CN107959007A - A kind of preparation method of coated graphite alkene-silicon lithium ion battery cathode material - Google Patents
A kind of preparation method of coated graphite alkene-silicon lithium ion battery cathode material Download PDFInfo
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- CN107959007A CN107959007A CN201711065161.9A CN201711065161A CN107959007A CN 107959007 A CN107959007 A CN 107959007A CN 201711065161 A CN201711065161 A CN 201711065161A CN 107959007 A CN107959007 A CN 107959007A
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- graphite alkene
- lithium ion
- ion battery
- cathode material
- battery cathode
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- 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
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- 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
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 coated graphite alkene silicon lithium ion battery cathode material, it is characterised in that：It is 12 first by mass ratio:1 graphene oxide and maleate is distributed in water, and dispersed spray drying, becomes powdered, high-temperature heat treatment, obtain spherical graphite alkene microballoon；By siliceous slurry and spherical graphite alkene microballoon after mixing, evaporate after solvent with hard pitch in mass ratio 12:After 1 high speed batch mixing, stirring and then heating pyrolysis, high-temperature heat treatment, then carries out graphitization under an inert atmosphere, obtains coated graphite alkene silicon lithium ion battery cathode material.Present invention has the advantages that：Spherical graphite alkene microballoon high degree of dispersion, maleate, silicon and carbon are evenly distributed, and discharge capacity is up to more than 860 first, and coulombic efficiency is up to discharge and recharge under more than 90%, 0.1C first, capacity retention ratio more than 82% after 500 circulations.
Description
Technical field
The invention belongs to lithium ion battery negative material preparing technical field, and in particular to a kind of coated graphite alkene-silicon lithium
The preparation method of ion battery cathode material.
Background technology
With the demand of production and the raising of environmental protection consciousness, new energy becomes the emphasis that various countries fall over each other development, wherein
The development of lithium ion battery is especially swift and violent, its application is related to the fields such as 3C Product, power set, energy storage device.
Current commercialized lithium ion battery negative material is mainly graphite, but theoretical capacity is only 372mAh/g, by
Cannot gradually meet the needs of market is to high-energy-density.
Silicon materials theoretical capacity can reach 4200mAh/g, than current commercial high an order of magnitude of carbon negative pole material.But
Silicon materials as lithium ion battery negative material there are one it is fatal the defects of, be exactly the absorption in lithium ion and desorption process
In, volume change is big, reaches 300%, so that silicium cathode fragmentation, causes charge-discharge performance very poor, it is difficult to realizes application.
At present, the composite material of silicon and graphene is frequently used to make the graphene negative material of high power capacity, use
Technology is substantially silicon nanowires, and either nano grain surface coated graphite alkene or other carbon materials are filling to suppress silicon materials
Fragmentation in discharge process.But the main problem of these methods is that silicon is still deposited in negative material in the form of little particle silicon
Charge and discharge process is just difficult to avoid that there are volume change, and long-term charge-discharge performance is still key issue.
The content of the invention
In order to solve the technical problem that graphite theoretical capacity in the prior art is low, silicon removal lithium embedded causes structure collapses, this hair
Bright purpose is to provide a kind of preparation method of coated graphite alkene-silicon lithium ion battery cathode material.
The technical scheme is that：
A kind of preparation method of coated graphite alkene-silicon lithium ion battery cathode material, is 1-2 first by mass ratio:1 oxygen
Graphite alkene and maleate are distributed in water, are obtained dispersion liquid after stirring 2h at 70-90 DEG C, are then sprayed at 150-200 DEG C
Mist dry, become it is powdered, 220-250 DEG C processing 5h after, then 300-350 DEG C handle 5h after, 450-500 DEG C processing
5h, then 5h is handled at 750-800 DEG C, obtain spherical graphite alkene microballoon；Siliceous slurry is uniformly mixed with spherical graphite alkene microballoon
Afterwards, evaporate after solvent with hard pitch 1-2 in mass ratio:After 1 high speed batch mixing, stirring and then heating pyrolysis, in inert atmosphere
Lower charing, carbonization temperature are 1000-1200 DEG C, when soaking time is 10-12 small, then carry out graphitization, graphitization temperature is
2800-3000 DEG C, when soaking time is 10-12 small, obtain coated graphite alkene-silicon lithium ion battery cathode material.
