CN105514395A - Method for preparing cathode material of graphene-doped lithium sulfur battery by adopting microwave liquid phase process - Google Patents
Method for preparing cathode material of graphene-doped lithium sulfur battery by adopting microwave liquid phase process Download PDFInfo
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- CN105514395A CN105514395A CN201610079316.3A CN201610079316A CN105514395A CN 105514395 A CN105514395 A CN 105514395A CN 201610079316 A CN201610079316 A CN 201610079316A CN 105514395 A CN105514395 A CN 105514395A
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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
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a method for preparing a cathode material of a graphene-doped lithium sulfur battery by adopting the microwave liquid phase process. The method comprises the following steps: 1) preparing graphite oxide by utilizing the Hummers method; 2) performing ultrasonic dispersion on graphite oxide to disperse graphite oxide in a dispersing agent; 3) adding ammonium bicarbonate into graphite oxide dispersion liquid for ultrasonic dispersion, and sealing in a microwave reaction still for microwave heating, so as to obtain a nitrogen-doped graphene solution; 4) performing ultrasonic dispersion on sodium sulphide to disperse sodium sulphide in the nitrogen-doped graphene solution; and sealing again in a microwave reaction still for microwave heating, so as to obtain a nitrogen and sulfur co-doped graphene solution; cooling to the room temperature, washing, centrifuging, and freeze drying, so as to obtain fluffy nitrogen and sulfur co-doped graphene powder; 5) mixing the nitrogen and sulfur co-doped graphene powder with sublimed sulfur for ball-milling, performing heat treatment on the product, so as to obtain the nitrogen and sulfur co-doped graphene lithium-sulfur cathode material. The method provided by the invention is simple in processes, and the obtained material is good in electrochemical performance.
Description
Technical field
The invention belongs to nano composite material technical field, relate to a kind of method that microwave liquid phase process prepares doped graphene lithium sulfur battery anode material.
Background technology
Along with social high speed development growing with each passing day to demand for energy, and the pollution of fossil fuel to environment and the exhaustion of reserves, make people day by day urgent to the demand of novel alternative energy source.Lithium-sulfur cell has very high energy density (2600Wh/kg), and its positive electrode sulphur has stores the advantages such as abundant, environmentally friendly, and therefore lithium-sulfur cell becomes the Research Emphasis of secondary cell of future generation.But the difficult problem such as change and the dissolving of intermediate product many sulphions of volume, makes lithium-sulfur cell be difficult at present realize commercialization in the high-insulativity of sulphur, charge and discharge process.Graphene has the conductivity of superelevation and excellent mechanical property, and the composite material itself and sulphur made can solve the problem effectively as cell positive material.
Graphene is the hexagon surrounded by six carbon atom, and thickness is an atomic layer.Connected by σ key between carbon atom, combination is sp
2hydridization, the electric property of its excellence causes domestic and international researchers to its concern in energy storage material application aspect.In order to expand further and the physico-chemical property of Effective Regulation Graphene, usually availablely close with C atomic electronegativity to adulterate as atoms such as N, S, B, P.
The existing method preparing doped graphene has vapour deposition process, arc discharge method, hydro thermal method, circumfluence method etc., but above method exists severe reaction conditions, complex process, needs to use hazardous gas, and the shortcoming such as consume energy large.Therefore need to develop a kind of low energy consumption, the doping method of environmental protection, microwave method, due to the feature such as energy-conservation, efficient, becomes the focus of concern gradually.The microwave absorption capacity of material with carbon element is the chemical composition and the structure that highly depend on them.Graphite oxide is with a large amount of oxygen-containing functional groups, in microwave irradiation process, the not oxidized conjugation region of graphite oxide is as microwave absorption district, produce instantaneous high heat, oxygen-containing functional group is decomposed into gas and sloughs, and produce avtive spot, doped source is decomposed into the active specy containing targeted heteroatom, after contact avtive spot, hetero-atom is embedded in Graphene lattice with the form of covalent bond, achieves the reduction of graphite oxide and the doping of Graphene simultaneously.
