CN110085820A - A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary - Google Patents

A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary Download PDF

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Publication number
CN110085820A
CN110085820A CN201910308545.1A CN201910308545A CN110085820A CN 110085820 A CN110085820 A CN 110085820A CN 201910308545 A CN201910308545 A CN 201910308545A CN 110085820 A CN110085820 A CN 110085820A
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graphene
metal oxide
silicon
supercritical fluid
cathode material
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齐新
燕绍九
陈翔
王继贤
王楠
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AECC Beijing Institute of Aeronautical Materials
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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
    • 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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 methods of porous graphene silicium cathode material based on supercritical fluid auxiliary, aiming at the problem that expansion of current silicium cathode material volume seriously causes structure collapses to cause energy rapid decay, the present invention utilizes the low-viscosity of supercritical fluid, high diffusibility, zero surface tension and it is easy to the characteristics of regulating and controlling, by metal oxide precursor uniform load in chemically inert graphene surface, by metal oxide-graphene composite material coated Si material surface, metal oxide is etched away with acid solution again, porous graphene silicium cathode material is obtained using carbon-thermal reduction principle.Wherein, the good electric conductivity and porous structure of high-quality graphene are conducive to the quick transmission of electronics and lithium ion, a variety of hole graphene-structureds can be obtained in regulation heating treatment time and temperature, can the condition according to needed for practical negative electrode material be adjusted flexibly, and the metal oxide etched away reserves cushion space, alleviating series of negative caused by silicon materials volume expansion influences.

