CN110034288A - A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method - Google Patents

A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method Download PDF

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CN110034288A
CN110034288A CN201910298514.2A CN201910298514A CN110034288A CN 110034288 A CN110034288 A CN 110034288A CN 201910298514 A CN201910298514 A CN 201910298514A CN 110034288 A CN110034288 A CN 110034288A
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sulphur
nanotube
lithium
graphene
composite material
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张永光
杜坚忠
李朋生
彭福生
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Shenzhen High Energy Battery Co Ltd
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Shenzhen High Energy Battery Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention is a kind of preparation method of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material.This method comprises the following steps: the first step, prepares graphene oxide grafted polypyrrole (GOppy) nanotube;Second step prepares graphene grafted polypyrrole (Gppy) nanotube;Third step; it prepares graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material: Gppy nanotube made from second step and nanometer sulphur powder is put into 2~4h of ball-milling treatment in ball mill; then under argon atmosphere protection; the resulting mixture of ball milling is put into using polytetrafluoroethylene (PTFE) as in the reaction kettle of substrate; reaction is 1~20h at 100~200 DEG C, and the compound lithium sulfur battery anode material of graphene grafted polypyrrole (Gppy) nanotube/sulphur is made.Lithium sulfur battery anode material prepared by the present invention can effectively inhibit shuttle effect, and then improve the chemical property and cyclical stability of lithium-sulfur cell on the whole.

Description

A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material Preparation method
Technical field
The present invention relates to the technical field of lithium sulfur battery anode material, in particular to a kind of lithium-sulphur cell positive electrode that can be used for The preparation method of graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material.
Background technique
A kind of device of the battery as energy storage and conversion plays irreplaceable in people's life, social production Effect even more had received widespread attention especially in mobile electronic device field.Lithium ion battery has high energy close Degree, high service life and it is environmentally protective the features such as, successfully realize commercialization.Currently, commercialized lithium ion battery Positive electrode is main are as follows: LiCoO2, LiMnO2, stratiform Li (Ni1/3Co1/3Mn1/3) O2 ternary material, spinel-type LiMn2O4 and olivine-type LiFePO_4.But above-mentioned material as anode material for lithium-ion batteries when be all individually present it is scarce Point.For example, LiCoO2 price is higher, there is toxicity;Lattice deformability is easily caused when LiMO2 charge and discharge, is caused under cycle performance Drop;Stratiform Li (Ni1/3Co1/3Mn1/3) O2 ternary material is not easily-synthesized;LiFePO4 poorly conductive etc..People are closed by improving The performance for improving the positive electrode of lithium ion battery at the methods of approach, optimization material composition, cannot but change above-mentioned material Smaller (150~400mAh/g) this fatal defects of theoretical specific capacity.With social development, people are to energy-storage battery of new generation It is required that also higher and higher, the specific capacity of positive electrode has been largely fixed the energy density of battery, from the ratio of positive electrode From the point of view of capacity, the energy density of current commercialized lithium-ion battery system has been difficult to continue to lift up, and therefore, exploitation has height Specific capacity, environmental protection, low cost energy-storage battery system become research hotspot.
The theoretical specific capacity of elemental sulfur is 1675mAh/g.It is anode with sulphur, lithium simple substance is the battery theory matter of cathode composition Amount specific energy can reach 2600Wh/kg, be the hot spot of energy battery exploitation of new generation.And elemental sulfur is rich reserves in the earth One of element has the characteristics that cheap, environmental-friendly.
Lithium-sulfur cell has won the extensive concern of domestic and foreign scholars with its high theoretical energy density, but wants Successful commercial Change, there is also some critical issues have it is to be solved.The problem of being primarily present has: (1) conductivity of sulphur and discharging product lithium sulfide Difference causes battery to be difficult charge and discharge under the conditions of high magnification;(2) sulphur is different with discharging product lithium sulfide density, leads to positive material Material volume in charge and discharge expands, and influences battery service performance;(3) the electric discharge more lithium sulfides of intermediate product are soluble in electrolysis Liquid leads to the irreversible decaying of battery capacity;(4) the more lithium sulfides of electric discharge intermediate product of electrolyte are dissolved in charge and discharge process In, spread and occur redox reaction back and forth between positive and negative anodes under the action of concentration difference and electric field, the more lithium sulfides in part exist Negative terminal surface is reduced into insoluble type solid lithium sulfide, and the coulombic efficiency of battery is caused to decline;(5) lithium anode is in charge and discharge In the process formed lithium Zhi Jing, puncture SEI film, SEI film is concatenated to form-ruptures, constantly consumption electrolyte, may be punctured when serious every Film causes battery that short circuit occurs.Problem above limits the commercialized process of lithium-sulfur cell.
