CN105958036A - Preparation method for carbon-coated silicon negative electrode material for lithium ion battery - Google Patents

Preparation method for carbon-coated silicon negative electrode material for lithium ion battery Download PDF

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CN105958036A
CN105958036A CN201610527851.0A CN201610527851A CN105958036A CN 105958036 A CN105958036 A CN 105958036A CN 201610527851 A CN201610527851 A CN 201610527851A CN 105958036 A CN105958036 A CN 105958036A
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carbon
preparation
lithium ion
ion battery
coated
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陈永胜
随东
谢玉青
徐艳红
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Tianjin Pulan Nano Technology Co Ltd
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Tianjin Pulan Nano Technology Co Ltd
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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 invention provides a preparation method for a carbon-coated silicon negative electrode material for a lithium ion battery. The negative electrode material for the lithium ion battery with excellent performance is obtained from silicon powder by two times of carbon coating; the preparation method comprises the following steps of carrying out liquid phase dispersion on the silicon powder, then carrying out dispersion on the silicon powder, the first carbon coating layer and a dispersing agent; removing the solvent, and carrying out high-temperature carbonization treatment on the obtained solid material to obtain primary carbon-coated silicon negative electrode material; preparing a dispersion solution of a second carbon-coated material, dispersing the primary carbon-coated silicon material to the dispersion solution of the second carbon-coated material, and then removing the solvent and carrying out secondary roasting to obtain the secondary carbon-coated silicon negative electrode material. According to the preparation method, the raw materials are low in cost and easily available; the ratio of silicon to carbon can be optionally regulated and controlled; and the preparation method is simple in equipment, easy to implement the technological process, and suitable for scale production.

Description

A kind of preparation method of the carbon coated Si negative material of lithium ion battery
Technical field
The present invention relates to field of lithium ion battery material, be specifically related to the carbon coated Si of a kind of lithium ion battery The preparation method of negative material.
Background technology
Due to the development of electronic product, especially smart mobile phone and new-energy automobile, to lithium ion battery Energy density requires the highest, and the current lithium battery with material with carbon elements such as graphite as negative pole is because of energy density, Theoretical specific capacity only 375mAh/g, poor safety performance, far from meeting the demand that people increase day by day. Such as, current smart mobile phone was fast due to the many power consumptions of function, almost will fill once electricity every several hours, Trip and life for people bring a lot of inconvenience.Environmental problem and energy crisis promote various countries to send out energetically Exhibition new-energy automobile, but continual mileage is short, be short of power, dangerous and cost is high hampers newly always The development of energy automobile.Therefore, the lithium cell negative pole material of exploitation high-energy-density has far-reaching economic effect Benefit and social meaning.
Silicon is considered as most potential negative material, because silicon can form alloy cpd Li with lithiumxSi (0 < x≤4.4), i.e. one silicon can combine with most 4.4 lithiums, and specific capacity reaches as high as 4200mAh/g, It is more than 11 times of graphite cathode, and the intercalation potential of silicon is higher than the deposition potential of lithium, improves high power The safety of rate discharge and recharge.But, silicium cathode distance large-scale commercial application is the most far, traces it to its cause Mainly silicon materials change in volume during embedding de-lithium is very big, and up to 300%, huge body Long-pending change cause solid liquid interface film persistently rupture with formed again, electrolyte decomposition, cause active substance easy Between efflorescence, collector, electrical contact deteriorates, thus causes that capacity attenuation is fast, cycle performance is poor, and these are Silicium cathode problem demanding prompt solution；Additionally, it is well known that, silicon materials are quasiconductors, therefore its electric conductivity Not as graphite cathode, which has limited its high rate performance, if silicium cathode therefore can be solved in embedding de-lithium process Change in volume and the problem of electric conductivity, for the silicium cathode application paving in electronic product and new-energy automobile field Level line road, is beneficial to improve the life of people and environment.
Summary of the invention
The technical problem to be solved in the present invention be to provide to solve the technical problem that be to provide one can scale Metaplasia is produced, is improved silicium cathode material conductivity and circulative ion cathode material lithium and preparation method thereof.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is to provide a kind of lithium ion battery Carbon coated Si negative material, the clad on silicon power raw material surface is by the first carbon coating layer and the second carbon coating layer Composition, the first carbon coating layer is wrapped in the outside of silicon power raw material, and the second carbon coating layer is wrapped in the first carbon bag The outside of coating.
