CN107359317A - Preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source - Google Patents
Preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source Download PDFInfo
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- CN107359317A CN107359317A CN201710368463.7A CN201710368463A CN107359317A CN 107359317 A CN107359317 A CN 107359317A CN 201710368463 A CN201710368463 A CN 201710368463A CN 107359317 A CN107359317 A CN 107359317A
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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
- H01M4/364—Composites as mixtures
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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Abstract
The present invention relates to a kind of preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source, it is characterised in that preparation technology, specific preparation process are as follows：Ludox pre-treatment, SiO2Prepared by intercalation expanded graphite, prepared by Silicon-rich graphite：Using the method for magnesiothermic reduction by SiO2SiO in intercalation expanded graphite2Elemental silicon is reduced into, afterwards after overpickling, washing, drying, just obtains Silicon-rich graphite material;Organic carbon source can select polyacrylonitrile, sucrose or glucose; it is dissolved in solvent; it is configured to 20% ~ 50% solution; wherein solvent is dimethylformamide; the Silicon-rich graphite obtained in step 3 is added thereto afterwards; by suspension at 25 ~ 80 DEG C stirring and drying, then high-temperature calcination 4 ~ 8 hours at a temperature of 500 ~ 800 DEG C under inert gas shielding, obtain product and the compound silicon-carbon cathode material of organic carbon are just obtained after crushing.Without using silica flour as raw material, material cost is reduced, while use organic carbon source as primary carbon source, further reduce material cost, and the method reduced after expanded graphite interlayer situ insertion silica obtains silicon source, preferably can provide cushion for silicon, improve material property.
Description
Technical field
The present invention relates to a kind of preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source, belong to lithium
Ion battery technology field.
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, therefore use carbon material to buffer the volumetric expansion and diminution of silicon materials, silicon-carbon is compound as cushioning frame
Negative material arises at the historic moment.The research to silicon-carbon cathode material is many at present, such as number of patent application
201210387258.2 a kind of preparation method of lithium ion battery silicon-carbon composite and a kind of 201210283761.3 high power capacity
Silicon-carbon cathode material is obtained using silica flour and expanded graphite mixed processing in the preparation method of lithium ion battery negative material,
But this method is limited by silica flour size and dispersing technology, it is difficult to really realize the mesh in silica flour insertion expanded graphite space
, nanoscale silica flour improves material cost, and all carbon sources select expanded graphite in 201210387258.2 patents in addition, significantly
Increase material cost.
The content of the invention
It is an object of the invention to provide a kind of preparation side using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source
Method, this method uses organic carbon as primary carbon source, compound to obtain Si-C composite material with Silicon-rich graphite.Silicon-rich graphite is with silicon
Colloidal sol is handled by early stage as silicon source, improves its binding ability and dispersibility between expanded graphite synusia, directly will
SiO2Insert between expanded graphite lamella.Afterwards, using the method for magnesiothermic reduction by SiO therein2Into after silicon, Silicon-rich is called
Graphite.Method in this patent, as raw material, reduces material cost, while use organic carbon source as main carbon without using silica flour
Source, material cost is further reduced, and the method reduced after expanded graphite interlayer situ insertion silica obtains silicon
Source, cushion preferably can be provided for silicon, improve material property.