With with high conductivity, morphology controllable conducting polymer and sulphur simple substance it is compound, lithium-sulfur cell can improved just Many chemical properties of pole material are the common methods for preparing lithium sulfur battery anode material at present.Chinese patent CN106159209A discloses a kind of sulfur-based composite anode material preparation method of containing graphene that can be used for lithium-sulphur cell positive electrode, For this method using nickel foam as template, graphite oxide is precursor preparation foamy graphite alkene/sulphur composite material, and sulphur simple substance can be Effectively adhere in the hole of foamy graphite alkene, improves the capacity of battery, but graphene involved by the technique is two dimension Non-polar material, it is not strong to the adsorption capacity of more sulphur intermediate products, it is difficult to effectively inhibit shuttle effect.Chinese patent CN107275580A discloses a kind of preparation method of the polyaniline that can be used for lithium-sulphur cell positive electrode/sulphur composite material, this method Conductive polymer polyanaline is prepared as raw material, ammonium persulfate are initiator using aminothiophenol, then passes through melting and mixes sulphur legal system For sulfur-based positive electrode material, the carbonnitrogen bond on polyaniline has polarity, and nitrogen can provide additional lone pair electrons, can inhale The attached lithium-sulfur cell electric discharge more lithium sulfides of intermediate product, so that the cycle performance of battery is improved, but this method has the disadvantages that (1) irreversible stacking can occur during aggregating into polyaniline for aminothiophenol causes polyaniline material porosity low, Specific surface area is not high, is unfavorable for sulphur and adheres on it;(2) this method when sulphur is mixed in melting 175 DEG C constant temperature 8 hours, this temperature Degree is higher than the fusing point of sulphur, will cause the loss of sulphur, energy density is caused to decline.Chinese patent CN106848319A discloses one kind It can be used for rutile titanium dioxide-titanium nitride/sulphur composite material preparation method of lithium-sulphur cell positive electrode, this method is with tetrachloro Change titanium and urea is raw material to prepare heterojunction nanometer material, then sulphur method is mixed by melting and is prepared for sulfur-based positive electrode material, the material Titanium dioxide and carbonitride are doping symbiotic structure in material, can be adsorbed to polysulfide, to improve lithium-sulfur cell Cycle performance, but the electric conductivity of either carbon dioxide or titanium nitride is all very poor, it is difficult to it is forthright to high power to meet lithium-sulfur cell The requirement of energy.
Summary of the invention
The technical problems to be solved by the present invention are: a kind of preparation method of lithium sulfur battery anode material is provided, it is specific next Say it is that one kind first passes through soft mode version method and prepares graphene grafted polypyrrole compound (Gppy) nanotube, then passes through fusion method and prepare The preparation method of Gppy nanotube/sulphur composite material lithium sulfur battery anode material.Lithium-sulphur cell positive electrode material prepared by the present invention Material can effectively inhibit shuttle effect, and then improve the chemical property and cyclical stability of lithium-sulfur cell on the whole.
