CN102769126A - Method for preparing nano-sulfur / graphene oxide composite electrode material - Google Patents
Method for preparing nano-sulfur / graphene oxide composite electrode material Download PDFInfo
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Abstract
The invention relates to a method for preparing a nano-sulfur / graphene oxide composite material with high specific capacity and belongs to the field of cross application of material synthesis and electrochemical power supplies. The nano-sulfur / graphene oxide composite material is applicable to an electrode material of a lithium sulfur secondary battery with the high specific capacity. The method is characterized by comprising the following steps of: synthesizing nano-sulfur particles by using a simple chemical method under the protection of a surfactant; and uniformly attracting graphene oxide and a carbon material to the surfaces of the nano-sulfur particles by interaction of the surfactant and the graphene oxide to form a core-shell type nano-sulfur / graphene oxide composite material. The graphene oxide and the carbon material coat a sulfur surface, so a sulfur electrode material is stable in structure, high in electric conductivity and high in cycle performance. Environmentally-harmful materials are not employed, and the method can be implemented at low temperature, and is low in energy consumption in the synthesis process and low in equipment requirement. The synthesized material is high in charging/discharging capacity, non-toxic and harmless to a human body, and sulfur is abundant in nature, so the material has a good industrial prospect and can be applied to large-scale industrial production.
Description
Technical field
The present invention adopt chemical method prepare nanoscale sulphur, with graphene oxide coat material modified, and, make up the lithium-sulphur cell positive electrode material of height ratio capacity and good cycle with its positive electrode as lithium-sulfur cell.
Background technology
In recent years, battery is being played the part of more and more important role in modern society, to the demands for higher performance of battery.So the preparation and the Electrochemical Properties of high-energy-density lithium-sulphur cell positive electrode material become popular project.The specific energy of tradition positive electrode is all lower, is that anodal material is compared with other battery systems at specific energy and specific power and all had greater advantage thereby receive extensive concern with the elemental sulfur.
Lithium-sulfur rechargeable battery be with the sulfur-bearing active component be positive pole, organic non-aqueous solution system of containing lithium salts is that electrolyte, lithium metal are that negative pole constitutes, with the electrochemical cleavage of S-S key and again bonding be the battery system of principle.According to final reduction reaction product Li
2S calculates, and the theoretical specific capacity of elemental sulfur is 1675 mAh/g, and lithium metal has theoretical specific capacity 3860 mAh/g, and the final theoretical energy density of Li/S battery is more than 5 times of lithium ion battery theoretical energy density up to 2600 Wh/kg.
Though lithium-sulfur rechargeable battery has plurality of advantages, its extensive use in reality that still had some issues limit to be solved.The lithium-sulphur cell positive electrode active material elemental sulfur is the insulator of electronics and ion, must contact closely with conductive agent and could accomplish reversible electrochemical reaction, but the affiliation that adds of conductive agent increases electrode weight, reduces the energy density of battery.The dispersity of active material sulphur in the conductive agent skeleton also determined the mass transfer rate and the electrical conductivity speed of electrochemical reaction, and be inhomogeneous if active material disperses, and will reduce active material utilization, thereby influence the discharge capacity and the cycle performance of battery.
The present invention is intended to study the application of nanometer sulphur on lithium-sulfur cell.Under influence of surfactant, coat after adopting chemical method to prepare nanometer sulphur with graphene oxide; Add suitable carbonaceous conductive agent simultaneously; To reach evenly compound purpose; The many sulphions that suppress as far as possible to produce in the electrochemical reaction process dissolve and shuttling back and forth at two interpolars; Improve the electrochemical stability and the cycle performance of positive electrode, realize discharging and recharging 100 cyclic discharge capacities and maintain 650 mAh/g above (with graphene oxide and sulphur total weight), the lithium-sulphur cell positive electrode material that the preparation high power capacity has the excellent cycle performance.
Summary of the invention
The objective of the invention is to the deficiency to prior art, invented a kind of composite material, can be used for the lithium-sulphur cell positive electrode material with nanometer sulphur/graphene oxide electro-chemical activity, high capacity density and high-energy-density.