Summary of the invention
The object of this invention is 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, need to use hazardous gas, consume energy large problem.
The technical solution adopted in the present invention is, a kind of microwave liquid phase process prepares the method for doped graphene lithium sulfur battery anode material, implements according to following steps:
Step 1) utilize Hummers legal system for graphite oxide;
Step 2) by step 1) graphite oxide of gained is even in dispersant for ultrasonic dispersion, the concentration of graphite oxide in dispersion liquid is 1 ~ 1.5g/L, ultrasonic time 1 ~ 2 hour;
Step 3) 0.1 ~ 0.2g ammonium hydrogencarbonate is added 40mL step 2) ultrasonic disperse is even in the graphite oxide dispersion of gained; Then be sealed in microwave reaction kettle and carry out microwave heating, obtain nitrogen-doped graphene solution;
Step 4) by vulcanized sodium ultrasonic disperse in step 3) in the nitrogen-doped graphene solution of gained, vulcanized sodium quality is 0.2 ~ 0.5g; Be sealed in again in microwave reaction kettle and carry out microwave heating, obtain nitrogen sulphur codope graphene solution; To be cooled to room temperature, washing, centrifugal, freeze drying, obtains fluffy nitrogen sulphur codope graphene powder;
Step 5) by step 4) gained nitrogen sulphur codope graphene powder and sublimed sulfur take mass ratio as ball milling after 1:0.67 ~ 2.33 mix; Then product is heat-treated, obtain nitrogen sulphur codope Graphene lithium sulphur positive electrode.
The invention has the beneficial effects as follows, main from mode of heating, the technique that tradition prepares doped graphene material to be improved, substitute traditional heating with microwave radiation technology to adulterate to Graphene simultaneously and to peel off, not only there is the feature of homogeneous heating, efficient energy-saving, and greatly can improve reaction rate, and avoid the use of poisonous reducing agent hydrazine hydrate, environmental protection; During using gained doped graphene as positive electrode, lithium-sulfur cell shows excellent chemical property.
Accompanying drawing explanation
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, and wherein abscissa is the angle of diffraction (2 θ), and unit is degree, and ordinate is diffracted intensity, and unit is cps;
Fig. 2 is the charging and discharging curve of nitrogen sulphur codope Graphene lithium sulphur composite positive pole under room temperature 0.1C multiplying power, and wherein abscissa is specific discharge capacity, and unit is mAh/g, and ordinate is voltage, and unit is V.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Microwave liquid phase process of the present invention prepares the method for doped graphene lithium sulfur battery anode material, implements according to following steps:
Step 1) utilize Hummers legal system for graphite oxide; (Hummers method is existing disclosed method, no longer carefully states at this);
Step 2) by step 1) graphite oxide of gained is even in dispersant for ultrasonic dispersion, the concentration of graphite oxide in dispersion liquid is 1 ~ 1.5g/L, ultrasonic time 1 ~ 2 hour; Dispersant selects one or more the combination in water, ethanol, ethylene glycol, 1-METHYLPYRROLIDONE;
Step 3) 0.1 ~ 0.2g ammonium hydrogencarbonate is added 40mL step 2) ultrasonic disperse is even in the graphite oxide dispersion of gained, ultrasonic time is 5 ~ 10 minutes; Then be sealed in microwave reaction kettle and carry out microwave heating, microwave power is 400-800W, and the reaction time is 30 ~ 60 seconds, obtains nitrogen-doped graphene solution;
Step 4) by vulcanized sodium ultrasonic disperse in step 3) in the nitrogen-doped graphene solution of gained, vulcanized sodium quality is 0.2 ~ 0.5g, and ultrasonic time is 20 ~ 30 minutes; Be sealed in microwave reaction kettle again and carry out microwave heating, microwave power is 400 ~ 800W, and the reaction time is 3 ~ 6 minutes, obtains nitrogen sulphur codope graphene solution; To be cooled to room temperature, washing, centrifugal, freeze drying, sublimation drying 24 hours, obtains fluffy nitrogen sulphur codope graphene powder;
Step 5) by step 4) gained nitrogen sulphur codope graphene powder and sublimed sulfur take mass ratio as ball milling after 1:0.67 ~ 2.33 mix, Ball-milling Time is 0.5 ~ 1 hour; Then heat-treated by product, heat treatment temperature is 155 ~ 160 DEG C, and the time is 10 ~ 12 hours, obtains nitrogen sulphur codope Graphene lithium sulphur positive electrode.
