CN103943833A - Microwave preparation method of sulfur loaded graphene as electrode material of lithium battery - Google Patents

Microwave preparation method of sulfur loaded graphene as electrode material of lithium battery Download PDF

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CN103943833A
CN103943833A CN201410110694.4A CN201410110694A CN103943833A CN 103943833 A CN103943833 A CN 103943833A CN 201410110694 A CN201410110694 A CN 201410110694A CN 103943833 A CN103943833 A CN 103943833A
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graphene
electrode material
sulphur
black
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CN103943833B (en
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王勇
肖索
郭蕾
孔少锋
金菲英
郭文翔
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University of Shanghai for Science and Technology
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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
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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 discloses a microwave preparation method of sulfur loaded graphene as an electrode material of a lithium battery. The method comprises the following steps: taking sublimed sulfur and natural graphite powder as the raw materials, preparing graphene oxides through a chemical oxidation stripping method, preparing graphene through a microwave method, mechanically dispersing the graphene to prepare electrode slurry, and finally drying the electrode slurry in vacuum so as to obtain a composite electrode material. The key point of the method is that a microwave method is adopted to prepare graphene, and then mechanical dispersion is carried out to evenly mix sublimed sulfur and the prepared graphene so as to load the sulfur onto the graphene. Electrochemical test results have shown that the composite electrode material namely the novel sulfur loaded graphene has the advantages of high relative specific capacity, good circulation stability, and positional for commercialization.