Preferably：It is 1.5 first by mass ratio:1 graphene oxide and maleate is distributed in water, is stirred at 80 DEG C
Obtain dispersion liquid after mixing 2h, be then spray-dried at 180 DEG C, become it is powdered, after 240 DEG C of processing 5h, then at 320 DEG C
After handling 5h, 480 DEG C of processing 5h, then 5h is handled at 780 DEG C, obtain spherical graphite alkene microballoon；By siliceous slurry and spherical graphite
Alkene microballoon after mixing, evaporate after solvent with hard pitch in mass ratio 1.5:After 1 high speed batch mixing, stirring and then heating heat
Solution, carbonizes under an inert atmosphere, and carbonization temperature is 1100 DEG C, when soaking time is 12 small, then carries out graphitization, graphitization temperature
Spend for 2900 DEG C, when soaking time is 12 small, obtain coated graphite alkene-silicon lithium ion battery cathode material.
Present invention has the advantages that：Spherical graphite alkene microballoon high degree of dispersion, maleate, silicon and carbon are evenly distributed, first
Discharge capacity is up to more than 860, and coulombic efficiency is up to discharge and recharge under more than 90%, 0.1C first, capacity retention ratio after 500 circulations
More than 82%.
Embodiment
Technical scheme is described in detail below.
Embodiment 1
It is 1 first by mass ratio:1 graphene oxide and maleate is distributed in water, is obtained after stirring 2h at 70 DEG C
Dispersion liquid, is then spray-dried at 150 DEG C, become it is powdered, 220 DEG C processing 5h after, then 350 DEG C handle 5h after,
450 DEG C of processing 5h, then 5h is handled at 750 DEG C, obtain spherical graphite alkene microballoon；Siliceous slurry is mixed with spherical graphite alkene microballoon
After uniformly, evaporate after solvent with hard pitch in mass ratio 1:After 1 high speed batch mixing, stirring and then heating pyrolysis, in indifferent gas
Being carbonized under atmosphere, carbonization temperature is 1000 DEG C, when soaking time is 10 small, then carries out graphitization, and graphitization temperature is 3000 DEG C,
When soaking time is 12 small, coated graphite alkene-silicon lithium ion battery cathode material is obtained.
Embodiment 2
It is 1.5 first by mass ratio:1 graphene oxide and maleate is distributed in water, is obtained after stirring 2h at 80 DEG C
To dispersion liquid, be then spray-dried at 180 DEG C, become it is powdered, 240 DEG C processing 5h after, then 320 DEG C handle 5h
Afterwards, 480 DEG C of processing 5h, then 5h is handled at 780 DEG C, obtain spherical graphite alkene microballoon；By siliceous slurry and spherical graphite alkene microballoon
After mixing, evaporate after solvent with hard pitch in mass ratio 1.5:After 1 high speed batch mixing, stirring and then heating pyrolysis,
Carbonized under inert atmosphere, carbonization temperature is 1100 DEG C, when soaking time is 12 small, then carries out graphitization, graphitization temperature is
2900 DEG C, when soaking time is 12 small, obtain coated graphite alkene-silicon lithium ion battery cathode material.
Embodiment 3
It is 2 first by mass ratio:1 graphene oxide and maleate is distributed in water, is obtained after stirring 2h at 90 DEG C
Dispersion liquid, is then spray-dried at 200 DEG C, become it is powdered, 220 DEG C processing 5h after, then 350 DEG C handle 5h after,
450-500 DEG C of processing 5h, then 5h is handled at 800 DEG C, obtain spherical graphite alkene microballoon；By siliceous slurry and spherical graphite alkene microballoon
After mixing, evaporate after solvent with hard pitch in mass ratio 2:After 1 high speed batch mixing, stirring and then heating pyrolysis, lazy
Property atmosphere under carbonize, carbonization temperature be 1200 DEG C, soaking time for 12 it is small when, then carry out graphitization, graphitization temperature is
2800 DEG C, when soaking time is 10 small, obtain coated graphite alkene-silicon lithium ion battery cathode material.
Material prepared by Example 1~3 is as negative material, and binding agent (LA132), conductive agent (Super-P) and
Dispersant (water and ethanol, volume ratio position 1：3) it is tuned into slurry, coated on copper foil, and vacuum dried, roll-in, it is prepared into negative
Pole piece；Cathode uses metal lithium sheet, and the organic electrolyte used is 1MLiPF6/EC+PC+DEC (molar ratios 1：1：1), membrane
For polypropylene, CR2025 type button cells are made.Test condition is room temperature, and discharge and recharge under 0.1C, charging/discharging voltage is limited to
0.005~1.5V.