The technical proposal of the invention is realized in this way：Using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source
Preparation method, it is characterised in that preparation technology, specific preparation process are as follows：Step 1: Ludox pre-treatment：Take Ludox,
Deionized water is added, the quality of deionized water is 15 ~ 30 times of expanded graphite quality in second step, adds surface wherein afterwards
Activating agent, surfactant are cetyl trimethylammonium bromide, and addition is SiO in Ludox2The 0.1% ~ 10% of quality, so
Afterwards by solution stir 3 ~ 5 hours it is standby;
Step 2: SiO2It is prepared by intercalation expanded graphite：Expanded graphite and Ludox pretreatment solution are weighed, makes SiO therein2Matter
Amount and expanded graphite mass ratio are between 0.5 ~ 1.5.Among Ludox pretreatment solution is added into expanded graphite, stirred
Make with ultrasound in 25 ~ 80 DEG C of drying after its uniform wet, then SiO is just obtained by pulverising step2Intercalation expanded graphite；
Step 3: prepared by Silicon-rich graphite：Using the method for magnesiothermic reduction by SiO2SiO in intercalation expanded graphite2It is reduced into list
Matter silicon, afterwards after overpickling, washing, drying, just obtain Silicon-rich graphite material;
Step 4: organic carbon is compound：Organic carbon source can select polyacrylonitrile, sucrose or glucose, be dissolved in solvent
In, be configured to 20% ~ 50% solution, wherein solvent is dimethylformamide, afterwards adds the Silicon-rich graphite obtained in step 3
Enter wherein, by suspension at 25 ~ 80 DEG C stirring and drying, then high temperature is forged at a temperature of 500 ~ 800 DEG C under inert gas shielding
Burn 4 ~ 8 hours, obtain product and the compound silicon-carbon cathode material of organic carbon is just obtained after crushing.
Surfactant in described step one can be replaced with by cetyl trimethylammonium bromide polyethylene glycol 400 or
Calgon.
Solvent in described step four can replace with water by dimethylformamide.
The positive effect of the present invention is that the advantage of this method is, using this cheap silicon source of Ludox, reduces material
Cost；By carrying out pre-treatment to Ludox, expanded graphite interlayer is inserted it into, it is empty more fully to provide buffering for silicon source
Between, improve silicon carbon material chemical property；Using organic carbon source as primary carbon source, material cost is further reduced.Pass through tune
The addition of section silica-rich material reaches the controllability of performance.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of Si-C composite material in embodiment 1.
Fig. 2 is the high rate performance test of Si-C composite material in embodiment 2.
Embodiment
The present invention will be further described with reference to the accompanying drawings and examples：
Embodiment 1
Weigh 7.5g Ludox, Ludox SiO2Content is 20%, adds 0.15g polyethylene glycol 400s and 20g water wherein, stirs
Mix 3 hours it is standby.1.2g expanded graphites are weighed, Ludox pretreatment solution is added thereto, are sufficiently stirred after soaking at ultrasound
Drying, crushing, obtain SiO after reason 20min2Intercalation expanded graphite.Take 1g SiO2Intercalation expanded graphite, add 0.68gMg mixing
750 DEG C are heated to after uniformly, under argon gas protection and is incubated 3 hours, by SiO therein2Reduction, after overpickling, washing drying, obtain
To Silicon-rich graphite.6 g polyacrylonitrile are weighed, are dissolved in 75g N,N-Dimethylformamides, add Silicon-rich graphite afterwards, fully
Dried after stirring, 700 DEG C of argon gas after the material disintegrating after drying are protected into lower carbonization 5 hours, by crushing again, just
To Si-C composite material.Fig. 1 is that the stereoscan photograph of the material its first discharge specific capacity is 396mAh/g.
Embodiment 2
Weigh 150 g Ludox, Ludox SiO2Content is 20%, adds 0.03 g cetyl trimethylammonium bromides wherein
With 333 g water, stirring 3 hours it is standby.20 g expanded graphites are weighed, Ludox pretreatment solution is added thereto, is sufficiently stirred
Drying, crushing after supersound process 40min, obtain SiO after wetting2Intercalation expanded graphite.Take 10g SiO2Intercalation expanded graphite, makes
With 4.8g Mg, 800 DEG C are heated under argon gas protection, magnesium steam is touched SiO2Intercalation expanded graphite, and reduced,
Reaction time is 4 hours.Dried after overpickling, washing, obtain Silicon-rich graphite.62g sucrose is dissolved in 100g water, completely
3g sodium carboxymethylcelluloses are added after dissolving to continue to dissolve, and are added to Silicon-rich graphite in solution fully after dissolving fully
Stirring, then after drying, crushing, 750 DEG C of temperature are heated under argon atmosphere and are carbonized 4 hours, product is by again
Crushing just obtains Si-C composite material.Fig. 2 provides discharge curve of the material under different multiplying, and first discharge specific capacity is
The mAh/g of 530.7mAh/g, 5C specific discharge capacity 113.