Description

A kind of microwave is prepared the preparation method of the electrode material of lithium battery of graphene-supported sulphur
Technical field
The present invention relates to a kind of microwave and prepare the preparation method of the electrode material of lithium battery of graphene-supported sulphur, its preparation process includes chemical oxidation stripping method, mechanical dispersion method and microwave heating method; Specifically, prepare by chemical oxidation stripping method exactly that graphene oxide, microwave method thermal reduction are prepared Graphene, mechanical dispersion method is prepared electrode material slurries, is finally dried by vacuum drying chamber the combination electrode material that obtains graphene-supported sulphur.The invention belongs to lithium-ion-power cell electrode material preparing technical field.
Background technology
Graphene (Graphene nanosheets, GNS) be within 2004, find can stable existence Two-dimensional Carbon material, it has very high specific area, conductivity and thermal stability.Simultaneously Graphene is also a kind of material that can be used for solid sulphur.Graphene prepared by microwave method because of it has can be compound with sulphur compared with the functional group of large specific area and remained on surface, in solid sulphur, can also increase the conductivity of sulphur, be the only selection of lithium-sulfur cell.Microwave method compared with other thermal reduction, the many merits such as the speed that responds is fast, energy-conserving and environment-protective, single reacting dose are large.The electrode material of the graphene-supported sulphur of this kind of method acquisition has higher cyclical stability, can give full play of the characteristic of the height ratio capacity of sulphur.And mechanical dispersion method condition is easily controlled, material homogeneous, has the potentiality of batch production, and this makes lithium-sulfur cell commercialization become possibility.
Along with social development, people's environmental consciousness is more and more stronger, and electric automobile (EV) receives increasing concern as a kind of vehicles of new green power.Lithium ion battery as its power becomes hot technology equally, and in order to adapt to the needs of electric motor car, it is high that preparation should be able to have specific capacity mutually, and energy density is large, and the electrode material of good cycle becomes the key of Development of Electric Vehicles technology.The theoretical specific capacity (1675mAh/g) of its superelevation of thioneine and theoretical specific energy density (2500KW/kg) most probable become the lithium ion battery as electric car power supply of future generation.And element sulphur itself is as the two large defects that have of electrode material.First sulphur simple substance itself is neither electronic conductor neither ion conductor, and it two is that sulphur can form polysulfide and be dissolved in the electrolyte of battery in the process discharging and recharging.This has directly caused the problems such as cycle life, coulomb efficiency of lithium-sulfur cell is low.The obstruction that these problems are serious the commercialization of lithium-sulfur cell.In order to limit this drawback, the technology such as other are as coated in carbon nano-tube encapsulation, carbon for general using, nucleocapsid or template lambda limiting process, macromolecule layer are coated, doping limit the dissolving of polysulfide.Although above method can both suppress the dissolving of polysulfide to a certain extent, improve the cycle performance of electrode material, because of its preparation method complexity, experiment condition harshness is all failed to realize and is commercially produced on a large scale.
Research about lithium-sulfur cell electrode material is more, and the conductivity of improving sulphur by different control method (the solid sulphur of porous mass, polymeric coating layer apply bag sulphur and three directions of doping) is the key technology of lithium-sulfur cell with the dissolving that suppresses polysulfide.Gao etc. carry out synthetic microporous carbon ball with glucose as presoma, and pore diameter distributes and is less than 1nm.Their material has high cyclical stability, and 42wt%'s carries sulfur content and exceed the height ratio capacity (Energy Environ. Sci. 2010,3,1531 – 1537.) of 900mAh/g.Active carbon is by Aurbach, and Garsuch etc. carry sulphur body as micropore and use.Peculiar part is that this material does not need adhesive.A kind of and inexpensive business active carbon has high specific area (2000m^2/g) and minimum pore-size distribution (<2nm), and he can carry the sulphur of 33wt%.Under the condition that is 150mAh/g in current density, can there is the specific discharge capacity of 1057mAh/g and have a very high coulomb efficiency (Adv.Mater. 2011,23,5641 – 5644.).Zhao etc., do not use sulfur-donor but have simply used conducting polymer polythiophene to wrap in the surface of sulphur.They have successfully synthesized the compound of the polythiophene of the about 72wt% of a kind of sulfur content, and this material has extremely good chemical property.With low viscous electrolyte DOL/DME, this kind of compound, under the current density of 100mAh/g, can keep 74% first circle specific capacity (1120mA/g) (Energy Environ. Sci. 2011,4,5053 – 5059.) after 80 circulations.
In a word, seek carrier a kind of porous, conduction and solve the effect and to improve the nonconducting characteristic of sulphur itself be to design the key of lithium-sulfur cell electrode material of shuttling back and forth of the generation of sulphur in charge and discharge process.
Summary of the invention
The present invention is taking sublimed sulfur, natural graphite powder as raw material, prepares graphene oxide by chemical oxidation stripping method, and microwave method is prepared Graphene, and mechanical dispersion is prepared electrode slurries, obtains combination electrode material after vacuumize.The method key is to be sent out and to be prepared Graphene by microwave, then by mechanical dispersion, sublimed sulfur is mixed with this graphene uniform, obtains sulphur and graphene combination electrode material after vacuumize.Through the combination electrode material of electro-chemical test known this novel graphite alkene sulfur loaded, the capacity that compares is high, good cycling stability, preparation aspect is simple, experiment condition is gentle, has business-likely may and to be applied to pure electric automobile.