Native graphite is through oxidation intercalation processing, and interlamellar spacing increases, and after microwave heating, functional group and the doped source of interlayer resolve into gas, and sloughing of oxygen-containing functional group provides avtive spot; Doped source catabolite contacts these avtive spots and forms chemical bond, and hetero-atom is embedded in Graphene lattice, and graphite oxide is reduced to Graphene.
Embodiment 1
Utilize Hummers legal system for graphite oxide, graphite oxide is dispersed in ethanol: within the mixed solution of water=9:1 ultrasonic 1 hour, make the graphite oxide dispersion that concentration is 1g/L; 40mL graphite oxide dispersion is dispersed in by ultrasonic for 0.1g ammonium hydrogencarbonate 7 minutes; Be sealed in microwave reaction kettle, in microwave reactor, carry out 400W microwave heating 60 seconds, obtain nitrogen-doped graphene solution suspension-turbid liquid; To be cooled to room temperature, in nitrogen-doped graphene solution, add 0.2g vulcanized sodium after ultrasonic 30 minutes, be sealed in microwave reaction kettle and carry out 800W microwave heating 5 minutes, obtain nitrogen sulphur codope Graphene suspension-turbid liquid; To be cooled to room temperature, spend deionized water, collected by centrifugation product, freeze drying obtains fluffy nitrogen sulphur codope graphene powder for 24 hours; By nitrogen sulphur codope graphene powder with sublimed sulfur with the quality of 1:0.67 than after ball milling 1h, in polytetrafluoroethylene reactor, heat treatment 10 hours at 158 DEG C, obtains nitrogen sulphur codope Graphene lithium sulphur composite positive pole.
Embodiment 2
Utilize Hummers legal system for graphite oxide, graphite oxide is dispersed in ethylene glycol: within the mixed solution of water=9:1 ultrasonic 1.5 hours, make the dispersion liquid that concentration is 1.2g/L; After being dispersed in 40mL graphite oxide dispersion by ultrasonic for 0.15g ammonium hydrogencarbonate 10 minutes, be sealed in microwave reaction kettle, in microwave reactor, carry out 500W microwave heating 60 seconds, obtain nitrogen-doped graphene solution suspension-turbid liquid; To be cooled to room temperature.In nitrogen-doped graphene solution, add 0.3g vulcanized sodium after ultrasonic 20 minutes, be sealed in microwave reaction kettle and carry out 600W microwave heating 6 minutes, obtain nitrogen sulphur codope Graphene suspension-turbid liquid; To be cooled to room temperature, spend deionized water, collected by centrifugation product, freeze drying obtains fluffy nitrogen sulphur codope graphene powder for 24 hours; After time less than ball milling 1 with the quality of 1:1.5 to nitrogen sulphur codope graphene powder and sublimed sulfur, in polytetrafluoroethylene reactor, heat treatment 11 hours at 158 DEG C, obtains nitrogen sulphur codope Graphene lithium/sulphur composite positive pole.