Description

A kind of preparation of the porous graphene silicium cathode material based on supercritical fluid auxiliary Method
Technical field
The invention belongs to lithium ion battery negative material fields, and in particular to a kind of based on the porous of supercritical fluid auxiliary The preparation method of graphene silicium cathode material, and the lithium ion battery using the negative electrode material.
Background technique
Silicon materials have high theoretical specific capacity (> 3000mA h g-1) as lithium cell cathode material, are expected to become Substitute the negative electrode material of new generation of the lower graphite type material of lithium storage content.But silicon volume expansion in charge and discharge process is serious (about 4 times) cause mutual extrusion between particle to lead to structure collapses, and silicon materials are easy to fall off from collector, therefore cause electricity The quick energy attenuation in pond, this problem limit the application of silicium cathode material.
Graphene, a kind of carbon material of two dimension sp2 hydridization, is the material of current most study.It is monoatomic layer thickness Carbon atom arrangement at honeycomb, become most thin in the world, most firmly, most tough material, and be heat and electricity excellence conductor.It will After graphene and silicon materials are compound, graphene flexible can provide cushion space, alleviate material powder caused by silicon volume expansion Broken phenomenon；Graphene also can avoid the reunion again of silicon, and electrolyte is avoided directly to contact with silicon particle；The superelevation of graphene is conductive Property, also it is conducive to the transmission and electronics transfer of lithium ion in system.Moreover, the porous structure of graphene is the transmission of lithium ion Channel is constructed, the advantage of silicon materials can be more effectively played.By the compound of porous graphene and silicon materials, can play While the advantage of the two alleviate there are the problem of, reach synergistic effect.
Since high-quality graphene surface is chemical inertness, lack the active site of hybrid material growth, it is difficult in Gao Pin Matter graphene surface grows other hybrid materials, thus using graphene surface growth oxide again etching processing as major programme The technology of preparing of existing porous graphene silicium cathode material mostly uses and grows metallic oxide precursor in surface of graphene oxide After body, then electronation or thermal reduction processing are carried out to graphene oxide.Main method is negative in redox graphene surface Carry metal oxide, then it is carried out reduction and etching processing, this method the destruction for being difficult to make up is caused to the structure of graphene, It is and lower using extremely toxic substances, yields such as a large amount of soda acids during the preparation process, it is difficult to large-scale production.In addition to this, it also uses The modes such as plasma sputtering, microwave method, ultrasonic treatment, gas etching, but these technologies involve great expense mostly, poor controllability and difficulty With scale application.
Summary of the invention
The purpose of the present invention is: the present invention is using the low-viscosity of supercritical fluid, high diffusibility, zero surface tension and is easy to The characteristics of regulation, by metal oxide precursor uniform load in chemically inert graphene surface.This method is directly in Gao Pin Matter graphene surface grows metal oxide, overcomes high-quality graphene surface and is difficult to grow the technical problem of hybrid material, Will not cause obvious destructiveness to the structure of graphene, keep the excellent properties of graphene itself, can to graphene hole into Row controllable adjustment prepares hole configurations of corresponding size according to practical application, and environment friendliness is high in manufacturing process, at This is low and is easy to prepare with scale.And the good electric conductivity and porous structure of high-quality graphene are conducive to electronics and lithium ion Quickly transmission, regulates and controls heating treatment time and a variety of hole graphene-structureds can be obtained in temperature, can be according to practical negative electrode material institute The metal oxide for needing condition to be adjusted flexibly, and etching away reserves cushion space, alleviates a system caused by silicon materials volume expansion Column negative effect.The present invention have mass, quickly, efficient advantages such as preparation, and have both safety, the feature of environmental protection, low energy consumption etc. Feature, is readily produced and cost is relatively low.
The technical scheme is that
A kind of preparation method of porous graphene silicium cathode material based on supercritical fluid auxiliary is provided, including is walked as follows It is rapid:
Step 1, using graphene and metallic compound as raw material, the two is placed in closed pressure vessel, in pressure vessel Filled with CO2Gas carries out high-pressure bottle to heat and keep certain pressure condition, so that the CO in container2Gas becomes super and faces Boundary's fluid, heating while, are uniformly mixed graphene, metallic compound and supercritical fluid, later drop pressure vessel After temperature to environment temperature (such as room temperature), CO is discharged2Gas obtains metallic compound-graphene composite material；Metallic compound-stone Black alkene composite material is to be attached with metallic compound on graphene film surface；
Step 2, heated metallic compound-graphene composite material to obtain metal oxide-graphene it is multiple Condensation material；
Metal oxide-graphene composite material is carried out cladding processing to silicon materials by step 3, obtains metal oxide- Graphene-silicon composite；(grapheme material coated Si material granule, is able to suppress silicon volume expansion band in charge and discharge process The negative effect come)
Metal oxide-graphene-silicon composite is carried out acid etch processing by step 4, and metal oxide is etched Fall, obtain porous graphene-silicon composite, the porous graphene-silicon composite is lithium ion battery negative material.
Further, silicon materials include at least one of silicon, the sub- silicon of oxidation, silicon carbide and silicon nitride.
Further, the temperature heated in step 1 is 30~200 DEG C, and pressure is maintained at 5~15MPa.Preferably, Heating and uniformly mixed processing time are 0.5~5 hour.
Further, concentration sour used in step 4 is 0.1~1mol, and etch period is 0.5~12 hour.
Further, in metal oxide-graphene composite material obtained in step 2, metal oxide is compound at this 10~80%wt is accounted in material, the metal oxide particle size in metal oxide-graphene composite material be 10~ 100nm。
Further, the temperature heated in step 2 is 400~700 DEG C, and preferably heating treatment time is 0.5~2 small When.