The technical solution of the present invention is as follows:
A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method, including such as Lower step:
The first step prepares graphene oxide grafted polypyrrole (GOppy) nanotube:
(1) graphene oxide (GO) powder mull is placed on ultrasonic disperse in DMF, and be poured into reactor, to Thionyl chloride is wherein added, ice bath is simultaneously stirred to react 1~5h, after having reacted, under the conditions of nitrogen atmosphere, 70~120 DEG C of oil baths Remaining thionyl chloride is dried up with nitrogen, the graphene oxide DMF dispersion liquid containing acid chloride groups is obtained, adds deionization Water obtains the graphene oxide water solution containing acid chloride groups;
Wherein, its volume of graphene oxide DMF dispersion liquid containing acid chloride groups is close with previous added DMF volume, gained Dispersion liquid volume presses original DMF volumetric enumeration;
Wherein, its mass concentration of graphene oxide DMF dispersion liquid containing acid chloride groups and graphene oxide DMF dispersion liquid are dense Spend close, gained dispersion liquid concentration is pressed former graphene oxide DMF dispersion liquid concentration and counted;
Wherein, every milliliter of DMF adds 10~50mg graphene oxide (GO) powder, 1~20mL thionyl chloride;Volume ratio is to go Ionized water: dispersion liquid=10 graphene oxide DMF~100:1 containing acid chloride groups;Nitrogen atmosphere is the speed with 0.1~1L/min Rate is passed through 10~30min of nitrogen.
The mode for being passed through nitrogen are as follows: nitrogen tube is goed deep into reaction solution bottom;
(2) pyrrole monomer is added in template aqueous solution, obtains pyrroles's dispersion liquid, then ultrasonic disperse is added and contains The graphene oxide water solution of acid chloride groups, ultrasonic disperse, the ice bath processing 0.5 in the case where revolving speed is the stirring condition of 50~200rpm ~5h obtains the aqueous solution of graphene oxide grafting pyrroles;
0.1~10mL pyrrole monomer, every 100 milliliters of pyrroles's dispersion liquids are wherein added in every 100 milliliters of template aqueous solutions Middle addition graphene oxide water solution of the 10~100mL containing acid chloride groups;The concentration of template aqueous solution is 0.1~100mg/ mL;
(3) it takes aqueous oxidizing agent solution to be added in the aqueous solution of graphene oxide grafting pyrroles, is then added dropwise 10mol/L's HCl solution adjusts PH to 3~7, and ultrasonic disperse stands ice bath and handles 4-12h;Finally, successively using deionized water and acetone washing Reaction gained mixture, filters and is dried to obtain black powder, i.e. graphene oxide grafted polypyrrole (GOppy) nanotube;
Wherein, volume ratio is aqueous oxidizing agent solution: graphene oxide is grafted pyrroles's aqueous solution=1:(1~5);Oxidant water 0.1~100mg/mL of concentration of solution;
Second step prepares graphene grafted polypyrrole (Gppy) nanotube:
Under argon atmosphere protection, black powder and hydrazine hydrate that the first step obtains are placed in using polytetrafluoroethylene (PTFE) as substrate In reaction kettle, 1~20h is reacted at 50~200 DEG C, reaction product is washed with ethyl alcohol and deionized water, filters and be dried to obtain stone Black alkene grafted polypyrrole (Gppy) nanotube;
Wherein, mass ratio is the black powder that the first step obtains: hydrazine hydrate=5~10:1;
Third step prepares graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material:
Gppy nanotube made from second step and nanometer sulphur powder are put into 2~4h of ball-milling treatment in ball mill, then argon gas Under atmosphere protection, the resulting mixture of ball milling is put into using polytetrafluoroethylene (PTFE) as in the reaction kettle of substrate, it is anti-at 100~200 DEG C It should be 1~20h, the compound lithium sulfur battery anode material of graphene grafted polypyrrole (Gppy) nanotube/sulphur be made;
Wherein, mass ratio is Gppy nanotube: nanometer sulphur powder=1:(1~5);
Preferably, the template agent is beta-naphthalenesulfonic-acid (β-NSA), tridecyl sulfate (SDS), dodecyl benzene sulfonic acid One of sodium (SDBS), methyl orange (MO) and cetyl trimethylammonium bromide (CTAB);
Preferably, the oxidant be ferric trichloride, ammonium persulfate (APS), hydrogen peroxide, potassium bichromate, silver nitrate and One of dichloride copper;
Preferably, the ultrasonic disperse time is 10~60min;
Preferably, the ice bath treatment temperature is -5~10 DEG C;
Preferably, the drying temperature is 40~60 DEG C, and drying time is 10~20h;
Preferably, the revolving speed of the ball mill is 100~500rpm;
The preparation side of above-mentioned graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material for lithium-sulphur cell positive electrode Method, wherein involved raw material are commercially available;
The preparation side of above-mentioned graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material for lithium-sulphur cell positive electrode Method, used in equipment and technique be known to those skilled in the art.