For achieving the above object, the present invention adopts following technical scheme:
1. prepare graphene oxide with existing chemical oxidation method;
2. the elemental sulfur for preparing nano-grade size with chemical method;
3. be adsorbed on the reunion that the sulphur surface prevents nanometer sulphur with different surface active agents such as TritonX, DTAB, neopelexes;
4. coat with graphene oxide, and an amount of carbonaceous conductive material that mixes therein is to improve the conductivity of sulphur;
5. prepared material is carried out conductivity and electrochemical property test.
The preparation method of a kind of nanometer sulphur of the present invention/graphene oxide combination electrode material, the processing step and the condition of this method are following:
The material that a. will be used for generating nanometer sulphur joins deionized water, through stirring, ultrasonic material being dissolved fully; Surfactant TritonX or DTAB or neopelex are joined in the there-necked flask that deionized water is housed, stir under the room temperature and make it to dissolve fully; Wherein the weight ratio of the nanometer sulphur of surfactant and generation is 0.01:1 ~ 0.1:1; Two solution are mixed at there-necked flask;
B. with above-mentioned there-necked flask constant temperature 20min in 25-70 ℃ of oil bath that solution is housed, slowly drip an amount of dense HCl, continue constant temperature 10min ~ 10h; Under vigorous stirring, add the 50mL water-alcohol solution that contains graphene oxide and material with carbon element acetylene black or single wall and multi-walled carbon nano-tubes; Wherein the weight ratio of graphene oxide and material with carbon element is 1:1 ~ 5:1; Continue to be cooled to room temperature behind reaction 10min ~ 1h;
C. with said mixture through centrifugal, washing with alcohol, after drying under 60 ~ 80 ℃ of temperature, obtain nanometer sulphur/graphene oxide composite material.
The described material that is used to generate nanometer sulphur is a sodium thiosulfate, or vulcanized sodium and sublimed sulfur, or vulcanized sodium and ferric trichloride.
Described graphene oxide is selected from Hummers chemical oxidation graphite method or improves resulting 3 ~ 10 layers of graphene oxide of Hummers method.
In order to test the electro-chemical activity of prepared material, it is 2016 lithium-sulfur cell that the present invention has assembled the model that can discharge and recharge with nanometer sulphur/graphene oxide composite material as positive pole.The assembling of electrode preparation and battery: active material/acetylene black/binding agent=80%/10%/10% (mass ratio); After magnetic mixes 5 ~ 10 h; Blade coating is in the aluminium foil surface of cleaning; 40 ~ 80 ℃ are descended dry 12 ~ 24h in vacuum drying chamber, process the positive plate of certain diameter again, through forcing press anode pole piece are flattened at last; Negative pole adopts business-like lithium sheet; 1 of two (trifluoromethane sulfonic acid) imines lithium of electrolyte employing 1mol/L, 3-dioxolanes-glycol dimethyl ether mixes organic mixed solution.Prepared secondary lithium-sulfur cell current density with 0.1C under 20 ℃ discharges and recharges, positive active material specific capacity 600 ~ 800 mAh/g, cycle charge-discharge 100 times, capability retention nearly 90%.
Good dispersion, the particle size that the nanometer sulphur/graphene oxide composite material of gained of the present invention has material novelty, sulphur is little, capacity is high, good stability, preparation technology simple, low cost and other advantages.
For understanding the present invention further, special elaborate with instance, and provide that accompanying drawing describes nanometer sulphur/graphene oxide composite material involved in the present invention synthetic with and as the chemical property of lithium-sulfur cell positive electrode.