Its preparation method comprises the following steps:
1) in the silica flour that granular size is 1-100 μm, add solvent, disperse, continue 3-20h, First silica flour dispersion is made the silicon grain of nanorize, alleviates silicon materials greatly in charge and discharge process Change in volume；
2) adding in solvent by first carbon encapsulated material of 1-50wt%, the dispersant adding 0.2-5wt% enters Row dispersion, obtains the first carbon encapsulated material dispersion liquid；
3) by first carbon encapsulated material dispersion liquid add step 1) in proceed dispersion；
4) removing step 3) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min 500-1400 DEG C carries out carbonization treatment 1-20h, obtains primary carbon coated Si negative material；
5) second carbon encapsulated material of 0.1-10wt% is dispersed in solvent, disperses, obtain second Carbon encapsulated material dispersion liquid；
6) the second carbon encapsulated material dispersion liquid and primary carbon coated Si negative material are stirred mixing；
7) removing step 6) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min 500-1400 DEG C carries out carbonization treatment 1-20h, obtains secondary carbon coated Si negative material.
Wherein, described first carbon encapsulated material is graphite, sucrose, glucose, maltose, lactose, shallow lake Powder, formaldehyde, acetaldehyde, propionic aldehyde, phenolic resin, epoxy resin, Polyethylene Glycol, cellulose, lignin, In polyvinyl alcohol, polrvinyl chloride, polyethylene glycol oxide, polyurethane, poly-furfural, citric acid, cyclodextrin At least one；Preferably, described first carbon encapsulated material is in graphite, starch, sucrose, polyvinyl alcohol At least one, above-mentioned carbon encapsulated material is containing the organic molecule such as oxygen element, protium or polymer As clad, the material with carbon element of the porous formed after roasting is uniformly wrapped on nano-silicon surface, plays buffering Silicon materials are the effect of change in volume in discharge and recharge；Preferably, the weight of described first carbon encapsulated material is divided Number is 5-20%, and amount is coated with insufficient less, has measured the advantage not embodying silicon materials more.
Described second carbon encapsulated material be multi-layer graphene, single-layer graphene, graphene oxide, polypyrrole, Polythiophene, polyphenyl, polyacetylene, polyaniline, redox graphene at least one；Preferably, institute Stating the second carbon encapsulated material is multi-layer graphene, single-layer graphene, graphene oxide, reduction-oxidation graphite At least one in alkene, uses its derivant graphene-based as the second clad, the graphite of high-crystallinity The material with carbon element electric conductivity of alkene structure is high, and electrochemical stability is good, and beneficially high rate charge-discharge, circulation are surely Qualitative good；Preferably, the part by weight of the second carbon encapsulated material is 1-5%, both can guarantee that second time bag Cover completely, can guarantee that again electric conductivity.
Described dispersant is in polyvinyl alcohol, polyethylene glycol oxide, polyacrylic acid, LA132, LA135 Kind or multiple combination.
Wherein, described solvent be water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, third At least one in ketone, dimethylformamide, dimethyl sulfoxide, ethyl acetate, it is preferable that preparation process Described in solvent be at least one in water, ethanol, isopropanol, ethyl acetate, it is highly preferred that preparation During described solvent be water and ethanol.
Wherein it is preferred to, step 1) in the particle diameter of silica flour be 5-30 μm.
Wherein it is preferred to, step 1) in jitter time be 5-10h.
Wherein it is preferred to, the weight fraction of described dispersant is 0.5-2%, and dispersant major function is auxiliary Helping covering material and solvent to mix, content is low, mixes uneven, and content is high causes covering material Relative amount reduces.
Wherein, step 2) employed in process for dispersing be ultrasonic, stirring, one or several in ball milling Being used in conjunction of the method for kind.
Wherein, step 4) and step 7) in the used method removing solvent be vacuum drying, spray dried Being used in conjunction of one or more methods in dry, lyophilization, filtration drying, preferred method is for for spraying It is dried.
Wherein it is preferred to, the temperature that high temperature cabonization processes is 700-1200 DEG C, and temperature is the lowest, and carbonization is not Thoroughly；The highest, there is side reaction and waste the energy.
Wherein, high temperature cabonization heating rate is 5-10 DEG C/min, and this heating rate has taken into account efficiency and effect.