Compared with prior art, the method for the present invention has substantive distinguishing features outstanding as follows:
(1) in design process of the present invention, to solve existing lithium-sulphur cell positive electrode active material sulphur and discharging product lithium sulfide The problem of poorly conductive, innovatively propose with graphene grafted polypyrrole (Gppy) nanotube with sulphur is compound prepares lithium-sulfur cell The technical method of positive electrode.Chloride processing is carried out to graphene oxide with thionyl chloride and introduces acid chloride groups (- COOCl), Since acid chloride groups (- COOCl) has high reactivity, is reacted with pyrrole monomer and generate amido bond (- CO-N <), from And it is grafted graphene sheet layer on polypyrrole, the electric conductivity of composite material is improved, to improve times of lithium-sulfur cell Rate performance;
(2) it in design process of the present invention, to solve the problems, such as that existing lithium-sulfur cell ionic conductivity is poor, innovatively utilizes Hydrazine hydrate in-situ reducing graphene oxide carrys out pore-creating.Graphene oxide can generate a large amount of micropore during reduction, this makes It obtains Gppy nanometers of tube walls and generates a large amount of micropores, improve the wetting capacity of electrolyte, shorten charge and discharge process intermediate ion biography Defeated distance, to improve the high rate performance of lithium-sulfur cell;
(3) in design process of the present invention, to solve the problems, such as that existing lithium-sulphur cell positive electrode active material utilization efficiency is low, wound It is proposed to new property a kind of preparation method of high-specific surface area Gppy nanotube.By the way that n,N-Dimethylformamide (DMF) is added Graphene oxide water solution, when DMF is then added in stencil solution, part DMF is dissolved in template agent, due to graphite oxide Alkene does not simultaneously dissolve in methyl orange, so that the concentration difference of graphene oxide is formed at the interface of methyl orange microlayer model and water, with grafting The polymerization reaction of reaction and pyrrole monomer carries out, and graphene oxide is higher in the inside content of nanotube, makes the inside of nanotube With coarse structure, the specific surface area of nanotube is improved, to improve the load of active sulfur, improves the ratio of lithium-sulfur cell Capacity;
(4) it in design process of the present invention, to solve the problems, such as that existing lithium-sulfur cell shuttle effect is serious, innovatively utilizes There is tube wall the Gppy nanotube of microcellular structure to carry out carrying active substance sulphur.Sulphur is encapsulated in nanotube, is limited and was reacted The dissolution of more sulphur intermediate products, the generation of shuttle effect is inhibited from source in journey;In addition, the carbonnitrogen bond of polypyrrole has pole Property, and nitrogen has additional lone pair electrons, can effectively adsorb more sulphur intermediate products, further improve lithium-sulfur cell Cycle performance;
(5) in design process of the present invention, to solve existing lithium sulfur battery anode material volume expansion in charge and discharge process Serious problem is innovatively grafted to improve polypyrrole material mechanical property using the graphene of good mechanical properties and polypyrrole Can, and by method of the Gppy/ sulphur composite material in High temperature storage certain time to evaporate a part of sulphur, to alleviate positive material Expect the volume expansion in charge and discharge process.Improve the security performance of battery.
