CN107342400A - A kind of preparation method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source - Google Patents

A kind of preparation method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source Download PDF

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Publication number
CN107342400A
CN107342400A CN201710369002.1A CN201710369002A CN107342400A CN 107342400 A CN107342400 A CN 107342400A CN 201710369002 A CN201710369002 A CN 201710369002A CN 107342400 A CN107342400 A CN 107342400A
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China
Prior art keywords
silicon
ludox
graphite
sio
expanded graphite
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Pending
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CN201710369002.1A
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Chinese (zh)
Inventor
陈慧明
王丹
姜涛
许德超
张克金
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FAW Group Corp
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FAW Group Corp
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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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • 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
    • 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
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source, it is characterised in that preparation method, specific preparation process are as follows：By 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；Silicon-rich graphite material is taken, is added in the electrostatic spinning solution configured, one-dimensional spinning material is prepared by electrostatic spinning process, the addition of Silicon-rich graphite is adjusted according to the different capabilities demand of material, and addition quality should ensure that theoretical silicone content below 20%.High-temperature calcination is carbonized for 4 ~ 8 hours between 500 ~ 800 DEG C under protective atmosphere afterwards, and one-dimensional silicon-carbon composite cathode material is just obtained after pulverising step.Without using silica flour as silicon source, reduction material cost on the other hand can be discrete between expanded graphite synusia by silica using the Ludox after pre-treatment, so as to ensure cushioning effect of the expanded graphite to silicon；Coordinate the performance for electrospinning process, further improving material.

Description

A kind of preparation method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source
Technical field
The present invention relates to a kind of preparation method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source, belong to lithium from Sub- cell art.
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 method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source, Silicon source of this method using Ludox as silicon-carbon cathode, is handled by early stage, improves its combination between expanded graphite synusia Ability and dispersibility, directly by SiO2Insert between expanded graphite lamella.Afterwards, using the method for magnesiothermic reduction by SiO2Insert Layer expanded graphite is reduced into Silicon-rich graphite.Silicon-rich graphite is added in spinning solution, master is used as using organic polymer binding agent Carbon source is wanted, is woven into silk, organic carbon source is reduced into by carbon by high temperature cabonization afterwards, finally gives silicon-carbon composite cathode material. For this method without using silica flour as silicon source, reduction material cost on the other hand can be by dioxy using the Ludox after pre-treatment SiClx is discrete between expanded graphite synusia, so as to ensure cushioning effect of the expanded graphite to silicon；Coordinate with electrospinning process, Further improve the performance of material.
The technical proposal of the invention is realized in this way：A kind of one-dimensional silicon-carbon composite cathode material using Ludox as silicon source Preparation method, it is characterised in that preparation method, specific preparation process are as follows：
Step 1: Ludox pre-treatment：Ludox is taken, adds deionized water, the quality of deionized water is to expand stone in second step 15 ~ 30 times of black quality, add surfactant wherein afterwards, surfactant include cetyl trimethylammonium bromide, Polyethylene glycol 400 or calgon, addition are the silica SiO in Ludox2The 0.1% ~ 10% of quality, then will be molten Liquid 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: Si-C composite material synthesizes：Take richness Silica ink material, it is added in the electrostatic spinning solution configured, one-dimensional spinning material is prepared by electrostatic spinning process, it is rich The addition of 3 SiC 2/graphite is adjusted according to the different capabilities demand of material, and addition quality should ensure that theoretical silicone content below 20%. High-temperature calcination is carbonized for 4 ~ 8 hours between 500 ~ 800 DEG C under protective atmosphere afterwards, and one-dimensional silicon-carbon is just obtained after pulverising step Composite negative pole material.
Surfactant in described described step one is cetyl trimethylammonium bromide, can be by cetyl trimethyl Ammonium bromide replaces with polyethylene glycol 400 or calgon.
The positive effect of the present invention is that it uses this cheap silicon source of Ludox, reduces the cost of material；By to silicon Colloidal sol carries out pre-treatment, inserts it into expanded graphite interlayer, more fully provides cushion space for silicon source, improves silicon carbon material electricity Chemical property；Using electrospinning process, on the one hand cost can be reduced as primary carbon source by introducing other carbon sources；On the other hand Form one-dimensional material, the significantly more efficient chemical property for improving material., can be with simultaneously by adjusting the addition of Silicon-rich graphite Accomplish capacity and the controllable purpose of cost.
Brief description of the drawings
Fig. 1 is silicon-carbon cathode 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
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 Silk is woven into by the method for classical spinning after stirring.By the silk of weaving after being carbonized 5 hours under 700 DEG C of argon gas are protected, By pulverising step, silicon-carbon composite cathode material is obtained.Fig. 1 is that the ESEM of silicon-carbon composite cathode material in the embodiment shines Piece, the silicon-carbon cathode material first discharge specific capacity reach 513mAh/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.After overpickling, washing drying, Silicon-rich graphite is obtained.Weigh 46 g polyvinylpyrrolidone conducts Carbon source and electrostatic spinning binding agent, are dissolved in absolute ethyl alcohol, Silicon-rich graphite are added afterwards, by quiet after being sufficiently stirred Material is woven into silk by the method for Electrospun.Weaving product is heated into 700 DEG C of insulations under argon gas protection to be carbonized within 6 hours, warp Si-C composite material is just obtained after crossing crushing.Fig. 2 is button cell first charge-discharge curve of the material using lithium piece as negative pole, Its specific discharge capacity can reach 543mAh/g.