Wherein, the high temperature cabonization time is 3-10h.
Wherein, the atmosphere of high temperature cabonization is nitrogen, argon, nitrogen hydrogen mixed gas, the mixing of argon hydrogen One in gas, it is preferable that high temperature cabonization atmosphere is for nitrogen, argon hydrogen mixed gas, these atmosphere There is provided inert environments during carbonization, it is ensured that covering material is coated on silicon materials surface.
The present invention has the advantage that with good effect:
1, the technical process that the present invention uses is simple, and device therefor is all conventional disperse equipment, technique Easily realize, low cost；Silicon materials used are the silica flours of industrialization, low cost, cheap and easily-available, first by silicon The sphere of powder is milled into the silicon grain of nanorize, alleviates silicon materials volume in charge and discharge process greatly and becomes Change；
2, the method using twice carbon cladding, carbon cladding uses containing oxygen element, protium etc. for the first time Organic molecule or polymer are as clad, and the material with carbon element of the porous formed after roasting is uniformly wrapped on to be received Rice silicon face, plays buffering silicon materials effect of change in volume in discharge and recharge；Carbon cladding uses for the second time Its derivant graphene-based is as the second clad, the material with carbon element electric conductivity of the graphene-structured of high-crystallinity Height, electrochemical stability is good, beneficially high rate charge-discharge, good cycling stability.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the secondary carbon coated Si material of example 1.
Fig. 2 is the half-cell charging and discharging curve of the secondary carbon coated Si material of example 1.
Fig. 3 is the cyclic curve under different electric current densities of the secondary carbon coated Si material of example 2.
Fig. 4 is the charging and discharging curve under different electric current densities of the secondary carbon coated Si material of example 3.
Fig. 5 is the cycle charge-discharge curve of the secondary carbon coated Si material of example 2.
Fig. 6 is the cycle charge-discharge curve of the secondary carbon coated Si material of example 4.
Detailed description of the invention
Embodiment 1 one kinds is the first carbon coating layer with sucrose, and Graphene is the lithium ion of the second carbon coating layer The preparation method of battery silicium cathode material, its step includes:
1) silica flour that 80 gram particle footpaths are 8 μm is added in ball mill, add 160ml water, ball milling 6 Hour；
2) 20g sucrose and 5g polyvinyl alcohol are dissolved in 40ml water, obtain the first carbon coating layer solution；
3) by step 2) the first carbon coating layer solution add step 1) in, continue ball milling 2 hours, Obtain silicon grain and the dispersion liquid of the first carbon encapsulated material of nanorize；
4) it is spray-dried removing step 3) water of the dispersion liquid of the nano-silicon of gained and the first carbon encapsulated material Point, obtain solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 5 DEG C / min, maintains 5 hours at 900 DEG C, obtains primary carbon coated Si negative material；
6) by 0.85g graphene dispersion to 200ml water, the dispersion liquid of the second carbon encapsulated material is obtained；
7) by step 6) the dispersion liquid of the second carbon encapsulated material and step 5) the primary carbon cladding that obtains Silicium cathode material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 10 DEG C / min, maintains 2 hours at 700 DEG C, obtains secondary carbon coated Si negative material；
As shown in Figure 2, the silicon materials gram volume of secondary carbon cladding is high, and electric discharge first reaches near 1200mAh/g。
Embodiment 2
A kind of is the first carbon coating layer with graphite, and graphene oxide is that the lithium ion battery silicon of the second clad is born The preparation method of pole material, its step includes:
1) silica flour that 100 grams of D50 are 25 μm is added in ball mill, add 200ml water, ball milling 10 hours；
2) by 10g graphite and 1.1g polyacrylic acid ultrasonic disperse in 30ml water, the first carbon cladding is obtained Layer dispersion liquid；
3) by step 2) the first carbon coating layer dispersion liquid add step 1) in, continue ball milling 3 hours, The silicon grain obtaining nanorize is dispersed in the first carbon coating layer；
4) it is spray-dried removing step 3) moisture in gains, obtain solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 10 DEG C / min, maintains 3 hours at 700 DEG C, obtains primary carbon coated Si negative material；
6) 3.3g graphene oxide is distributed in 100ml water, obtains the solution of the second carbon encapsulated material；
7) by step 6) the solution of the second carbon encapsulated material and step 5) the primary carbon coated Si that obtains Negative material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process under an argon atmosphere, heating rate is 5 DEG C / min, maintains 3 hours at 850 DEG C, obtains secondary carbon coated Si negative material.