Embodiment 3
Utilize Hummers legal system for graphite oxide, graphite oxide is dispersed in 1-METHYLPYRROLIDONE: within the mixed solution of water=8:2 ultrasonic 2 hours, make the dispersion liquid that concentration is 1.5g/L; After being dispersed in 40mL graphite oxide dispersion by ultrasonic for 0.2g ammonium hydrogencarbonate 5 minutes, be sealed in microwave reaction kettle, in microwave reactor, carry out 700W microwave heating 60 seconds, obtain nitrogen-doped graphene solution suspension-turbid liquid; To be cooled to room temperature.In nitrogen-doped graphene solution, add 0.4g vulcanized sodium after ultrasonic 25 minutes, be sealed in microwave reaction kettle and carry out 500W microwave heating 3 minutes, obtain nitrogen sulphur codope Graphene suspension-turbid liquid; To be cooled to room temperature, spend deionized water, collected by centrifugation product, freeze drying obtains fluffy nitrogen sulphur codope graphene powder for 24 hours; After time less than ball milling 1 with the quality of 1:2.33 to nitrogen sulphur codope graphene powder and sublimed sulfur, in polytetrafluoroethylene reactor, heat treatment 12 hours at 158 DEG C, obtains nitrogen sulphur codope Graphene lithium sulphur composite positive pole.
Comprehensive above-described embodiment, adopts the sample prepared by embodiment 1 ~ 3 to carry out battery assembling further:
1) preparation of positive pole
The nitrogen sulphur codope Graphene lithium sulphur composite material powder respectively 0.35g obtained by embodiment 1 ~ 3 and 0.1gKS-6, the mixed grinding of 0.05g binding agent Kynoar (PVDF), add 2mLN-methyl pyrrolidone, stir and form even anode sizing agent.
Evenly be coated in by this anode sizing agent on the aluminium foil of 20 μm, then at 60 DEG C after dry desolventizing, punching, obtained area is 1.22cm
2positive pole disk, make work electrode through vacuumize, wherein containing 2mg active material sulphur of having an appointment.
2) negative pole adopts commercially available lithium ion battery lithium sheet.
3) battery assembling
Button cell CR2025 is adopted to assemble experimental cell test material performance, assemble sequence is negative electrode casing-lithium sheet-electrolyte-barrier film-electrolyte-positive plate-pad-shell fragment-anode cover, encapsulated by the battery assembled, whole process all completes in argon gas glove box again.
Test analysis is carried out to each performance of above-mentioned assembled battery
Cycle performance is tested: be placed on respectively on test macro by above-mentioned obtained CR2025 button cell, after leaving standstill 12h, first carries out constant current discharge to 1.5V with 0.1C, then shelves 2min, then carry out constant current charge to 3V with 0.1C.The discharge capacity first of record battery, in embodiment 1, the first discharge specific capacity of material is 1373mAh/g, then above-mentioned steps 50 times are repeated, the discharge capacity of record battery, after 50 circulations, discharge capacity maintains 425mAh/g, and capability retention is 31%, compared with homogeneous electrode material, effectively improve the capability retention of battery, other embodiment data are as shown in table 1 below.
Table 1, cycle performance test performance Data Comparison
The XRD collection of illustrative plates of Fig. 1 product obtained by embodiment 1: native graphite is about 25 ° at 2 θ a sharp-pointed characteristic diffraction peak, represents the structure of graphite high-sequential.By the graphite oxide that Hummers legal system is standby, 2 θ are that the characteristic peak of about 25 ° disappears, and the substitute is 2 θ is the sharp-pointed diffraction maximum of about 10 ° one, is the characteristic peak of graphite oxide.As can be seen from the XRD collection of illustrative plates of nitrogen sulphur codope Graphene, after microwave irradiation, the characteristic peak of graphite oxide disappears, and is about 25 ° and presents wide bag, illustrate that graphite oxide is reduced, present disordered structure at 2 θ.
