein the volume ratio of de-ionate and ethanol is 9: 1, and the concentration of polyvinyl alcohol is 0.2wt.%, stir after 30 minutes and filter, obtain surfactant and coat native graphite; Again this graphite is joined in the mixed solution of 100ml de-ionate and ethanol, wherein the volume ratio of de-ionate and ethanol is the same, stirs down to add 0.3g acetylene black, continues to stir after 30 minutes and filters, 110 ℃ of vacuumizes are standby after 3 hours, obtain the acetylene black coated natural graphite; Join after this graphite pulverized and be dissolved with in the mixed solution that the 2.44g softening point is 280 ℃ the oxolane of pitch and acetone, wherein the volume ratio of oxolane and acetone is 1: 1, be heated to 50-100 ℃ in the whipping process, after evaporating oxolane and acetone, obtain the pitch-coating native graphite; Pulverize this graphite, put it in the heating furnace, in dry oxygen that flows or air,, take out after being cooled to room temperature in 330-350 ℃ of insulation 3 hours; This graphite is joined in the 50ml ethanolic solution that contains vinyltriethoxysilane 5g, under stirring, be heated to 83 ℃, react evaporate to dryness ethanol after 30 minutes, obtain the silane coated natural graphite; Insulation is 3 hours this graphite is heated to 500 ℃ in the heating furnace that contains pure argon or nitrogen after, is warmed up to 1100-1300 ℃ of insulation 1 hour again, with the stove cooling, promptly gets surface treated lithium ion battery native graphite.
Claims (3)
1, the lithium ion battery surface treatment method of native graphite, it is characterized in that: its surface treatment method comprises following technical process:
(1) the dose volume ratio is 9: 1, contains the de-ionate of 0.2wt% surfactant and the mixed solution of ethanol, puts into graphite in the whipping process, filters out graphite after continuing to stir;
(2) prepare the de-ionate that do not contain surfactant and the mixed solution of ethanol again according to aforementioned proportion, put into the graphite after the above-mentioned filtration in the whipping process, be that 3: 100 ratio adds acetylene black in acetylene black and graphite weight ratio when stirring, continue to filter out graphite after the stirring;
(3) graphite that filters out in (2) step is placed vacuum drying chamber dry, then graphite is pulverized; To pulverize in the mixed solution that graphite joins the oxolane that is dissolved with organic polymer and acetone, described graphite and described organic polymer weight ratio are 5: 1, the volume ratio of oxolane and acetone is 1: 1 in the described mixed solution, be heated to 50-100 ℃ in the whipping process, after evaporating oxolane and acetone, again graphite is pulverized;
(4) graphite of pulverizing in (3) step is placed the heating furnace of mobile dry oxygen or air, kept 2-4 hour, take out behind the cool to room temperature in 300-400 ℃ of constant temperature;
(5) graphite under the above-mentioned room temperature being put into weight ratio is 1: 10 the vinyltriethoxysilane and the mixed solution of ethanol, be heated to 70-100 ℃ under stirring, evaporated fully until ethanol, again graphite is placed the heating furnace of logical pure argon or nitrogen, when temperature is elevated to 500-600 ℃, be incubated 2-4 hour, and then furnace temp is elevated to 1000-1300 ℃, be incubated 1-2 hour again, be cooled to normal temperature, promptly get surface treated lithium ion battery native graphite with stove.
2, the lithium ion battery according to claim 1 surface treatment method of native graphite, it is characterized in that: described surfactant is a polyvinyl alcohol.
3, the lithium ion battery according to claim 1 surface treatment method of native graphite, it is characterized in that: described organic substance is pitch or resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031442781A CN1251341C (en) | 2003-09-16 | 2003-09-16 | Method for processing surface of natural griaphite for lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031442781A CN1251341C (en) | 2003-09-16 | 2003-09-16 | Method for processing surface of natural griaphite for lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1599102A CN1599102A (en) | 2005-03-23 |
| CN1251341C true CN1251341C (en) | 2006-04-12 |
Family
ID=34659459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031442781A Expired - Fee Related CN1251341C (en) | 2003-09-16 | 2003-09-16 | Method for processing surface of natural griaphite for lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1251341C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354739B (en) * | 2011-09-26 | 2015-01-07 | 浙江南都电源动力股份有限公司 | Silicon-carbon composite anode material for lithium ion battery and preparation method thereof |
| CN102376944B (en) * | 2011-11-24 | 2013-04-24 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing silicon carbide alloy negative electrode material for lithium ion battery |
| CN102593438B (en) * | 2012-03-01 | 2014-07-02 | 合肥国轩高科动力能源股份公司 | Carbon-coating and surface film performing co-modification preparation method of anode material of lithium ion secondary battery |
| CN103579624B (en) * | 2013-10-17 | 2016-03-02 | 东莞市凯金新能源科技股份有限公司 | Modified lithium battery graphite crucible waste material negative material and preparation method thereof and application |
| CN105990580A (en) * | 2015-02-12 | 2016-10-05 | 深圳市比克电池有限公司 | Negative electrode material, and negative plate of lithium ion battery and preparation method thereof |
-
2003
- 2003-09-16 CN CNB031442781A patent/CN1251341C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1599102A (en) | 2005-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107170965B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN104638240B (en) | Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method | |
| 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 | |
| CN109148847B (en) | Boron-doped modified hard carbon-coated negative electrode material with high rate performance and liquid-phase preparation method thereof | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN109817957B (en) | Preparation method of asphalt-coated silicon-doped natural crystalline flake graphite negative electrode material | |
| CN113620272B (en) | Preparation method of negative electrode material of sodium ion battery | |
| CN108400297B (en) | Silicon-based lithium ion battery cathode material and preparation method thereof | |
| CN109920995B (en) | Silicon or oxide @ titanium oxide core-shell structure composite material and preparation method thereof | |
| CN103078092A (en) | Method for preparing Si/C composite cathode material of lithium ion battery | |
| CN109904387B (en) | Preparation method of high-performance lithium battery positive plate | |
| CN111697218A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN113998700B (en) | Method for preparing Si/SiC@C anode material by taking micro silicon powder as raw material | |
| CN111916732A (en) | Modified lithium iron phosphate material and preparation method thereof | |
| CN1251341C (en) | Method for processing surface of natural griaphite for lithium ion battery | |
| CN108565427A (en) | A kind of preparation method of carbon/lithium titanate composite material | |
| CN112174119B (en) | Method for preparing graphene foam from antibiotic fungi residues | |
| CN112018355B (en) | Preparation method of three-dimensional rod-shaped potassium titanate material | |
| CN113782718A (en) | High-voltage lithium ion battery material, lithium ion battery and preparation method thereof | |
| CN113078320A (en) | Melamine modified graphite negative electrode material and preparation method and application thereof | |
| CN109473648B (en) | Silicon-carbon composite material for lithium ion battery and preparation method thereof | |
| CN116666589A (en) | Nano silicon carbon composite negative electrode material with core-shell structure, and preparation method and application thereof | |
| CN114944480B (en) | Preparation method of honeycomb porous tin-carbon composite material | |
| CN109360959B (en) | Carbon selenium material, preparation method thereof and application thereof in energy storage device | |
| CN112687861A (en) | Silicon oxide and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060412 Termination date: 20150916 |
|
| EXPY | Termination of patent right or utility model |