As seen from Figure 3, along with the increase of electric current density, gram volume decreases, but protects Holdup is the highest, Fig. 5 can absolutely prove that carbon cladding can improve the cyclical stability of silicon materials.
Embodiment 3
A kind of is the first carbon coating layer with starch, and multi-layer graphene is that the lithium ion battery silicon of the second clad is born The preparation method of pole material, its step includes:
1) silica flour that 60 grams of D50 are 15 μm is added in ball mill, add 150ml water, ball milling 7 Hour；
2) by 6g starch ultrasonic disperse in 50ml water, the first carbon coating layer dispersion liquid is obtained；
3) by step 2) starch dispersion liquid add step 1) in, continue ball milling 3 hours, received The silicon grain of riceization is dispersed in the first carbon coating layer solution；
4) it is spray-dried removing step 3) moisture in the nano-silicon of gained and the dispersion liquid of starch, obtain Solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 6 DEG C / min, maintains 5 hours at 850 DEG C, obtains primary carbon coated Si negative material；
6) 2g multi-layer graphene is distributed in 200ml water, obtains the dispersion liquid of the second carbon coating layer；
7) by step 6) the dispersion liquid of the second carbon coating layer and step 5) the primary carbon coated Si that obtains Negative material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 8 DEG C / min, maintains 3 hours at 800 DEG C, obtains secondary carbon coated Si negative material.
As shown in Figure 4, carbon cladding can improve the high rate performance of silicon materials.
Embodiment 4
A kind of is the first carbon coating layer with polyvinyl alcohol, and Graphene is the lithium ion battery silicon of the second carbon coating layer The preparation method of carbon negative pole material, its step includes:
1) silica flour that 100 grams of D50 are 8 μm is added in ball mill, add 150ml water, ball milling 4 Hour；
2) by 20g polyvinyl alcohol dispersed with stirring in 100ml water, the dispersion liquid of the first carbon coating layer is obtained；
3) by step 2) polyvinyl alcohol dispersion liquid add step 1) in, continue ball milling 2 hours, Silicon grain to nanorize is dispersed in the dispersion liquid of the first carbon coating layer；
4) it is spray-dried removing step 3) moisture in the nano-silicon of gained and polyvinyl alcohol dispersion liquid, To solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 6 DEG C / min, maintains 5 hours at 900 DEG C, obtains primary carbon coated Si negative material；
6) by 1.5g graphene dispersion to 300ml water, the dispersion liquid of the second carbon coating layer is obtained；
7) by step 6) the dispersion liquid of the second carbon coating layer and step 5) the primary carbon coated Si that obtains Negative material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid under hydrogen/argon mixed atmosphere, carry out high temperature cabonization process, heat up speed Rate is 10 DEG C/min, maintains 2 hours at 800 DEG C, obtains secondary carbon coated Si negative material. Can be absolutely proved that carbon cladding can improve the cyclical stability of silicon materials by Fig. 6.
Embodiment 5
A kind of is the first carbon coating layer with glucose, and redox graphene is the lithium ion of the second what is said or talked about clad The preparation method of battery silicon-carbon cathode material, its step includes:
1) silica flour that 100 grams of D50 are 20 μm is added in ball mill, add 200ml water, ball milling 8 hours；
2) it is dissolved in ultrasonic to 25g glucose and 1.5g polyacrylic acid in 50ml water, obtains the first carbon cladding Layer solution；
3) by step 2) the first carbon coating layer solution add step 1) in, continue ball milling 2.5 hours, The silicon grain obtaining nanorize is dispersed in the first carbon coating layer solution；
4) it is spray-dried removing step 3) moisture in gains, obtain solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 6 DEG C / min, maintains 6 hours at 850 DEG C, obtains primary carbon coated Si negative material；
6) 4g redox graphene is distributed in 100ml water, obtains dividing of the second carbon encapsulated material Dissipate liquid；
7) by step 6) the dispersion liquid of the second carbon encapsulated material and step 5) the primary carbon cladding that obtains Silicium cathode material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process under an argon atmosphere, heating rate is 5 DEG C / min, maintains 3 hours at 850 DEG C, obtains secondary carbon coated Si negative material
The secondary carbon coated Si negative material of embodiment 1-5 gained is carried out electrical property detection, key step Including:
1) the N-Methyl pyrrolidone solution of the Kynoar (PVDF) of 5% solid content is configured；
2) weigh a certain amount of secondary carbon coated Si negative material, conductive agent Super-P first grinds mixed Even, then the N-first class pyrrolidone solution dripping PVDF continues to be ground, and obtains slurry；Silicon-carbon Material, the part by weight of conductive agent Super-P and PVDF are 80:10:10；
3) slurry is coated on Copper Foil, and vacuum dried, roll-in, cut-parts, it is prepared as pole piece；
4) using lithium sheet as to electrode, barrier film is polyethylene, polypropylene composite materials barrier film, uses 1.2 mol/L LiPF6Three component mixed solvent EC/DMC/EMC (three solvent volume ratios are 1: 1: 1) molten Liquid is electrolyte, is assembled into button cell.Charging/discharging voltage is limited in 0.05～1.5V.