Description of drawings
Fig. 1 is to be the XRD comparison diagram of feedstock production nanometer sulphur/graphene oxide composite material and sublimed sulfur with sodium thiosulfate;
Fig. 2 is to be the electrochemical property test figure of feedstock production nanometer sulphur/graphene oxide composite material with sodium thiosulfate;
Fig. 3 is to be the XRD figure of feedstock production sulphur/graphene oxide composite material and sublimed sulfur with vulcanized sodium and sublimed sulfur;
Fig. 4 is to be the electrochemical property test figure of feedstock production sulphur/graphene oxide composite material with vulcanized sodium and sublimed sulfur;
Fig. 5 is that employing vulcanized sodium and ferric trichloride are the XRD comparison diagram of feedstock production nanometer sulphur/graphene oxide composite material and sublimed sulfur;
Fig. 6 uses vulcanized sodium and the ferric trichloride electrochemical property test figure as feedstock production sulphur/graphene oxide composite material.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment one
Prepare nanometer sulphur/graphene oxide composite material with chemical method, its process and step are following:
Adopting sodium thiosulfate is feedstock production nanometer sulphur/graphene oxide composite material: with 1.5g Na
2S
2O
3Be dissolved in the deionized water of 250ml, add 10 mL concentration and be 1% neopelex, in a clean there-necked flask, stir 1h; Carefully be transferred to 70 ℃ of oil baths, slowly drip the dense HCl of 12mL, insulation 10min; Under vigorous stirring, add the 50mL water-alcohol solution that contains 20mg graphene oxide and 10mg acetylene black, be cooled to room temperature behind the 20min, centrifugal, behind 60 ℃ of vacuumize 12h, get positive electrode.
Referring to accompanying drawing 1, Fig. 1 is the XRD figure spectrum of sublimed sulfur and S graphene oxide (GO).Retrieval can find out with sodium thiosulfate to be the sulphur well-crystallized that raw material reaction generates according to the PCPDS card; Diffraction maximum is obvious; Calculate the about 65nm of sulfur granules size according to the Scherrer formula; The diffraction maximum of graphene oxide embodies not obvious owing to its content is less relatively, but can judge that through the increase of product shade and quality nanometer sulphur can be compound preferably with graphene oxide.
The gained composite material is processed electrode as follows: take by weighing 80mg nanometer sulphur/graphene oxide composite material, 10mg acetylene black stirs the back with both and adds binding agent; After stirring 5h; Slurry is coated on the aluminium foil of surface cleaning, in 80 ℃ of vacuumize 12h, diameter 9mm pole piece is cut into as positive pole with slicing machine in the back; Metal lithium sheet is to electrode; Polypropylene microporous film is a barrier film, 1 of two (trifluoromethane sulfonic acid) imines lithium of electrolyte employing 1mol/L, and 3-dioxolanes-glycol dimethyl ether mixes organic mixed solution.In the argon gas glove box, be assembled into 2016 button cells and carry out electro-chemical test.Probe temperature is 20 ℃, discharges and recharges between 1.0 to 3.0 volts with the charge-discharge velocity of 0.1mA.Referring to accompanying drawing 2, the initial charge specific capacity of measured S-graphene oxide composite material is 1350 mAh/g (calculating with S-graphene oxide composite material weight), first discharge specific capacity 730 mAh/g, and 100 discharge capacities that circulate maintain 650 mAh/g.Demonstrated electrochemical stability preferably.And bright sulfur is without the graphene oxide modification, and chemical property is very poor, charges and discharge specific capacity first and is merely 420 mAh/g, and circulating, capacity only has 300 mAh/g after 100 times.
Embodiment two
Prepare nanometer sulphur/graphene oxide composite material with chemical method, its process and step are following:
Adopting vulcanized sodium and sublimed sulfur is feedstock production nanometer sulphur/graphene oxide composite material: with 0.3g sublimed sulfur and 0.3gNa
2S joins in the deionized water, and ultrasonic 5h treats that sublimed sulfur dissolves fully, the 100mg DTAB is distributed in the there-necked flask of 250 mL deionized waters, evenly is stirred to dissolving fully.Above-mentioned two kinds of solution are mixed stirring 2h to being crocus; Carefully be transferred to 70 ℃ of oil baths, slowly drip the dense HCl of 12mL, insulation 10min; Under vigorous stirring, add the 20mg graphene oxide and with the 50mL water-alcohol solution of 10mg acetylene black, be cooled to room temperature behind the 20min, centrifugal, after 60 ℃ of vacuumize positive electrode.
