CN105514395B - The method that microwave liquid phase process prepares doped graphene lithium sulfur battery anode material - Google Patents
The method that microwave liquid phase process prepares doped graphene lithium sulfur battery anode material Download PDFInfo
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- CN105514395B CN105514395B CN201610079316.3A CN201610079316A CN105514395B CN 105514395 B CN105514395 B CN 105514395B CN 201610079316 A CN201610079316 A CN 201610079316A CN 105514395 B CN105514395 B CN 105514395B
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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
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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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
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- 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 kind of method that microwave liquid phase process prepares doped graphene lithium sulfur battery anode material, step includes：1) graphite oxide is prepared using Hummers methods；2) by graphite oxide in dispersant for ultrasonic dispersion；3) ammonium hydrogencarbonate is added into ultrasonic disperse in graphite oxide dispersion；Then it is sealed in microwave in microwave reaction kettle to heat, obtains nitrogen-doped graphene solution；4) by vulcanized sodium ultrasonic disperse in nitrogen-doped graphene solution；Microwave in microwave reaction kettle is sealed in again to heat, and obtains nitrogen sulphur codope graphene solution；After being cooled to room temperature, wash, centrifuge, freeze-drying, obtain fluffy nitrogen sulphur codope graphene powder；5) ball milling after nitrogen sulphur codope graphene powder is mixed with sublimed sulfur, product is heat-treated, and obtains nitrogen sulphur codope graphene lithium sulphur positive electrode.The method of the present invention, step is simple, and the electro-chemical properties of resulting materials are good.
Description
Technical field
The invention belongs to nano composite material technical field, is related to a kind of microwave liquid phase process and prepares doped graphene lithium sulphur electricity
The method of pond positive electrode.
Background technology
As social high speed development is to the growing day by day of demand for energy, and pollution and reserves of the fossil fuel to environment
Exhaustion so that people are increasingly urgent to the demand of new alternative energy source.Lithium-sulfur cell has very high energy density
(2600Wh/kg), its positive electrode sulphur has the advantages that storage is abundant, environmentally friendly, therefore lithium-sulfur cell turns into the next generation
The Research Emphasis of secondary cell.However, in the high-insulativity of sulphur, charge and discharge process the change of volume and the more sulphur of intermediate product from
The problems such as son dissolving, make lithium-sulfur cell be difficult to realize commercialization at present.Graphene has the electric conductivity of superelevation and excellent mechanics
Performance, using its with sulphur made of composite can efficiently solve above mentioned problem as cell positive material.
Graphene is the hexagon surrounded by six carbon atom, and thickness is an atomic layer.Connected between carbon atom by σ keys
Connect, combination sp2Hydridization, its excellent electric property cause domestic and international researchers to it in energy storage material application side
The concern in face.In order to further expand the physico-chemical property with Effective Regulation graphene, similar in generally available and C atomic electronegativities
Such as N, S, B, P atom is doped.
The existing method for preparing doped graphene has vapour deposition process, arc discharge method, hydro-thermal method, circumfluence method etc., but with
There are severe reaction conditions in upper method, complex process is consumed energy the shortcomings of big, it is necessary to using hazardous gas.Therefore development one is needed
Kind of low energy consumption, green doping method, microwave method due to energy-conservation, it is efficient the features such as, be increasingly becoming the focus of concern.Carbon materials
The microwave absorption capacity of material is to be highly dependent on their chemical composition and structure.Graphite oxide carries substantial amounts of oxygen-containing function
Group, during microwave irradiation, the not oxidized conjugation region of graphite oxide produces instantaneous high fever as microwave absorption area
Amount, oxygen-containing functional group are decomposed into gas and sloughed, and produce avtive spot, and doped source is decomposed into the active matter containing targeted heteroatom
Kind, hetero atom is embedded into the form of covalent bond in graphene lattice after contacting avtive spot, while realizes graphite oxide
Reduction and the doping of graphene.
The content of the invention
It is an object of the invention to provide a kind of method that microwave liquid phase process prepares doped graphene lithium sulfur battery anode material,
Solve the preparation method of prior art, severe reaction conditions, complex process is consumed energy the problem of big, it is necessary to using hazardous gas.