The amount adjusting glucose in embodiment 5 is 20g, 15g, 10g, repeats the process of step 1-9, system Standby different silicon and the silicon-carbon cathode material of glucose ratio.
Specific capacity under the different electric current densities of the secondary carbon coated Si material of table 1 example 5
From test result, along with the raising of glucose content, glucose is as the first clad Silicon materials gram volume is the lowest, but the capability retention under different electric current density is the highest.

Claims (13)

1. the preparation method of the carbon coated Si negative material of a lithium ion battery, it is characterised in that: bag Include following steps:
1) in the silica flour that granular size is 1-100 μm, add solvent to disperse, continue 3-20h；
2) first carbon encapsulated material of 1-50wt% is added in solvent, add the dispersant of 0.2-5wt% Disperse, obtain the first carbon encapsulated material dispersion liquid；
3) by first carbon encapsulated material dispersion liquid add step 1) in proceed dispersion；
4) removing step 3) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min 500-1400 DEG C carries out carbonization treatment 1-20h, obtains primary carbon coated Si negative material；
5) second carbon encapsulated material of 0.1-10wt% is dispersed in solvent, disperses, obtain second Carbon encapsulated material dispersion liquid；
6) the second carbon encapsulated material dispersion liquid and primary carbon coated Si negative material are stirred mixing；
7) removing step 6) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min 500-1400 DEG C carries out carbonization treatment 1-20h, obtains secondary carbon coated Si negative material.
Wherein, described first carbon encapsulated material is graphite, sucrose, glucose, maltose, lactose, shallow lake Powder, formaldehyde, acetaldehyde, propionic aldehyde, phenolic resin, epoxy resin, Polyethylene Glycol, cellulose, lignin, In polyvinyl alcohol, polrvinyl chloride, polyethylene glycol oxide, polyurethane, poly-furfural, citric acid, cyclodextrin At least one；
Described second carbon encapsulated material be multi-layer graphene, single-layer graphene, graphene oxide, polypyrrole, Polythiophene, polyphenyl, polyacetylene, polyaniline, redox graphene at least one；
Described dispersant is in polyvinyl alcohol, polyethylene glycol oxide, polyacrylic acid, LA132, LA135 Kind or multiple combination.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: the clad on silicon power raw material surface is made up of the first carbon coating layer and the second carbon coating layer, First carbon coating layer is wrapped in the outside of silicon power raw material, and the second carbon coating layer is wrapped in the first carbon coating layer Outside.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: described solvent be water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, At least one in acetone, dimethylformamide, dimethyl sulfoxide, ethyl acetate.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: step 1) in jitter time be 5-10h.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: preferably, described first carbon encapsulated material is graphite, starch, sucrose, polyvinyl alcohol In at least one, the weight fraction of described first carbon encapsulated material is 5-20%.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: preferably, the weight fraction of described dispersant is 0.5-2%.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: step 2) employed in process for dispersing be ultrasonic, stirring, one in ball milling or Being used in conjunction of several method.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: preferably, described second carbon encapsulated material is multi-layer graphene, single-layer graphene, oxygen At least one in functionalized graphene, redox graphene, the part by weight of described second carbon encapsulated material For 1-5%.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1, It is characterized in that: step 4) and step 7) in the used method removing solvent be vacuum drying, spraying Be dried, lyophilization, being used in conjunction of one or more methods in filtration drying.