Compared with prior art, the marked improvement of the method for the present invention is as follows:
1, compared with prior art CN106159209A, lithium sulfur battery anode material provided by the present invention is having conduction Property good redox graphene (rGO) on the basis of this, introducing, there is the polypyrrole material of good adsorption ability to adsorb More lithium sulfides, to limit the irreversible loss that more lithium sulfides are dissolved in electrolyte and cause battery capacity, it is provided by the invention just For battery prepared by the material of pole under the current density of 0.1C, first discharge specific capacity reaches 1226mAh/g, compares after 100 circulations Capacity is still able to maintain 883mAh/g, and battery capacity attenuation rate is only 0.27%/time;
2, compared with prior art China patent CN107275580A, the present invention is led on the basis of preparing conducting polymer It crosses template and prepares the composite material with porous structure, be that a kind of physics and chemistry combine to limit more lithium sulfides dissolutions Method;
3, compared with prior art CN106848319A, the present invention is by the method that is graft-polymerized by graphene and polypyrrole Compound, prepared material is carried out with excellent conductive capability, the present invention is prepared by template with porous structure Composite material, porous structure is conducive to the infiltration of electrolyte, therefore the material also has excellent lithium ion ducting capacity, this hair Battery prepared by the positive electrode of bright offer can discharge under the conditions of high magnification, and be able to maintain good specific capacity, with Current charging and discharging currents density increase to 2C from 0.5C, bagasse/sulphur composite material discharge capacity by 781mAh/g to 608mAh/g.For the battery of composite material preparation, when current density is reduced to 0.5C from 2C, discharge capacity can big portion Divide and restore, shows outstanding high rate performance;
4, compared with prior art CN106463703A, preparation condition of the invention is mild, preparation process 200 DEG C with Lower completion.
In short, graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by the present invention is a kind of great quotient The lithium sulfur battery anode material of industryization value.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram of embodiment 1;
Fig. 2 is graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by embodiment 1 as lithium sulphur electricity When the anode of pond, constant current charge-discharge curve graph and the 100th charging and discharging curve figure three times before being under 0.1C in current density;
Fig. 3 is graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by embodiment 1 as lithium sulphur electricity The cycle performance figure when anode of pond, in the case where current density is 0.1C;
Fig. 4 is graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by embodiment 1 as lithium sulphur electricity High rate performance figure when the anode of pond.
Specific embodiment
Embodiment 1
The first step prepares graphene oxide grafted polypyrrole (GOppy) nanotube:
(1) 50mg graphite oxide powder is weighed, grinding is placed on ultrasonic disperse 30min in 2mLDMF, and by scattered oxygen Graphite (GO) solution pours into three-necked flask, and 10mL thionyl chloride is added thereto, and ice bath is simultaneously stirred to react 2h, has reacted Afterwards, under the conditions of 80 DEG C of oil baths, nitrogen tube gos deep into reaction solution bottom, dries up remaining thionyl chloride with nitrogen, adds 48mL deionized water obtains the graphene oxide water solution containing acid chloride groups;(2) take 100mL (0.66mg/mL) methyl orange water-soluble 0.5mL pyrroles, and ultrasonic disperse 30min is added in liquid, and graphene oxide water solution of the 50mL containing acid chloride groups is then added, and Ultrasonic disperse 30min, in the case where revolving speed is the stirring condition of 200rpm, ice bath handles 30min, and ice bath temperature is -5 DEG C, is aoxidized Graphene is grafted the aqueous solution (150 milliliters) of pyrroles, and (3) take the ferric chloride solution of 50mL (21mg/mL) to be added to graphite oxide Alkene is grafted in the aqueous solution of pyrroles, and the HCl solution that appropriate 10mol/L is then added dropwise adjusts PH to 4.5, ultrasonic disperse 30min, quiet Ice bath processing 8h is set, ice bath temperature is -5 DEG C;Finally, washing 3 secondary responses gained mixture repeatedly with deionized water and acetone, take out It filters and dry 12h obtains black powder, i.e. graphene oxide grafted polypyrrole (GOppy) nanotube at 45 DEG C;
(explanation: it is passed through nitrogen from solution bottom at such a temperature, thionyl chloride can be taken out of solution, because of the temperature The quality of DMF can't be made during drying up thionyl chloride higher than the boiling point of thionyl chloride, and far below DMF boiling point At loss.During graphene oxide chloride, only fraction-the COOH on graphene oxide participates in acyl chloride reaction, can It is approximately equal to former graphene oxide quality to be approximately considered the graphene oxide quality containing acid chloride groups, therefore can be approximately considered The amount of substance concentration of the two does not change.)