The technical solution adopted in the present invention is that a kind of microwave liquid phase process prepares doped graphene lithium sulfur battery anode material
Method, implement according to following steps：
Step 1) prepares graphite oxide using Hummers methods；
Step 2) is uniform in dispersant for ultrasonic dispersion by the graphite oxide obtained by step 1), and graphite oxide is in dispersion liquid
Concentration be 1~1.5g/L, ultrasonic time 1~2 hour；
Step 3) adds 0.1~0.2g ammonium hydrogencarbonates ultrasonic disperse in the graphite oxide dispersion obtained by 40mL steps 2)
Uniformly；Then progress microwave heating in microwave reaction kettle is sealed in, obtains nitrogen-doped graphene solution；
By vulcanized sodium ultrasonic disperse in the nitrogen-doped graphene solution obtained by step 3), vulcanized sodium quality is step 4)
0.2~0.5g；Progress microwave heating in microwave reaction kettle is sealed in again, obtains nitrogen sulphur codope graphene solution；It is cooled to
After room temperature, wash, centrifuge, freeze-drying, obtain fluffy nitrogen sulphur codope graphene powder；
Step 5) is by nitrogen sulphur codope graphene powder obtained by step 4) with sublimed sulfur using mass ratio as 1：0.67~2.33
Ball milling after mixing；Then product is heat-treated, obtains nitrogen sulphur codope graphene lithium sulphur positive electrode.
The invention has the advantages that the technique for mainly preparing doped graphene material to tradition from mode of heating is carried out
Improve, substituting traditional heating with microwave radiation technology is doped and peels off simultaneously to graphene, not only with homogeneous heating, energy-conservation
The characteristics of efficient, and reaction rate can be greatly improved, and the use of poisonous reducing agent hydrazine hydrate is avoided, it is green；
Using gained doped graphene as during positive electrode, lithium-sulfur cell shows excellent chemical property.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of nitrogen sulphur codope graphene prepared by the embodiment of the present invention 1, wherein horizontal
Coordinate is the angle of diffraction (2 θ), and unit is degree, and ordinate is diffracted intensity, unit cps；
Fig. 2 is charging and discharging curve of the nitrogen sulphur codope graphene lithium sulphur composite positive pole under room temperature 0.1C multiplying powers, its
Middle abscissa is specific discharge capacity, unit mAh/g, and ordinate is voltage, unit V.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The method that microwave liquid phase process of the present invention prepares doped graphene lithium sulfur battery anode material, it is real according to following steps
Apply：
Step 1) prepares graphite oxide using Hummers methods；(Hummers methods are existing disclosed methods, no longer thin herein
State)；
Step 2) is uniform in dispersant for ultrasonic dispersion by the graphite oxide obtained by step 1), and graphite oxide is in dispersion liquid
Concentration be 1~1.5g/L, ultrasonic time 1~2 hour；Dispersant is from water, ethanol, ethylene glycol, 1-METHYLPYRROLIDONE
One or more kinds of combinations；
Step 3) adds 0.1~0.2g ammonium hydrogencarbonates ultrasonic disperse in the graphite oxide dispersion obtained by 40mL steps 2)
Uniformly, ultrasonic time is 5~10 minutes；Then progress microwave heating, microwave power 400- in microwave reaction kettle are sealed in
800W, reaction time are 30~60 seconds, obtain nitrogen-doped graphene solution；
By vulcanized sodium ultrasonic disperse in the nitrogen-doped graphene solution obtained by step 3), vulcanized sodium quality is step 4)
0.2~0.5g, ultrasonic time are 20~30 minutes；Progress microwave heating, microwave power 400 in microwave reaction kettle are sealed in again
~800W, reaction time are 3~6 minutes, obtain nitrogen sulphur codope graphene solution；After being cooled to room temperature, wash, centrifugation,
Freeze-drying, sublimation drying 24 hours, obtains fluffy nitrogen sulphur codope graphene powder；
Step 5) is by nitrogen sulphur codope graphene powder obtained by step 4) with sublimed sulfur using mass ratio as 1：0.67~2.33
Ball milling after mixing, Ball-milling Time are 0.5~1 hour；Then product being heat-treated, heat treatment temperature is 155~160 DEG C,
Time is 10~12 hours, obtains nitrogen sulphur codope graphene lithium sulphur positive electrode.