The preparation side of the carbon coated Si negative material of lithium ion battery the most according to claim 1 Method, it is characterised in that: preferably, the temperature that high temperature cabonization processes is 700-1200 DEG C.
The preparation method of the carbon coated Si negative material of 11. lithium ion batteries according to claim 1, It is characterized in that: preferably, high temperature cabonization heating rate is 5-10 DEG C/min.
The preparation method of the carbon coated Si negative material of 12. lithium ion batteries according to claim 1, It is characterized in that: preferably, the high temperature cabonization time is 3-10h.
The preparation method of the carbon coated Si negative material of 13. lithium ion batteries according to claim 1, It is characterized in that: the atmosphere of high temperature cabonization be nitrogen, argon, nitrogen hydrogen mixed gas, argon hydrogen mix Close the one in gas.
CN201610527851.0A 2016-07-07 2016-07-07 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery Pending CN105958036A (en)

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CN107565109A (en) * 2017-08-23 2018-01-09 山东精工电子科技有限公司 A kind of lithium-ion battery silicon-carbon anode material of high stable and preparation method thereof
CN108149343A (en) * 2017-12-12 2018-06-12 东华大学 The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation
CN108417782A (en) * 2017-02-09 2018-08-17 韩国地质资源研究院 The method for manufacturing silico-carbo-graphene synthetic, the synthetic manufactured by the manufacturing method and the accumulator for applying the synthetic
CN108470891A (en) * 2018-03-16 2018-08-31 四川大学 The method for preparing silicon-carbon cathode material based on micron silica
CN108511734A (en) * 2018-05-18 2018-09-07 深圳市优特利电源有限公司 The preparation method of Si-C composite material
CN109378456A (en) * 2018-10-15 2019-02-22 陕西煤业化工技术研究院有限责任公司 A kind of high-capacity cathode material and its preparation method and application
CN109449423A (en) * 2018-11-13 2019-03-08 东莞市凯金新能源科技股份有限公司 Hollow/porous structure the silicon based composite material of one kind and its preparation method
CN109524643A (en) * 2018-11-01 2019-03-26 贵州梅岭电源有限公司 A kind of preparation method and applications of multilayer carbon shell core-shell structure silicon based anode material
CN109599551A (en) * 2018-12-28 2019-04-09 安普瑞斯（南京）有限公司 A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery
CN109742372A (en) * 2019-01-15 2019-05-10 北京交通大学 A method of preparing high performance lithium ion battery silicon-carbon cathode composite material
CN110021749A (en) * 2019-04-26 2019-07-16 蜂巢能源科技有限公司 Silicon-carbon cathode material and preparation method thereof, battery
CN110085850A (en) * 2019-05-20 2019-08-02 深圳市斯诺实业发展有限公司 A kind of preparation method of the carbon-coated Si-C composite material of multilayer
CN110289412A (en) * 2019-07-25 2019-09-27 银隆新能源股份有限公司 Si-C composite material and the preparation method and application thereof
CN110690433A (en) * 2019-10-16 2020-01-14 北京卫蓝新能源科技有限公司 Silicon-based negative electrode material for lithium ion battery and preparation method thereof
CN110767892A (en) * 2019-11-04 2020-02-07 北京卫蓝新能源科技有限公司 Preparation method of silicon-carbon material of lithium ion battery
CN111048759A (en) * 2019-12-18 2020-04-21 昆山宝创新能源科技有限公司 Negative active material for lithium battery, and preparation method and application thereof
CN111180729A (en) * 2019-12-31 2020-05-19 宁波杉元石墨烯科技有限公司 Silicon-based negative electrode material adopting different graphene for multiple coating
CN111170364A (en) * 2019-12-30 2020-05-19 北方奥钛纳米技术有限公司 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery
CN111342010A (en) * 2020-03-02 2020-06-26 新奥石墨烯技术有限公司 Silicon-carbon composite material with double-layer carbon-coated structure and preparation method and application thereof
CN111416110A (en) * 2020-04-02 2020-07-14 上海电气集团股份有限公司 Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof
CN111517317A (en) * 2020-01-21 2020-08-11 西安隆基锂电新材料有限公司 Silicon-carbon composite negative electrode material and preparation method thereof
CN111525115A (en) * 2020-05-11 2020-08-11 福州大学 Etched nano-silicon double-layer carbon-coated lithium ion battery negative electrode material, negative electrode plate and preparation method of negative electrode plate
CN111540896A (en) * 2020-05-07 2020-08-14 七台河万锂泰电材有限公司 Preparation method of silicon-carbon composite negative electrode material
CN111584233A (en) * 2020-06-08 2020-08-25 江苏国瓷泓源光电科技有限公司 Multilayer ceramic capacitor copper electrode slurry
CN112002888A (en) * 2020-08-26 2020-11-27 成都新柯力化工科技有限公司 Method for preparing lithium battery silicon-carbon cathode by using screw extruder
EP3817100A4 (en) * 2018-08-23 2021-10-20 Lg Chem, Ltd. Anode active material, anode comprising same, and lithium secondary battery
CN113998701A (en) * 2021-11-05 2022-02-01 北京清研华创新能源科技有限公司 Silicon-carbon negative electrode material and preparation method thereof
CN114171722A (en) * 2020-09-11 2022-03-11 北京清创硅谷科技有限公司 Preparation method of silicon-carbon composite material
CN114400310A (en) * 2022-01-14 2022-04-26 中国科学院宁波材料技术与工程研究所 High-first-efficiency graphene composite silicon-carbon negative electrode material, preparation method thereof and battery
CN114520314A (en) * 2020-11-19 2022-05-20 湖南中科星城石墨有限公司 Negative electrode material with porous carbon coating layer, preparation method of negative electrode material and lithium ion battery
CN115295785A (en) * 2022-08-23 2022-11-04 广东比沃新能源有限公司 Nano silicon-carbon composite electrode material and lithium battery thereof

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CN106784765A (en) * 2016-12-15 2017-05-31 电子科技大学 Graphene enhancing Si-C composite material and its production and use
CN108417782B (en) * 2017-02-09 2021-03-02 韩国地质资源研究院 Method of making silicon-carbon-graphene compositions
CN108417782A (en) * 2017-02-09 2018-08-17 韩国地质资源研究院 The method for manufacturing silico-carbo-graphene synthetic, the synthetic manufactured by the manufacturing method and the accumulator for applying the synthetic
CN107565109A (en) * 2017-08-23 2018-01-09 山东精工电子科技有限公司 A kind of lithium-ion battery silicon-carbon anode material of high stable and preparation method thereof
CN107565109B (en) * 2017-08-23 2019-10-18 山东精工电子科技有限公司 A kind of lithium-ion battery silicon-carbon anode material of high stable and preparation method thereof
CN108149343A (en) * 2017-12-12 2018-06-12 东华大学 The composite nano fiber of N doping porous carbon cladding nano silicon particles and preparation
CN108149343B (en) * 2017-12-12 2019-12-10 东华大学 Composite nanofiber with silicon nanoparticles coated with nitrogen-doped porous carbon and preparation method thereof
CN108470891A (en) * 2018-03-16 2018-08-31 四川大学 The method for preparing silicon-carbon cathode material based on micron silica
CN108470891B (en) * 2018-03-16 2020-12-15 四川大学 Method for preparing silicon-carbon negative electrode material based on micron silicon dioxide
CN108511734A (en) * 2018-05-18 2018-09-07 深圳市优特利电源有限公司 The preparation method of Si-C composite material
EP3817100A4 (en) * 2018-08-23 2021-10-20 Lg Chem, Ltd. Anode active material, anode comprising same, and lithium secondary battery
CN109378456A (en) * 2018-10-15 2019-02-22 陕西煤业化工技术研究院有限责任公司 A kind of high-capacity cathode material and its preparation method and application
CN109524643A (en) * 2018-11-01 2019-03-26 贵州梅岭电源有限公司 A kind of preparation method and applications of multilayer carbon shell core-shell structure silicon based anode material
CN109524643B (en) * 2018-11-01 2021-05-07 贵州梅岭电源有限公司 Preparation method and application of silicon-based negative electrode material with multilayer carbon shell core-shell structure
CN109449423A (en) * 2018-11-13 2019-03-08 东莞市凯金新能源科技股份有限公司 Hollow/porous structure the silicon based composite material of one kind and its preparation method