Referring to accompanying drawing 3, Fig. 3 is the XRD figure spectrum of sublimed sulfur and S graphene oxide (GO).Retrieval can find out that with vulcanized sodium and sublimed sulfur be the sulphur well-crystallized that raw material reaction generates according to the PCPDS card; Diffraction maximum is obvious; Calculate the about 65nm of sulfur granules size according to the Scherrer formula; The diffraction maximum of graphene oxide embodies not obvious owing to its content is less relatively, but can judge that through the increase of product shade and quality nanometer sulphur can be compound preferably with graphene oxide.
The gained composite material is processed electrode as follows: take by weighing 80mg nanometer sulphur/graphene oxide composite material, 10mg acetylene black stirs the back with both and adds binding agent; After stirring 5h; Slurry is coated on the aluminium foil of surface cleaning, in 80 ℃ of vacuumize 12h, diameter 9mm pole piece is cut into as positive pole with slicing machine in the back; Metal lithium sheet is a negative pole; Polypropylene microporous film is a barrier film, 1 of two (trifluoromethane sulfonic acid) imines lithium of electrolyte employing 1mol/L, and 3-dioxolanes-glycol dimethyl ether mixes organic mixed solution.In the argon gas glove box, be assembled into 2016 button cells and carry out electro-chemical test.Probe temperature is 20 ℃, discharges and recharges between 1.0 to 3.0 volts with the charge-discharge velocity of 0.1mA.Referring to accompanying drawing 4; The initial charge specific capacity of measured S-graphene oxide composite material is 1145 mAh/g (calculating with S-graphene oxide composite material weight); First discharge specific capacity 690 mAh/g; 100 discharge capacities that circulate maintain 640 mAh/g, have demonstrated electrochemical stability preferably.And bright sulfur is without the graphene oxide modification, and chemical property is very poor, charges and discharge specific capacity first and is merely 420 mAh/g, and circulating, capacity only has 300 mAh/g after 100 times.
Embodiment three
Prepare nanometer sulphur/graphene oxide composite material with chemical method, its process and step are following:
Adopting vulcanized sodium and ferric trichloride is feedstock production nanometer sulphur/graphene oxide composite material; Specific as follows: that 1g vulcanized sodium and 0.01g TritonX are dissolved in respectively in the deionized water of 100ml; In a clean there-necked flask, both are mixed and stir 1h, under 25 ℃, to wherein adding the dense HCl of 2mL; The liquor ferri trichloridi that after vulcanized sodium and dense HCl reaction generates hydrogen sulfide, slowly adds the 1mol/L of 100mL with constant pressure funnel; And the sealing there-necked flask, strong agitation reaction 10h makes ferric trichloride can the abundant oxidation of hydrogen sulfide be generated elemental sulfur; Under vigorous stirring, add the 50mL water-alcohol solution of 20mg graphene oxide and 10mg acetylene black, be cooled to room temperature behind the 20min, centrifugal, behind 80 ℃ of vacuumize 12h, get positive electrode.
Referring to accompanying drawing 5, Fig. 5 is the XRD figure spectrum of sublimed sulfur and S graphene oxide (GO).Retrieval can find out that with vulcanized sodium and ferric trichloride be the sulphur well-crystallized that raw material reaction generates according to the PCPDS card; Diffraction maximum is obvious; Calculate about 78 nm of sulfur granules size according to the Scherrer formula; The diffraction maximum of graphene oxide embodies not obvious owing to its content is less relatively, but can judge that through the increase of product shade and quality nanometer sulphur can be compound preferably with graphene oxide.