1 half-cell test performance of table
Claims (4)
- A kind of 1. preparation method of coated graphite alkene-silicon lithium ion battery cathode material, it is characterised in that：It is by mass ratio first 1-2:1 graphene oxide and maleate is distributed in water, dispersion liquid is obtained after stirring 2h at 70-90 DEG C, then in 150- Be spray-dried at 200 DEG C, become it is powdered, 220-250 DEG C processing 5h after, then 300-350 DEG C handle 5h after, 450- 500 DEG C of processing 5h, then 5h is handled at 750-800 DEG C, obtain spherical graphite alkene microballoon；By siliceous slurry and spherical graphite alkene microballoon After mixing, evaporate after solvent with hard pitch 1-2 in mass ratio:After 1 high speed batch mixing, stirring and then heating pyrolysis, Carbonized under inert atmosphere, carbonization temperature is 1000-1200 DEG C, when soaking time is 10-12 small, then carries out graphitization, graphite It is 2800-3000 DEG C to change temperature, when soaking time is 10-12 small, obtains coated graphite alkene-silicon lithium ion battery cathode material.
- 2. a kind of preparation method of coated graphite alkene-silicon lithium ion battery cathode material as claimed in claim 1, its feature exist In：It is 1.5 first by mass ratio:1 graphene oxide and maleate is distributed in water, is disperseed after stirring 2h at 80 DEG C Liquid, is then spray-dried at 180 DEG C, become it is powdered, 240 DEG C processing 5h after, then 320 DEG C handle 5h after, 480 DEG C 5h is handled, then 5h is handled at 780 DEG C, obtains spherical graphite alkene microballoon；Siliceous slurry is uniformly mixed with spherical graphite alkene microballoon Afterwards, evaporate after solvent with hard pitch in mass ratio 1.5:After 1 high speed batch mixing, stirring and then heating pyrolysis, in inert atmosphere Lower charing, carbonization temperature are 1100 DEG C, when soaking time is 12 small, then carry out graphitization, graphitization temperature is 2900 DEG C, is protected When the warm time is 12 small, coated graphite alkene-silicon lithium ion battery cathode material is obtained.
- A kind of 3. lithium ion battery negative material, it is characterised in that：Prepared using method as claimed in claim 1 or 2.
- A kind of 4. lithium ion battery, it is characterised in that：Using negative material as claimed in claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711065161.9A CN107959007B (en) | 2017-11-02 | 2017-11-02 | Preparation method of graphene-silicon-coated lithium ion battery negative electrode material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711065161.9A CN107959007B (en) | 2017-11-02 | 2017-11-02 | Preparation method of graphene-silicon-coated lithium ion battery negative electrode material |
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| CN107959007A true CN107959007A (en) | 2018-04-24 |
| CN107959007B CN107959007B (en) | 2020-10-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112054165A (en) * | 2019-06-05 | 2020-12-08 | 上海杉杉科技有限公司 | Mesocarbon microbeads, graphite negative electrode material, preparation method of mesocarbon microbeads and graphite negative electrode material, and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591177A (en) * | 2015-02-03 | 2015-05-06 | 辽宁工程技术大学 | Method for preparing self-supporting three-dimensional porous graphene composite microsphere |
| CN106067547A (en) * | 2016-08-10 | 2016-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite |
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2017
- 2017-11-02 CN CN201711065161.9A patent/CN107959007B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591177A (en) * | 2015-02-03 | 2015-05-06 | 辽宁工程技术大学 | Method for preparing self-supporting three-dimensional porous graphene composite microsphere |
| CN106067547A (en) * | 2016-08-10 | 2016-11-02 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon-coated nano 3 SiC 2/graphite alkene cracks carbon-coating composite, preparation method and the lithium ion battery comprising this composite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112054165A (en) * | 2019-06-05 | 2020-12-08 | 上海杉杉科技有限公司 | Mesocarbon microbeads, graphite negative electrode material, preparation method of mesocarbon microbeads and graphite negative electrode material, and lithium ion battery |
| CN112054165B (en) * | 2019-06-05 | 2022-02-08 | 上海杉杉科技有限公司 | Mesocarbon microbeads, graphite negative electrode material, preparation method of mesocarbon microbeads and graphite negative electrode material, and lithium ion battery |
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