Further, the processing step of processing is coated in step 3 are as follows: by silicon materials and surfactant-dispersed in solvent It is ultrasonically treated, obtains silicon dispersion liquid；It again disperses metal oxide-graphene composite material in solvent and carries out at ultrasound Reason, obtains metal oxide-graphene dispersing solution；Silicon dispersion liquid is added dropwise to the metal oxide-graphite being vigorously stirred In alkene dispersion liquid, suction filtration obtains metal oxide-graphene-silicon composite.Preferably, the surfactant is hexadecane One of base trimethylammonium bromide, polyvinylpyrrolidone, polyethylene glycol or polyvinyl alcohol or at least two combination.It is preferred that Ground, it is 1~100mm/min that rate, which is added dropwise, in the silicon dispersion liquid, and metal oxide-graphene dispersing solution speed of agitator is 100~2000r/min.Preferably, the solvent is ethyl alcohol, methanol, acetone, isopropanol, n,N-Dimethylformamide or N- first One of base pyrrolidones or at least two combination and water mixed solution.
The invention has the advantages that this method is using the low-viscosity of supercritical fluid, high diffusibility, zero surface tension and is easy to The characteristics of regulation, by metal oxide precursor uniform load in chemically inert graphene surface, make high-quality graphene with Metal oxide is combined closely；Controllable growth is carried out to the size of metal oxide, stone in traditional preparation methods can also be avoided The irreversible breaking of black alkene structure, graphene of the invention structural regularity still with higher.
Specific embodiment
The present invention is described in further details below with reference to embodiment.
Embodiment 1
1g graphene and 10g nitric hydrate copper are added in 100mL methanol, ultrasonic 1h forms uniform mixed solution. Then, mixed solution is sealed in stainless steel autoclave, and is 30 DEG C by the temperature setting of autoclave, to height after temperature is stable CO is filled in pressure kettle2, pressure in kettle is made to reach 7MPa.Stirring is opened, being to slowly warm up to 150 DEG C makes system reach supercritical state State.It reacts and is cooled to room temperature autoclave after continuing 2h, then slow release CO2, product ethyl alcohol and aqueous solution are taken out respectively Filter washing is dried afterwards for several times.Place the product in being heated in Muffle furnace, 600 DEG C keep the temperature 2 hours, obtain copper oxide-stone Black alkene composite material.Disperse 1g copper oxide-graphene composite material in 500mL water and alcohol mixed solution (proportion is 5: 1), 1g silicon materials and CTAB are scattered in same 500mL water and alcohol mixed solution, carry out ultrasonic treatment respectively 30 minutes, Silicon materials dispersion liquid is slowly added dropwise in the graphene solution in being vigorously stirred, after carrying out suction filtration drying, obtains copper oxide-stone Black alkene-silicon composite.Copper oxide-graphene-silicon composite is soaked in dilute hydrochloric acid, is slowly stirred 6 hours, stands and divides Supernatant liquid is removed after layer, is carried out filtering and washing 3 times with deionized water, porous graphene silicium cathode material is obtained after drying.
Embodiment 2
1.4g graphene microchip and 15g nitric hydrate iron are added in 100mL ethyl alcohol, ultrasonic 1h forms uniform mixing Solution.Then, mixed solution is sealed in stainless steel autoclave, and is 40 DEG C by the temperature setting of autoclave, temperature is stablized CO is filled in backward autoclave2, pressure in kettle is made to reach 6.5MPa.Stirring is opened, being to slowly warm up to 120 DEG C makes system reach super Critical state.It reacts and is cooled to room temperature autoclave after continuing 3h, then slow release CO2, by product ethyl alcohol and aqueous solution Filtering and washing is dried afterwards for several times respectively.Place the product in being heated in Muffle furnace, 500 DEG C keep the temperature 1 hour, are aoxidized Iron-graphite alkene composite material.(proportion is dispersed in 500mL water and alcohol mixed solution by 5g iron oxide-graphene composite material For 5:1), 4g silicon materials and CTAB are scattered in same 500mL water and alcohol mixed solution, carry out 30 points of ultrasonic treatment respectively Silicon materials dispersion liquid is slowly added dropwise in the graphene solution in being vigorously stirred, after carrying out suction filtration drying, is aoxidized by clock Iron-graphite alkene-silicon composite.Iron oxide-graphene-silicon composite is soaked in dilute hydrochloric acid, is slowly stirred 6 hours, Supernatant liquid is removed after stratification, is carried out filtering and washing 3 times with deionized water, porous graphene silicium cathode material is obtained after drying Material.
Embodiment 3
2.1g is heat-treated into graphene oxide and 16.5g nickel chloride is added in 150mL acetone, ultrasonic 1h forms uniform Mixed solution.Then, mixed solution is sealed in stainless steel autoclave, and is 40 DEG C by the temperature setting of autoclave, temperature CO is filled with after stabilization into autoclave2, pressure in kettle is made to reach 6.5MPa.Stirring is opened, being to slowly warm up to 160 DEG C reaches system To supercriticality.It reacts and is cooled to room temperature autoclave after continuing 2h, then slow release CO2, by product second alcohol and water Solution distinguishes filtering and washing dries afterwards for several times.Place the product in being heated in Muffle furnace, 600 DEG C keep the temperature 1 hour, obtain Iron oxide-graphene composite material.It disperses 3g nickel oxide-graphene composite material in 500mL water and alcohol mixed solution (proportion is 5:1), 1.5g silicon materials and CTAB are scattered in same 500mL water and alcohol mixed solution, carry out ultrasound respectively Processing 30 minutes, silicon materials dispersion liquid is slowly added dropwise in the graphene solution in being vigorously stirred, after carrying out suction filtration drying, is obtained To nickel oxide-graphene-silicon composite.Nickel oxide-graphene-silicon composite is soaked in dilute hydrochloric acid, is slowly stirred 6 Hour, supernatant liquid is removed after stratification, is carried out filtering and washing 3 times with deionized water, porous graphene silicon is obtained after drying Negative electrode material.
Embodiment 4
3.1g high-quality graphene and 20.5g manganese chloride are added in 150mL ethyl alcohol, ultrasonic 1h forms uniform mixing Solution.Then, mixed solution is sealed in stainless steel autoclave, and is 30 DEG C by the temperature setting of autoclave, temperature is stablized CO is filled in backward autoclave2, pressure in kettle is made to reach 5MPa.Stirring is opened, is to slowly warm up to 160 DEG C system is made to reach super to face Boundary's state.It reacts and is cooled to room temperature autoclave after continuing 2h, then slow release CO2, by product ethyl alcohol and aqueous solution point Other filtering and washing is dried afterwards for several times.Place the product in being heated in Muffle furnace, 600 DEG C keep the temperature 1 hour, are aoxidized Iron-graphite alkene composite material.It disperses 10g manganese oxide-graphene composite material in 1000mL water and isopropyl alcohol mixture (proportion is 4:1), 10g silicon materials and PVA are scattered in same 1000mL water and isopropyl alcohol mixture, carry out ultrasound respectively Processing 60 minutes, silicon materials dispersion liquid is slowly added dropwise in the graphene solution in being vigorously stirred, after carrying out suction filtration drying, is obtained To manganese oxide-graphene-silicon composite.Manganese oxide-graphene-silicon composite is soaked in dilute hydrochloric acid, is slowly stirred 5 Hour, supernatant liquid is removed after stratification, is carried out filtering and washing 3 times with deionized water, porous graphene silicon is obtained after drying Negative electrode material.