Second step prepares graphene grafted polypyrrole (Gppy) nanotube:
The black powder that the first step obtains and hydrazine hydrate are placed in using polytetrafluoroethylene (PTFE) as the anti-of substrate by 10:1 in mass ratio Heating and thermal insulation in kettle is answered, this process of reaction kettle is put into and is completed in the glove box under argon atmosphere protection, reaction time 2h, Reaction temperature is 95 DEG C, reaction product ethyl alcohol and the repeated multiple times washing of deionized water, filters and is dried to obtain graphene grafting Polypyrrole (Gppy) nanotube;
Third step prepares graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material:
Gppy nanotube and nano-sulfur made from required above-mentioned second step are weighed respectively according to the ratio that mass ratio is 1:1 Powder, and the two is put into ball-milling treatment 2h in ball mill, then the resulting mixture of ball milling is put into polytetrafluoroethylene (PTFE) as lining Heating and thermal insulation in the reaction kettle at bottom is put into this process of reaction kettle and completes in the glove box under argon atmosphere protection, when reaction Between be 12h, reaction temperature be 155 DEG C, thus be made the compound lithium-sulfur cell of graphene grafted polypyrrole (Gppy) nanotube/sulphur just Pole material;
4th step, prepares lithium-sulfur cell:
By graphene grafted polypyrrole (Gppy) nanotube obtained/sulphur composite material, SuperP and binder according to matter Amount is placed in mortar than the ratio for 8: 1: 1 and grinds uniformly, suitable N-Methyl pyrrolidone is added, and be ground into slurry, will Slurry uniformly scratches on carbon containing aluminium foil, and wherein coating thickness is 15um, and drying for 24 hours, is pressed using tablet press machine in 5MPa at 55 DEG C Power pushes flakiness, obtains positive plate.Be anode with gained graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material, Metal Li piece is cathode, and electrolyte is added, battery assembly is carried out in glove box, obtains button CR2025 half-cell.
Chemical property analysis (BTS-800, new prestige) is carried out to prepared sample.
Fig. 1 is that the process flow of the present embodiment illustrates;
Fig. 2 is graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by the present embodiment as lithium sulphur Discharge curve for the first time, second of charging and discharging curve, third time charging and discharging curve when anode, in the case where current density is 0.1C And the 100th charging and discharging curve.Under the current density of 0.1C, first discharge specific capacity reaches 1226mAh/g, 100 circulations Specific capacity is still able to maintain 883mAh/g afterwards;
Fig. 3 is graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by the present embodiment as lithium sulphur Cycle performance figure when anode, in the case where current density is 0.1C.Under the current density of 0.1C, first discharge specific capacity reaches 1226mAh/g, specific capacity is still able to maintain 883mAh/g after 100 circulations, and battery capacity attenuation rate is 0.27%/time.
Fig. 4 is graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material prepared by the present embodiment as lithium sulphur High rate performance figure when anode.As current charging and discharging currents density increases to 2C, graphene grafted polypyrrole from 0.5C (Gppy) nanotube/sulphur composite material discharge capacity is by 781mAh/g to 608mAh/g.For the composite material preparation battery, When current density is reduced to 0.5C from 2C, discharge capacity can largely be restored, and show outstanding high rate performance.
Embodiment 2
Other replace iron chloride to make initiator by the first step with embodiment 1, difference with ammonium persulfate (APS).? The performance and embodiment 1 of the material arrived are close.
Embodiment 3
, with embodiment 1, difference is third step graphene grafted polypyrrole (Gppy) nanotube and nanometer sulphur powder for other Mass ratio be 1:2.
Embodiment 4
, with embodiment 1, difference is third step graphene grafted polypyrrole (Gppy) nanotube and nanometer sulphur powder for other Mass ratio be 1:3.
Through the foregoing embodiment, it can be seen that the present invention first passes through soft mode version method, and to prepare graphene grafted polypyrrole compound Object (Gppy) nanotube, then Gppy nanotube/sulphur composite material lithium sulfur battery anode material is prepared by fusion method.By this The lithium-sulfur cell of material preparation has excellent specific discharge capacity, cycle performance and high rate performance.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, but wants compound with the principles and novel features disclosed herein phase one The widest scope of cause.
Unaccomplished matter of the present invention is well-known technique.