The gained composite material is processed electrode as follows: take by weighing 80mg nanometer sulphur/graphene oxide composite material, 10mg acetylene black stirs the back with both and adds binding agent; After stirring 5h; Slurry is coated on the aluminium foil of surface cleaning, in 80 ℃ of vacuumize 12h, diameter 9mm pole piece is cut into as positive pole with slicing machine in the back; Metal lithium sheet is a negative pole; Polypropylene microporous film is a barrier film, 1 of two (trifluoromethane sulfonic acid) imines lithium of electrolyte employing 1mol/L, and 3-dioxolanes-glycol dimethyl ether mixes organic mixed solution.In the argon gas glove box, be assembled into 2016 button cells and carry out electro-chemical test.Probe temperature is 20 ℃, discharges and recharges between 1.0 to 3.0 volts with the charge-discharge velocity of 0.1mA.Referring to Fig. 6; The initial charge specific capacity of measured S-graphene oxide composite material is 975 mAh/g (calculating with S-graphene oxide composite material weight); First discharge specific capacity 730 mAh/g; 100 discharge capacities that circulate maintain 700 mAh/g, have demonstrated electrochemical stability preferably.And bright sulfur is without the graphene oxide modification, and chemical property is very poor, charges and discharge specific capacity first and is merely 420 mAh/g, and circulating, capacity only has 300 mAh/g after 100 times.
Claims (3)
1. the preparation method of nanometer sulphur/graphene oxide combination electrode material, the processing step and the condition of this method are following:
The material that a. will be used for generating nanometer sulphur joins deionized water, through stirring, ultrasonic material being dissolved fully; Surfactant TritonX or DTAB or neopelex are joined in the there-necked flask that deionized water is housed, stir under the room temperature and make it to dissolve fully; Wherein the weight ratio of the nanometer sulphur of surfactant and generation is 0.01:1 ~ 0.1:1; Two solution are mixed at there-necked flask;
B. with above-mentioned there-necked flask constant temperature 20min in 30-70 ℃ of oil bath that solution is housed, slowly drip an amount of dense HCl, continue constant temperature 10min ~ 1h; Under vigorous stirring, add the 50mL water-alcohol solution that contains graphene oxide and material with carbon element acetylene black or single wall and multi-walled carbon nano-tubes; Wherein the weight ratio of graphene oxide and material with carbon element is 1:1 ~ 5:1; Continue to be cooled to room temperature behind reaction 10min ~ 1h;
C. with said mixture through centrifugal, washing with alcohol, after drying under 60 ~ 80 ℃ of temperature, obtain nanometer sulphur/graphene oxide composite material.
2. the preparation method of nanometer sulphur as claimed in claim 1/graphene oxide combination electrode material is characterized in that the wherein said material that is used to generate nanometer sulphur is a sodium thiosulfate, or vulcanized sodium and sublimed sulfur, or vulcanized sodium and ferric trichloride.
3. nanometer sulphur as claimed in claim 1/graphene oxide combination electrode material preparation method is characterized in that described graphene oxide is selected from Hummers chemical oxidation graphite method or improves resulting 3 ~ 10 layers of graphene oxide of Hummers method.
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| CN103219519A (en) * | 2013-04-28 | 2013-07-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of lithium-sulphur battery positive pole material with sulfur-graphene composite structure |
| CN104043481A (en) * | 2014-06-12 | 2014-09-17 | 河南农业大学 | Preparation method for functionalized graphene loaded noble metal nano-crystalline composite catalyst |
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| CN104078661A (en) * | 2014-05-23 | 2014-10-01 | 南京中储新能源有限公司 | Carbon nanotube-nanosulfur composite material and secondary aluminium battery using same |
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| WO2017139939A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Method for preparing graphene/polyaniline/sulfur composite positive electrode material |
| WO2017139986A1 (en) * | 2016-02-19 | 2017-08-24 | 肖丽芳 | Preparation method for phosphorus-doped lithium-sulfur battery anode material having three-dimensional structure |
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-
2012
- 2012-07-18 CN CN2012102480095A patent/CN102769126A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| HAILIANG WANG ET.AL: "Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium Sulfur Battery Cathode Material with High Capacity and Cycling Stability", 《NANO LETT》 * |
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| WO2017139939A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Method for preparing graphene/polyaniline/sulfur composite positive electrode material |
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| CN110010857B (en) * | 2018-01-04 | 2022-07-05 | 天津大学 | Composite material based on metal phthalocyanine compound-carbon and application thereof in lithium-sulfur battery |
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