The present invention is achieved by the following technical solutions.
The preparation method of the electrode of lithium cell utmost point material of the graphene-supported sulphur of a kind of microwave method of the present invention, is characterized in that having following technical process and step:
A. take 2-2.5g natural graphite powder ice-water bath and keep 0 DEG C of lower magnetic force to stir, first add 1-1.25g NaNO 3and the H of 100-150ml concentration 98% 2sO 4, then add 8-15g KMnO 4, be warming up to 30-40 DEG C of reaction 2-3 h; Be warming up to again 70-90 DEG C of reaction 1-2 h; After adding 300-500 ml ultra-pure water dilution concentrated acid, obtain black colloidal material; Add again 30% H of 20-30 ml 2o 2and the 10% HCl cleaning of 100-150 ml, obtain brown yellow solution; Centrifugal water is washed till neutrality; At 50-60 DEG C, air drying obtains graphene oxide; Graphene oxide is placed in to microwave oven, and 800-1000W heats 5-10min, obtains the cotton-shaped Graphene of black.
B. the above-mentioned Graphene of sublimed sulfur, 0.15g conductive carbon, 0.15g of getting respectively 0.6g grinds 30min-1h and mixes, and obtains the fine powder of black; Mixture is transferred to the adhesive that adds 0.1g in small beaker, fully mix and blend 10min, obtains gluey black liquor; With high speed inner-rotary type beater dispersion slurries, each one minute repeats 5-10 time, obtains the gluey electrode slurry of black of the sulphur/Graphene/conductive carbon of homogeneous; Wherein the ratio of Graphene and conductive carbon is 1:1, and the ratio of sulphur and Graphene is between 2.5:1-4:1, and the ratio of electrode material and adhesive is 8:1-9:1;
C. above-mentioned black paste is coated on the metallic copper collector of handling well in advance uniformly, is placed in vacuum drying oven dry, it is 60-80 DEG C that temperature arranges scope, drying time 20-24h; Finally make the electrode material of lithium battery of graphene-supported sulphur.
Brief description of the drawings
X-ray diffraction (XRD) collection of illustrative plates of the composite material of the graphene-supported sulphur of Fig. 1.
ESEM (SEM) photo of the composite material of the graphene-supported sulphur of Fig. 2.
The cycle performance figure that the grading current of the composite material of the graphene-supported sulphur of Fig. 3 discharges and recharges.
The cycle performance figure that the little electric current (0.1C) of the composite material of the graphene-supported sulphur of Fig. 4 discharges and recharges.
Embodiment
After now specific embodiments of the invention being described in.
embodiment 1
Get in the flask that 2.5g natural graphite powder adds 1000mL, flask is placed in to frozen water, ice-water bath maintains the temperature at 0 DEG C of left and right, first adds 1.2g NaNO 3, then carry out magnetic agitation 10min, then add 120mlH 2sO 4(98%), stir 1h, 20 DEG C of left and right of temperature, slowly add 10gKMnO 4, avoid temperature sharply to rise, temperature remains on 35 DEG C, adds KMnO 4after carry out magnetic agitation 2h, then add 400ml ultra-pure water, obtain black colloidal material, then add the H of 40ml 30% 2o 2, solution is brown color, adds the HCl of 100ml 10% to clean, centrifugation, and rotating speed is about: 15000-18000rpm, with ultra-pure water cleaning 3 times, until sample is neutral, be finally dried, obtain graphene oxide.Graphene oxide is shredded and is placed in microwave oven, the cotton-shaped Graphene of black that high fire heating 5-10min obtains.
The above-mentioned Graphene of sublimed sulfur, 0.15g conductive carbon, 0.15g of getting respectively 0.6g grinds 45min and mixes, and obtains the fine powder of black; Mixture is transferred to the adhesive that adds 0.1g in small beaker, fully mix and blend 10min, obtains gluey black liquor; With high speed inner-rotary type beater dispersion slurries, each one minute repeats 10 times, obtains the gluey slurry of black of the sulphur/Graphene/conductive carbon of homogeneous.
Above-mentioned black paste is coated on the metallic copper collector of handling well in advance uniformly, is placed in vacuum drying oven dry, 80 DEG C of temperature, drying time, 22h, finally made the electrode material of lithium battery of graphene-supported sulphur.
the assembling of battery and test thereof
The above-mentioned electrode to be measured preparing is put into self-control stainless steel battery mould to be tested.Using high purity lithium sheet as negative pole, polypropylene porous film (Celgard 2400) is barrier film, the mixed solution of the trifluoromethanesulfonyl chloride LiTFSI that electrolyte is 1mol/L and polyethylene glycol (PEG)/dimethyl ether (DME) (weight ratio is 1:1).Being assembled in the glove box that is full of high-purity argon gas of battery carried out.Measuring current density is 0.1C, 0.5C, 1C, 2C and 5C, and wherein 1C equals 1675 mA/g, and test voltage scope is 1-3V.
Shown in accompanying drawing 1: the analysis showed that product is that the sulphur that degree of crystallinity is higher loads on the composite material on Graphene.Accompanying drawing 2 is its SEM photo: can find out graphene-supported sulphur composite material, Graphene presents diaphanous film, and sulphur and conductive carbon are evenly dispersed in the surfaces externally and internally of Graphene, and particle diameter is between 30-40nm.Fig. 3 is the ladder charging and discharging capacity performance map of graphene-supported S composite material front 60 circles under different current densities.As can be seen from Figure 3, current density is 161mA/g(0.1C) circulation 20 circle after specific capacity remain on 964 mAh/g; Current density is 1610 mA/g (1C) circulation, 35 circles remain on ~ 600 mAh/g of specific capacity afterwards.As can be seen from Figure 4, battery can remain on ~ 1000mAh/g of specific capacity after little electric current charges and discharge circulation 50 circles.Visible this material specific capacity is high, and stable circulation performance is good, has business-like potentiality.