The oxidized intercalation processing of native graphite, interlamellar spacing increase, after microwave heating, the functional group of interlayer and doped source are decomposed
Into gas, oxygen-containing functional group sloughs offer avtive spot；Doped source catabolite contacts these avtive spots and forms chemical bond,
Hetero atom is embedded into graphene lattice, and graphite oxide is reduced to graphene.
Embodiment 1
Graphite oxide is prepared using Hummers methods, graphite oxide is dispersed in ethanol：Water=9：Surpass in 1 mixed solution
The graphite oxide dispersion that concentration is 1g/L is made for 1 hour in sound；0.1g ammonium hydrogencarbonates ultrasound is dispersed in 40mL oxidation stones for 7 minutes
Black dispersion liquid；It is sealed in microwave reaction kettle, 400W microwaves is carried out in microwave reactor and are heated 60 seconds, obtain N doping graphite
Alkene solution suspension；After being cooled to room temperature, 0.2g vulcanized sodium ultrasound is added into nitrogen-doped graphene solution after 30 minutes, it is close
It is encapsulated in microwave reaction kettle and carries out 800W microwaves heating 5 minutes, obtains nitrogen sulphur codope graphene suspension；It is cooled to room temperature
Afterwards, it is washed with deionized, product is collected by centrifugation, freeze-drying obtains fluffy nitrogen sulphur codope graphene powder in 24 hours；
By nitrogen sulphur codope graphene powder and sublimed sulfur with 1：After 0.67 quality is than ball milling 1h, in ptfe autoclave
It is heat-treated 10 hours at 158 DEG C, obtains nitrogen sulphur codope graphene lithium sulphur composite positive pole.
Embodiment 2
Graphite oxide is prepared using Hummers methods, graphite oxide is dispersed in ethylene glycol：Water=9：In 1 mixed solution
The dispersion liquid that concentration is 1.2g/L is made for 1.5 hours in ultrasound；0.15g ammonium hydrogencarbonates ultrasound is dispersed in 40mL oxidation stones for 10 minutes
After black dispersion liquid, it is sealed in microwave reaction kettle, 500W microwaves is carried out in microwave reactor and are heated 60 seconds, obtain N doping stone
Black alkene solution suspension；After being cooled to room temperature.0.3g vulcanized sodium ultrasound is added into nitrogen-doped graphene solution after 20 minutes,
It is sealed in microwave reaction kettle and carries out 600W microwaves heating 6 minutes, obtains nitrogen sulphur codope graphene suspension；It is cooled to room
Wen Hou, it is washed with deionized, product is collected by centrifugation, freeze-drying obtains fluffy nitrogen sulphur codope Graphene powder in 24 hours
End；By nitrogen sulphur codope graphene powder and sublimed sulfur with 1:After 1.5 quality was than ball milling 1 hour, in polytetrafluoroethyl-ne alkene reaction
It is heat-treated 11 hours at 158 DEG C in kettle, obtains nitrogen sulphur codope graphene lithium/sulphur composite positive pole.
Embodiment 3
Graphite oxide is prepared using Hummers methods, graphite oxide is dispersed in 1-METHYLPYRROLIDONE：Water=8：2 it is mixed
Close ultrasound in solution and the dispersion liquid that concentration is 1.5g/L is made within 2 hours；0.2g ammonium hydrogencarbonates ultrasound is dispersed in 40mL oxygen in 5 minutes
After graphite dispersion liquid, it is sealed in microwave reaction kettle, 700W microwaves is carried out in microwave reactor and are heated 60 seconds, nitrogen is obtained and mixes
Miscellaneous graphene solution suspension；After being cooled to room temperature.25 points of 0.4g vulcanized sodium ultrasound is added into nitrogen-doped graphene solution
Zhong Hou, it is sealed in microwave reaction kettle and carries out 500W microwaves heating 3 minutes, obtain nitrogen sulphur codope graphene suspension；Treat cold
But to after room temperature, it is washed with deionized, product is collected by centrifugation, freeze-drying obtains fluffy nitrogen sulphur codope graphite in 24 hours
Alkene powder；By nitrogen sulphur codope graphene powder and sublimed sulfur with 1:After 2.33 quality was than ball milling 1 hour, in polytetrafluoroethylene (PTFE)
It is heat-treated 12 hours at 158 DEG C in reactor, obtains nitrogen sulphur codope graphene lithium sulphur composite positive pole.