CN109599551A (en) * 2018-12-28 2019-04-09 安普瑞斯（南京）有限公司 A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery
CN109742372A (en) * 2019-01-15 2019-05-10 北京交通大学 A method of preparing high performance lithium ion battery silicon-carbon cathode composite material
CN110021749A (en) * 2019-04-26 2019-07-16 蜂巢能源科技有限公司 Silicon-carbon cathode material and preparation method thereof, battery
CN110085850A (en) * 2019-05-20 2019-08-02 深圳市斯诺实业发展有限公司 A kind of preparation method of the carbon-coated Si-C composite material of multilayer
CN110289412A (en) * 2019-07-25 2019-09-27 银隆新能源股份有限公司 Si-C composite material and the preparation method and application thereof
CN110690433A (en) * 2019-10-16 2020-01-14 北京卫蓝新能源科技有限公司 Silicon-based negative electrode material for lithium ion battery and preparation method thereof
CN110690433B (en) * 2019-10-16 2021-08-17 北京卫蓝新能源科技有限公司 Silicon-based negative electrode material for lithium ion battery and preparation method thereof
CN110767892A (en) * 2019-11-04 2020-02-07 北京卫蓝新能源科技有限公司 Preparation method of silicon-carbon material of lithium ion battery
CN111048759A (en) * 2019-12-18 2020-04-21 昆山宝创新能源科技有限公司 Negative active material for lithium battery, and preparation method and application thereof
CN111170364A (en) * 2019-12-30 2020-05-19 北方奥钛纳米技术有限公司 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery
CN111180729A (en) * 2019-12-31 2020-05-19 宁波杉元石墨烯科技有限公司 Silicon-based negative electrode material adopting different graphene for multiple coating
CN111517317A (en) * 2020-01-21 2020-08-11 西安隆基锂电新材料有限公司 Silicon-carbon composite negative electrode material and preparation method thereof
CN111517317B (en) * 2020-01-21 2023-02-17 西安隆基锂电新材料有限公司 Silicon-carbon composite negative electrode material and preparation method thereof
CN111342010B (en) * 2020-03-02 2021-09-10 新奥石墨烯技术有限公司 Silicon-carbon composite material with double-layer carbon-coated structure and preparation method and application thereof
CN111342010A (en) * 2020-03-02 2020-06-26 新奥石墨烯技术有限公司 Silicon-carbon composite material with double-layer carbon-coated structure and preparation method and application thereof
CN111416110A (en) * 2020-04-02 2020-07-14 上海电气集团股份有限公司 Graphene modified pre-lithiated silicon negative electrode material and preparation method thereof
CN111540896A (en) * 2020-05-07 2020-08-14 七台河万锂泰电材有限公司 Preparation method of silicon-carbon composite negative electrode material
CN111525115A (en) * 2020-05-11 2020-08-11 福州大学 Etched nano-silicon double-layer carbon-coated lithium ion battery negative electrode material, negative electrode plate and preparation method of negative electrode plate
CN111584233B (en) * 2020-06-08 2022-03-18 江苏国瓷泓源光电科技有限公司 Multilayer ceramic capacitor copper electrode slurry
CN111584233A (en) * 2020-06-08 2020-08-25 江苏国瓷泓源光电科技有限公司 Multilayer ceramic capacitor copper electrode slurry
CN112002888A (en) * 2020-08-26 2020-11-27 成都新柯力化工科技有限公司 Method for preparing lithium battery silicon-carbon cathode by using screw extruder
CN114171722A (en) * 2020-09-11 2022-03-11 北京清创硅谷科技有限公司 Preparation method of silicon-carbon composite material
CN114520314A (en) * 2020-11-19 2022-05-20 湖南中科星城石墨有限公司 Negative electrode material with porous carbon coating layer, preparation method of negative electrode material and lithium ion battery
CN114520314B (en) * 2020-11-19 2024-02-27 湖南中科星城石墨有限公司 Negative electrode material with porous carbon coating layer, preparation method thereof and lithium ion battery
CN113998701A (en) * 2021-11-05 2022-02-01 北京清研华创新能源科技有限公司 Silicon-carbon negative electrode material and preparation method thereof
CN114400310A (en) * 2022-01-14 2022-04-26 中国科学院宁波材料技术与工程研究所 High-first-efficiency graphene composite silicon-carbon negative electrode material, preparation method thereof and battery
CN115295785A (en) * 2022-08-23 2022-11-04 广东比沃新能源有限公司 Nano silicon-carbon composite electrode material and lithium battery thereof

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Application publication date: 20160921