Claims (1)

1. microwave is prepared a preparation method for the electrode material of lithium battery of graphene-supported sulphur, it is characterized in that having following technical process and step:
A. take 2-2.5 g natural graphite powder ice-water bath and keep 0 DEG C of lower magnetic force to stir, first add 1-1.25g NaNO 3and the H of 100-150ml concentration 98% 2sO 4, then add 8-15g KMnO 4, be warming up to 30-40 DEG C of reaction 2-3 h; Be warming up to again 70-90 DEG C of reaction 1-2 h; After adding 300-500 ml ultra-pure water dilution concentrated acid, obtain black colloidal material; Add again 30% H of 20-30 ml 2o 2and the 10% HCl cleaning of 100-150 ml, obtain brown yellow solution; Centrifugal water is washed till neutrality; At 50-60 DEG C, air drying obtains graphene oxide; Graphene oxide is placed in to microwave oven, and 800W-1000W heats 5-10min, obtains the cotton-shaped Graphene of black;
B. the above-mentioned Graphene of sublimed sulfur, 0.15g conductive carbon, 0.15g of getting respectively 0.6g grinds 30min-1h and mixes, and obtains the fine powder of black; Mixture is transferred to the adhesive that adds 0.1g in small beaker, fully mix and blend 10min, obtains gluey black liquor; With high speed inner-rotary type beater dispersion slurries, each one minute repeats 5-10 time, obtains the gluey slurry of black of the sulphur/Graphene/conductive carbon of homogeneous; Wherein the ratio of Graphene and conductive carbon is 1:1, and the ratio of sulphur and Graphene is between 2.5:1-4:1, and the ratio of electrode material and adhesive is 8:1-9:1;
C. above-mentioned black paste is coated on the metallic copper collector of handling well in advance uniformly, is placed in vacuum drying oven dry, it is 60-80 DEG C that temperature arranges scope, drying time 20-24h; Finally obtain the electrode material of lithium battery of graphene-supported sulphur.
CN201410110694.4A 2014-03-24 2014-03-24 A kind of microwave prepares the preparation method of the electrode material of lithium battery of graphene-supported sulphur Expired - Fee Related CN103943833B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105261755A (en) * 2015-09-09 2016-01-20 上海大学 Preparation method for nano-rod iron molybdate electrode material of lithium ion battery
CN111247096A (en) * 2017-06-14 2020-06-05 新泽西鲁特格斯州立大学 Scalable preparation of pristine porous graphene nanoplatelets by dry microwave radiation
CN112620643A (en) * 2020-11-20 2021-04-09 浙江南都电源动力股份有限公司 Preparation method of graphene-coated lithium metal
CN114792777A (en) * 2022-04-28 2022-07-26 西安交通大学 Ultra-fine sulfur/carbon composite material and preparation method and application thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105261755A (en) * 2015-09-09 2016-01-20 上海大学 Preparation method for nano-rod iron molybdate electrode material of lithium ion battery
CN111247096A (en) * 2017-06-14 2020-06-05 新泽西鲁特格斯州立大学 Scalable preparation of pristine porous graphene nanoplatelets by dry microwave radiation
CN112620643A (en) * 2020-11-20 2021-04-09 浙江南都电源动力股份有限公司 Preparation method of graphene-coated lithium metal
CN112620643B (en) * 2020-11-20 2023-04-07 浙江南都电源动力股份有限公司 Preparation method of graphene-coated lithium metal
CN114792777A (en) * 2022-04-28 2022-07-26 西安交通大学 Ultra-fine sulfur/carbon composite material and preparation method and application thereof

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