Summary embodiment, battery assembling is further carried out using the sample prepared by embodiment 1~3：
1) preparation of positive pole
Respectively by 0.35g nitrogen sulphur codope graphene lithium sulphur composite material powder and 0.1g as made from embodiment 1~3
KS-6,0.05g binding agent Kynoar (PVDF) mix grinding, add 2mL 1-METHYLPYRROLIDONEs, and stirring forms uniform
Anode sizing agent.
The anode sizing agent is coated uniformly on 20 μm of aluminium foil, then dries after removing solvent, punching, be made at 60 DEG C
Area is 1.22cm2Positive pole disk, working electrode is made by vacuum drying, wherein containing about 2mg active material sulphur.
2) negative pole uses commercially available lithium ion battery lithium piece.
3) battery assembles
Experimental cell test material performance is assembled using button cell CR2025, assemble sequence is negative electrode casing-lithium piece-electrolysis
Liquid-barrier film-electrolyte-positive plate-pad-shell fragment-anode cover, then the battery assembled is packaged, whole process exists
Completed in argon gas glove box.
Test analysis is carried out to the above-mentioned each performance of assembled battery
Cycle performance is tested：CR2025 button cells obtained above are individually positioned in test system, stand 12h
Afterwards, constant current discharge is first carried out to 1.5V with 0.1C, then shelves 2min, constant current charge is then carried out to 3V with 0.1C.Record
The discharge capacity first of battery, the first discharge specific capacity of material is 1373mAh/g in embodiment 1, is then repeated the above steps
50 times, the discharge capacity of battery is recorded, discharge capacity maintains 425mAh/g after 50 circulations, capability retention 31%,
Compared with homogeneous electrode material, the capability retention of battery is effectively increased, other embodiments data are as shown in table 1 below.
Table 1, cycle performance test performance data comparison
Fig. 1 is the XRD spectrum of product obtained by embodiment 1：Native graphite is 25 ° or so in 2 θ a sharp feature
Diffraction maximum, represent the structure of graphite high-sequential.The graphite oxide prepared by Hummers methods, 2 θ are 25 ° or so of feature
Peak disappears, and the substitute is the sharp diffraction maximum that 2 θ are 10 ° or so, is the characteristic peak of graphite oxide.It is total to from nitrogen sulphur
In the XRD spectrum of doped graphene as can be seen that after microwave irradiation, the characteristic peak of graphite oxide disappears, and is 25 ° or so in 2 θ
Wide bag is presented, illustrates that graphite oxide is reduced, disordered structure is presented.
Fig. 2 is the charge-discharge test result of the nitrogen sulphur codope graphene lithium sulphur composite positive pole synthesized by embodiment 1.
Under room temperature 0.1C multiplying powers, specific discharge capacity is 425mAh/g after charge and discharge cycles 50 times.It can be seen that the nitrogen sulphur that the present invention synthesizes is total to
When doped graphene lithium sulphur composite is used as lithium sulfur battery anode material, the compound is with excellent cycle performance.
From the result of above-described embodiment, under different reaction conditions, nitrogen sulphur codope stone graphene lithium can be obtained
Sulphur composite positive pole, and material has good chemical property, the nitrogen sulphur for understanding to have the present invention to be prepared from the data of table 1
Battery made of codope graphene has higher initial discharge specific capacity, and repeatedly after circulation, remaining reversible capacity is higher, says
Caused avtive spot can effectively adsorb polysulfide after the bright progress Heteroatom doping to graphene, reduce the damage of active material
Lose, so as to lift the cycle performance of battery；And this law preparation technology is simple, and cost is low, can effectively solve sulphur just really
The applied defect of pole material.