Claims (10)

1. a kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary, which is characterized in that including Following steps:
Step 1, using graphene and metallic compound as raw material, the two is placed in closed pressure vessel, in pressure vessel filled with CO2Gas carries out high-pressure bottle to heat and keep certain pressure condition, so that the CO in container2Gas becomes shooting flow Body, heating while, are uniformly mixed graphene, metallic compound and supercritical fluid, are later cooled to pressure vessel After environment temperature (such as room temperature), CO is discharged2Gas obtains metallic compound-graphene composite material；Metallic compound-graphene Composite material is to be attached with metallic compound on graphene film surface；
Step 2 is heated metallic compound-graphene composite material to obtain metal oxide-graphene composite wood Material；
Metal oxide-graphene composite material is carried out cladding processing to silicon materials by step 3, obtains metal oxide-graphite Alkene-silicon composite；
Metal oxide-graphene-silicon composite is carried out acid etch processing by step 4, and metal oxide is etched away, is obtained To porous graphene-silicon composite, the porous graphene-silicon composite is lithium ion battery negative material.
2. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as described in claim 1 Method, it is characterised in that: the temperature heated in step 1 is 30~200 DEG C, and pressure is maintained at 5~15MPa.
3. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as described in claim 1 Method, it is characterised in that: silicon materials include at least one of silicon, the sub- silicon of oxidation, silicon carbide and silicon nitride.
4. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as claimed in claim 2 Method, it is characterised in that: heat and the uniformly mixed processing time is 0.5~5 hour.
5. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as described in claim 1 Method, it is characterised in that: sour concentration used in step 4 is 0.1~1mol, and etch period is 0.5~12 hour.
6. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as described in claim 1 Method, it is characterised in that: in metal oxide-graphene composite material obtained in step 2, metal oxide is in the composite material In account for 10~80%wt, the metal oxide particle size in metal oxide-graphene composite material be 10~100nm.
7. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as described in claim 1 Method, it is characterised in that: the processing step of processing is coated in step 3 are as follows: by silicon materials and surfactant-dispersed in solvent into Row ultrasonic treatment, obtains silicon dispersion liquid；It again disperses metal oxide-graphene composite material in solvent and carries out at ultrasound Reason, obtains metal oxide-graphene dispersing solution；Silicon dispersion liquid is added dropwise to the metal oxide-graphite being vigorously stirred In alkene dispersion liquid, suction filtration obtains metal oxide-graphene-silicon composite.
8. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as claimed in claim 7 Method, it is characterised in that: the surfactant be cetyl trimethylammonium bromide, polyvinylpyrrolidone, polyethylene glycol or One of polyvinyl alcohol or at least two combination.
9. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as described in claim 1 Method, it is characterised in that: the temperature heated in step 2 is 400~700 DEG C.
10. a kind of preparation side of porous graphene silicium cathode material based on supercritical fluid auxiliary as claimed in claim 9 Method, it is characterised in that: heating treatment time is 0.5~2 hour in step 2.
CN201910308545.1A 2019-04-17 2019-04-17 A kind of preparation method of the porous graphene silicium cathode material based on supercritical fluid auxiliary Pending CN110085820A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110474040A (en) * 2019-09-05 2019-11-19 中国科学院过程工程研究所 A kind of negative electrode material, and its preparation method and application

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CN107069038A (en) * 2017-04-24 2017-08-18 广东烛光新能源科技有限公司 A kind of silicon-carbon cathode material and preparation method thereof
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CN107069038A (en) * 2017-04-24 2017-08-18 广东烛光新能源科技有限公司 A kind of silicon-carbon cathode material and preparation method thereof
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* Cited by examiner, † Cited by third party
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CN110474040A (en) * 2019-09-05 2019-11-19 中国科学院过程工程研究所 A kind of negative electrode material, and its preparation method and application

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Application publication date: 20190802