The charge-discharge test result of the nitrogen sulphur codope Graphene lithium sulphur composite positive pole of Fig. 2 synthesized by embodiment 1.Under room temperature 0.1C multiplying power, after charge and discharge cycles 50 times, specific discharge capacity is 425mAh/g.Visible, when the nitrogen sulphur codope Graphene lithium sulphur composite material of the present invention's synthesis is used as lithium sulfur battery anode material, this compound has excellent cycle performance.
From the result of above-described embodiment, under different reaction conditions, all can obtain nitrogen sulphur codope stone Graphene lithium sulphur composite positive pole, and material has good chemical property, the battery that the nitrogen sulphur codope Graphene prepared from the known the present invention of having of table 1 data is made has higher initial discharge specific capacity, repeatedly after circulation, residue reversible capacity is higher, illustrate that the avtive spot produced after carrying out Heteroatom doping to Graphene effectively can adsorb polysulfide, reduce the loss of active material, thus promote the cycle performance of battery; And this law preparation technology is simple, and cost is low, really effectively can solve the applied defect of sulphur positive electrode.
Claims (5)
1. microwave liquid phase process prepares a method for doped graphene lithium sulfur battery anode material, it is characterized in that, implements according to following steps:
Step 1) utilize Hummers legal system for graphite oxide;
Step 2) by step 1) graphite oxide of gained is even in dispersant for ultrasonic dispersion, the concentration of graphite oxide in dispersion liquid is 1 ~ 1.5g/L, ultrasonic time 1 ~ 2 hour;
Step 3) 0.1 ~ 0.2g ammonium hydrogencarbonate is added 40mL step 2) ultrasonic disperse is even in the graphite oxide dispersion of gained; Then be sealed in microwave reaction kettle and carry out microwave heating, obtain nitrogen-doped graphene solution;
Step 4) by vulcanized sodium ultrasonic disperse in step 3) in the nitrogen-doped graphene solution of gained, vulcanized sodium quality is 0.2 ~ 0.5g; Be sealed in again in microwave reaction kettle and carry out microwave heating, obtain nitrogen sulphur codope graphene solution; To be cooled to room temperature, washing, centrifugal, freeze drying, obtains fluffy nitrogen sulphur codope graphene powder;
Step 5) by step 4) gained nitrogen sulphur codope graphene powder and sublimed sulfur take mass ratio as ball milling after 1:0.67 ~ 2.33 mix; Then product is heat-treated, obtain nitrogen sulphur codope Graphene lithium sulphur positive electrode.
2. microwave liquid phase process according to claim 1 prepares the method for doped graphene lithium sulfur battery anode material, it is characterized in that: described step 2) in, dispersant selects one or more the combination in water, ethanol, ethylene glycol, 1-METHYLPYRROLIDONE.
3. microwave liquid phase process according to claim 1 prepares the method for doped graphene lithium sulfur battery anode material, it is characterized in that: described step 3) in, ultrasonic time is 5 ~ 10 minutes; Microwave power is 400-800W, and the reaction time is 30 ~ 60 seconds.
4. microwave liquid phase process according to claim 1 prepares the method for doped graphene lithium sulfur battery anode material, it is characterized in that: described step 4) in, ultrasonic time is 20 ~ 30 minutes; Microwave power is 400 ~ 800W, and the reaction time is 3 ~ 6 minutes; Sublimation drying 24 hours.
5. microwave liquid phase process according to claim 1 prepares the method for doped graphene lithium sulfur battery anode material, it is characterized in that: described step 5) in, Ball-milling Time is 0.5 ~ 1 hour; Heat treatment temperature is 155 ~ 160 DEG C, and the time is 10 ~ 12 hours.
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| CN109037678A (en) * | 2018-06-15 | 2018-12-18 | 陕西科技大学 | A kind of preparation method of nitrogen sulphur codope three-dimensional graphene foam electrode active material |
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| CN113423254A (en) * | 2021-05-26 | 2021-09-21 | 西安理工大学 | Composite wave absorbing agent with electromagnetic wave absorbing performance and preparation method thereof |
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| 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 |
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