Claims (3)
1. using Ludox as the preparation method of the compound silicon-carbon cathode of the organic carbon of silicon source, it is characterised in that preparation technology, tool
The preparation process of body is as follows：Step 1: Ludox pre-treatment：Ludox is taken, adds deionized water, the quality of deionized water is
15 ~ 30 times of expanded graphite quality in second step, add surfactant wherein afterwards, and surfactant is cetyl three
Methyl bromide ammonium, addition are SiO in Ludox2The 0.1% ~ 10% of quality, then by solution stir 3 ~ 5 hours it is standby;
Step 2: SiO2It is prepared by intercalation expanded graphite：Expanded graphite and Ludox pretreatment solution are weighed, makes SiO therein2Matter
Amount and expanded graphite mass ratio are between 0.5 ~ 1.5；Among Ludox pretreatment solution is added into expanded graphite, stirred
Make with ultrasound in 25 ~ 80 DEG C of drying after its uniform wet, then SiO is just obtained by pulverising step2Intercalation expanded graphite；
Step 3: prepared by Silicon-rich graphite：Using the method for magnesiothermic reduction by SiO2SiO in intercalation expanded graphite2It is reduced into simple substance
Silicon, afterwards after overpickling, washing, drying, just obtain Silicon-rich graphite material;
Step 4: organic carbon is compound：Organic carbon source can select polyacrylonitrile, sucrose or glucose, be dissolved in solvent
In, be configured to 20% ~ 50% solution, wherein solvent is dimethylformamide, afterwards adds the Silicon-rich graphite obtained in step 3
Enter wherein, by suspension at 25 ~ 80 DEG C stirring and drying, then high temperature is forged at a temperature of 500 ~ 800 DEG C under inert gas shielding
Burn 4 ~ 8 hours, obtain product and the compound silicon-carbon cathode material of organic carbon is just obtained after crushing.
2. according to the preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source described in claim 1,
It is characterized in that the surfactant in described step one can replace with polyethylene glycol 400 by cetyl trimethylammonium bromide
Or calgon.
3. according to the preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source described in claim 1,
It is characterized in that the solvent in described step four can replace with water by dimethylformamide.
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| CN201710368463.7A CN107359317A (en) | 2017-05-23 | 2017-05-23 | Preparation method using Ludox as the compound silicon-carbon cathode of the organic carbon of silicon source |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111785969A (en) * | 2020-07-08 | 2020-10-16 | 吴耀帮 | Preparation method of porous nano Si-SiO2-C @ graphite composite lithium ion battery cathode powder and lithium ion battery |
| CN111834610A (en) * | 2019-04-16 | 2020-10-27 | 南京工业大学 | Preparation method of lithium ion battery silicon-carbon composite negative electrode material based on magnesium thermal reduction |
| CN112086624A (en) * | 2019-06-12 | 2020-12-15 | 识骅科技股份有限公司 | Manufacturing method of composite carbon-silicon cathode substrate and composite carbon-silicon cathode substrate manufactured by manufacturing method |
| CN112421043A (en) * | 2020-11-20 | 2021-02-26 | 中南大学 | Natural graphite negative electrode material and application thereof |
| CN113285066A (en) * | 2021-04-07 | 2021-08-20 | 中南大学 | Vanadium phosphate @ carbon/expanded microcrystalline graphite composite negative electrode active material for potassium ion battery and preparation and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111834610A (en) * | 2019-04-16 | 2020-10-27 | 南京工业大学 | Preparation method of lithium ion battery silicon-carbon composite negative electrode material based on magnesium thermal reduction |
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| CN111785969A (en) * | 2020-07-08 | 2020-10-16 | 吴耀帮 | Preparation method of porous nano Si-SiO2-C @ graphite composite lithium ion battery cathode powder and lithium ion battery |
| CN112421043A (en) * | 2020-11-20 | 2021-02-26 | 中南大学 | Natural graphite negative electrode material and application thereof |
| CN113285066A (en) * | 2021-04-07 | 2021-08-20 | 中南大学 | Vanadium phosphate @ carbon/expanded microcrystalline graphite composite negative electrode active material for potassium ion battery and preparation and application thereof |
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Application publication date: 20171117 |