Claims (2)

  1. A kind of 1. preparation method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source, it is characterised in that preparation method, Specific preparation process is as follows：
    Step 1: Ludox pre-treatment：Ludox is taken, adds deionized water, the quality of deionized water is to expand stone in second step 15 ~ 30 times of black quality, add surfactant wherein afterwards, surfactant include cetyl trimethylammonium bromide, Polyethylene glycol 400 or calgon, addition are the silica SiO in Ludox2The 0.1% ~ 10% of quality, then will be molten Liquid 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: Si-C composite material synthesizes：Take Silicon-rich Graphite material, it is added in the electrostatic spinning solution configured, one-dimensional spinning material, Silicon-rich is prepared by electrostatic spinning process The addition of graphite is adjusted according to the different capabilities demand of material, and addition quality should ensure that theoretical silicone content below 20%；It High-temperature calcination is carbonized for 4 ~ 8 hours between 500 ~ 800 DEG C under protective atmosphere afterwards, and just obtaining one-dimensional silicon-carbon after pulverising step answers Close negative material.
  2. 2. according to a kind of preparation side using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source described in claim 1 Method, it is characterised in that the surfactant in described described step one is cetyl trimethylammonium bromide, can be by 16 Alkyl trimethyl ammonium bromide replaces with polyethylene glycol 400 or calgon.
CN201710369002.1A 2017-05-23 2017-05-23 A kind of preparation method using Ludox as the one-dimensional silicon-carbon composite cathode material of silicon source Pending CN107342400A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108598434A (en) * 2018-04-24 2018-09-28 盐城师范学院 A kind of electrostatic self-assembled preparation method of graphene/silicon electrode material
CN111834611A (en) * 2019-04-16 2020-10-27 南京工业大学 Preparation method of uniformly dispersed silicon-carbon composite negative electrode material based on magnesiothermic reduction

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102769139A (en) * 2012-08-10 2012-11-07 深圳市斯诺实业发展有限公司永丰县分公司 Preparation method of high power capacity lithium ion battery cathode material
CN103985846A (en) * 2014-05-30 2014-08-13 西安交通大学 Carbon-loaded silica nanoparticle structure as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102769139A (en) * 2012-08-10 2012-11-07 深圳市斯诺实业发展有限公司永丰县分公司 Preparation method of high power capacity lithium ion battery cathode material
CN103985846A (en) * 2014-05-30 2014-08-13 西安交通大学 Carbon-loaded silica nanoparticle structure as well as preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108598434A (en) * 2018-04-24 2018-09-28 盐城师范学院 A kind of electrostatic self-assembled preparation method of graphene/silicon electrode material
CN111834611A (en) * 2019-04-16 2020-10-27 南京工业大学 Preparation method of uniformly dispersed silicon-carbon composite negative electrode material based on magnesiothermic reduction

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