Claims (1)
1. a kind of method that microwave liquid phase process prepares doped graphene lithium sulfur battery anode material, it is characterised in that according to following
Step is implemented：
Step 1) prepares graphite oxide using Hummers methods；
Step 2) is uniform in dispersant for ultrasonic dispersion by the graphite oxide obtained by step 1), ultrasonic time 1~2 hour, oxidation
Concentration of the graphite in dispersion liquid is 1~1.5g/L, and dispersant is from one in water, ethanol, ethylene glycol, 1-METHYLPYRROLIDONE
Kind or two or more combinations；
It is equal that step 3) adds 0.1~0.2g ammonium hydrogencarbonates ultrasonic disperse in the graphite oxide dispersion obtained by 40mL steps 2)
Even, ultrasonic time is 5~10 minutes；Microwave power is 400-800W, and the reaction time is 30~60 seconds；Then it is anti-to be sealed in microwave
Progress microwave heating in kettle is answered, obtains nitrogen-doped graphene solution；
Step 4) by vulcanized sodium ultrasonic disperse in the nitrogen-doped graphene solution obtained by step 3), vulcanized sodium quality be 0.2~
0.5g, ultrasonic time are 20~30 minutes；Microwave power is 400~800W, and the reaction time is 3~6 minutes；Sublimation drying
24 hours；
Progress microwave heating in microwave reaction kettle is sealed in again, obtains nitrogen sulphur codope graphene solution；After being cooled to room temperature,
Washing, centrifuge, freeze-drying, obtain fluffy nitrogen sulphur codope graphene powder；
Step 5) is by nitrogen sulphur codope graphene powder obtained by step 4) with sublimed sulfur using mass ratio as 1：0.67~2.33 mixing
Ball milling afterwards, Ball-milling Time are 0.5~1 hour；Then product is heat-treated, heat treatment temperature is 155~160 DEG C, the time
For 10~12 hours；Obtain nitrogen sulphur codope graphene lithium sulphur positive electrode.
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| CN106848185A (en) * | 2017-02-27 | 2017-06-13 | 华南师范大学 | A kind of positive electrode of sulfur-bearing nitrogen-doped graphene, positive pole and lithium/thinly chloride battery |
| JP7118139B2 (en) * | 2017-11-16 | 2022-08-15 | エルジー エナジー ソリューション リミテッド | Sulfur-carbon composite, method for producing the same, and lithium secondary battery containing the same |
| CN109037678B (en) * | 2018-06-15 | 2022-02-01 | 陕西科技大学 | Preparation method of nitrogen and sulfur co-doped three-dimensional graphene foam electrode active material |
| CN112320796B (en) * | 2020-10-30 | 2022-04-05 | 浙江锂宸新材料科技有限公司 | Preparation method for simply increasing graphite layer spacing |
| CN113423254B (en) * | 2021-05-26 | 2023-03-24 | 西安理工大学 | Composite wave absorbing agent with electromagnetic wave absorbing performance and preparation method thereof |
| CN114400313A (en) * | 2021-12-06 | 2022-04-26 | 西安理工大学 | Evaluation method and device for preparing graphene-sulfur composite cathode material by microwave method |
| CN114388737B (en) * | 2021-12-24 | 2022-12-02 | 西安理工大学 | Self-supporting electrode, preparation method thereof and lithium-sulfur battery |
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| CN103840160A (en) * | 2012-11-23 | 2014-06-04 | 海洋王照明科技股份有限公司 | Nitrogen-doped graphene composite material and preparation method thereof |
| CN103172057B (en) * | 2013-03-07 | 2015-08-26 | 华南理工大学 | A kind of preparation method of nitrogen sulphur codoped Graphene |
| CN103700859B (en) * | 2013-12-30 | 2016-01-06 | 温州大学 | Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application |
| CN106458601B (en) * | 2014-06-17 | 2019-09-20 | 埃琳娜·莫洛卡诺瓦 | The relevant material of graphene and graphene for manipulating cell membrane potential |
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| CN104766967A (en) * | 2015-03-18 | 2015-07-08 | 南京师范大学 | Preparation method of S/C composite material used in positive pole of Li-S battery |
| CN105271203B (en) * | 2015-11-18 | 2017-05-10 | 深圳大学 | porous co-doped graphene and preparation method thereof |
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