Claims (8)

1. a kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method, it is characterized in that Include the following steps:
The first step prepares graphene oxide grafted polypyrrole (GOppy) nanotube:
(1) graphene oxide (GO) powder mull is placed on ultrasonic disperse in DMF, and be poured into reactor, thereto Thionyl chloride is added, ice bath is simultaneously stirred to react 1~5h, after having reacted, nitrogen under the conditions of nitrogen atmosphere, 70~120 DEG C of oil baths Gas dries up remaining thionyl chloride, obtains the graphene oxide DMF dispersion liquid containing acid chloride groups, adds deionized water, obtain To the graphene oxide water solution containing acid chloride groups;
Wherein, every milliliter of DMF adds 10~50mg graphene oxide (GO) powder, 1~20mL thionyl chloride;Volume ratio is deionization Water: dispersion liquid=10 graphene oxide DMF~100:1 containing acid chloride groups;
(2) pyrrole monomer is added in template aqueous solution, obtains pyrroles's dispersion liquid, then ultrasonic disperse is added and contains acyl chlorides The graphene oxide water solution of group, ultrasonic disperse, revolving speed be 50~200rpm stirring condition under ice bath processing 0.5~ 5h obtains the aqueous solution of graphene oxide grafting pyrroles;
0.1~10mL pyrrole monomer is wherein added in every 100 milliliters of template aqueous solutions, is added in every 100 milliliters of pyrroles's dispersion liquids Enter graphene oxide water solution of the 10~100mL containing acid chloride groups;The concentration of template aqueous solution is 0.1~100mg/mL;
(3) it takes aqueous oxidizing agent solution to be added in the aqueous solution of graphene oxide grafting pyrroles, the HCl of 10mol/L is then added dropwise Solution adjusts pH to 3~7, and ultrasonic disperse stands ice bath and handles 4~12h;Finally, successively anti-with deionized water and acetone washing Gained mixture is answered, black powder, i.e. graphene oxide grafted polypyrrole (GOppy) nanotube are filtered and be dried to obtain;
Wherein, volume ratio is aqueous oxidizing agent solution: graphene oxide is grafted pyrroles's aqueous solution=1:(1~5);Aqueous oxidizing agent solution 0.1~100mg/mL of concentration;
Second step prepares graphene grafted polypyrrole (Gppy) nanotube:
Under argon atmosphere protection, black powder and hydrazine hydrate that the first step obtains are placed in the reaction using polytetrafluoroethylene (PTFE) as substrate In kettle, 1~20h is reacted at 50~200 DEG C, reaction product is washed with ethyl alcohol and deionized water, filters and be dried to obtain graphene Grafted polypyrrole (Gppy) nanotube;
Wherein, mass ratio is the black powder that the first step obtains: hydrazine hydrate=5~10:1;
Third step prepares graphene grafted polypyrrole (Gppy) nanotube/sulphur composite material:
Gppy nanotube made from second step and nanometer sulphur powder are put into 2~4h of ball-milling treatment in ball mill, then argon atmosphere Under protection, the resulting mixture of ball milling is put into using polytetrafluoroethylene (PTFE) as in the reaction kettle of substrate, reaction is 1 at 100~200 DEG C The compound lithium sulfur battery anode material of graphene grafted polypyrrole (Gppy) nanotube/sulphur is made in~20h;
Wherein, mass ratio is Gppy nanotube: nanometer sulphur powder=1:(1~5).
2. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that the template agent is beta-naphthalenesulfonic-acid (β-NSA), tridecyl sulfate (SDS), neopelex (SDBS), one of methyl orange (MO) and cetyl trimethylammonium bromide (CTAB).
3. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that the oxidant is ferric trichloride, ammonium persulfate (APS), hydrogen peroxide, potassium bichromate, silver nitrate and two One of copper chloride.
4. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that the ultrasonic disperse time is 10~60min.
5. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that the ice bath treatment temperature is -5~10 DEG C.
6. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that the drying temperature is 40~60 DEG C, drying time is 10~20h.
7. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that the revolving speed of the ball mill is 100~500rpm.
8. lithium-sulphur cell positive electrode as described in claim 1 graphene grafted polypyrrole nanotube/sulphur composite material preparation Method, it is characterized in that nitrogen atmosphere is to be passed through 10~30min of nitrogen with the rate of 0.1~1L/min.
CN201910298514.2A 2019-04-15 2019-04-15 A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method Pending CN110034288A (en)

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