CN103178247B - Sulfur/carbon composite material and preparation method thereof - Google Patents

Sulfur/carbon composite material and preparation method thereof Download PDF

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CN103178247B
CN103178247B CN201310094871.XA CN201310094871A CN103178247B CN 103178247 B CN103178247 B CN 103178247B CN 201310094871 A CN201310094871 A CN 201310094871A CN 103178247 B CN103178247 B CN 103178247B
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sulphur
carbon
sulfur
carbon composite
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CN103178247A (en
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张治安
李劼
蒋绍峰
赖延清
张凯
刘晋
贾明
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Central South University
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Abstract

The invention discloses a sulfur/carbon composite material and a preparation method thereof. Nanometer sulfur is uniformly filled in a pore path of a carbon material in the sulfur/carbon composite material to form the nanometer sulfur particle/carbon composite material. The preparation method comprises the following steps of: (1) reacting an aluminum sulfide solution with a sulfur source to generate an aluminum polysulfide solution; (2) adding a surface active agent and the carbon material into the aluminum polysulfide solution, uniformly stirring the resulting product, placing the uniformly stirred solution in an ultrasonic cleaner to carry out ultrasonic oscillation, and heating the resulting product to cause the sulfur generated by decomposition to in situ deposit to the pore path of the carbon material to obtain the sulfur/carbon composite material. According to the sulfur/carbon composite material, a sulfur particle and a carbon particle are tightly bound, the application of the sulfur/carbon composite material as the positive material of a lithium sulfur battery facilitates the reduction of solution loss of an active substance and the inhibition of shuttle effect, aluminum sulfide is generated from the ammonia gas and the hydrogen sulfide, which are generated by the decomposition of the aluminum polysulfide, through a condenser to be recycled, the technical process causes little pollution, the preparation method is simple in technology, low in cost and short in time, sulfur content is high, controllable, and strong in repeatability, and the sulfur/carbon composite material is easy for mass production.

Description

A kind of sulphur/carbon composite and preparation method thereof
Technical field
The invention belongs to electrochemical field, be specifically related to a kind of sulphur/carbon composite and preparation method thereof.
Background technology
Along with portable type electronic product is popularized, the fast development of energy storage technology and electric automobile, more and more higher to the requirement of lithium ion battery energy density and power density.Have prediction to claim, following 4G mobile communication requires that the energy density of battery reaches more than 500Wh/Kg.Lithium-sulfur cell has the feature of height ratio capacity (1675mAh/g) and high-energy-density (2600Wh/kg), and raw material elemental sulfur aboundresources, cheap, environmental friendliness; Therefore, lithium-sulfur cell is the high-energy density secondary battery having development potentiality and application prospect.But there is the shortcoming of positive active material elemental sulfur poorly conductive, the intermediate product polysulfide of discharge process is soluble in electrolyte, there is " effect of shuttling back and forth " in the electrolytic solution, cause irreversible loss and the capacity attenuation of active material; Meanwhile, final discharging product Li 2the indissolubility of S and electrical insulating property can cause the passivation of positive pole and negative pole.At present, sulphur positive electrode mainly by elemental sulfur is adsorbed onto there is satisfactory electrical conductivity, high-ratio surface sum high porosity carbon material on, form sulphur carbon composite.The preparation method of existing sulphur/carbon composite has: ball-milling method, vapor phase method, liquid phase method etc.
Sulphur/carbon composite anode material is prepared after elemental sulfur simply mixes with conductive carbon black high energy ball mill by Chung etc. (J.Power Sources, 2002,109,89-97).The method flow process is simple, but with in the obtained sulphur/carbon composite of this method, carbon sulfur granules combines not tight.
(the Chem.Commun such as Shi; 2012; 48; 4106-4108.) use vapor phase method; first by after material with carbon element and sulphur ball milling, 155 DEG C of heating a period of times under protective atmosphere, molten sulfur is allowed to immerse in the pore space structure of material with carbon element; and then be warming up to the sulphur that 300-350 DEG C is removed carbon material surface, thus prepare sulphur/carbon composite.The particle of sulphur/carbon composite that this method is prepared combines closely, but it is low to carry sulfur content.
Chinese patent net CN 101891930A discloses a kind of method that vapor phase method prepares the sulfur-based composite anode material of carbon nano-tube, and this method is conducive to the dispersion of carbon nano-tube and being uniformly distributed of sulphur, but in composite material sulfur content low and be difficult to control.
Chinese patent net CN 102832379A discloses a kind of method of Liquid preparation methods lithium sulfur battery anode material: mixed with organic solvent by elemental sulfur and elemental sulfur is dissolved completely, Carbon Materials is added in sulphur-organic solution, stir, solvent is removed, obtained sulphur-carbon composite by the method for volatilization or heating volatilization naturally.This preparation method is simple, and composite material to carry sulfur content high; But have sulphur to be attached to the surface of carbon, and most of molten sulphur organic solvent is all toxic; In addition, by naturally volatilization or heating volatilization remove solvent time long; Volatilization process is slow, and sulphur can slow crystallization, causes that the sulfur granules of precipitation is large and granularity is uneven.
(the J.Mater.Chem.A.2013 such as Ho Suk Ryu, 1,1573 – 1578.) use the method for liquid impregnation, elemental sulfur is dissolved in dimethyl sulfoxide (DMSO) (DMSO), then active carbon is added wherein, stirring 3h makes the organic solvent of sulfur-bearing fully infiltrate active carbon, is then cooled to room temperature, and elemental sulfur recrystallization in the hole of active carbon is separated out and obtained active carbon/sulphur composite material.This method is simple to operate, but has sulphur to be attached to the surface of carbon, and most of molten sulphur organic solvent is all toxic.
Therefore, need exploitation one badly and carbon sulfur granules can be made to combine closely, carry sulfur content high, controlled, and pollution-free, cost is low, and the preparation method of the simple sulphur/carbon composite of preparation technology, to improve its chemical property.
Summary of the invention
The object of the present invention is to provide a kind of sulphur/carbon composite and preparation method thereof, in sulphur/carbon composite, sulphur/carbon combines closely, and simple by the method preparation technology; Cost is low; Time is short; Energy consumption is low; Sulfur content is high and controlled, and repeatability is strong; Be easy to large-scale production.
Object of the present invention is achieved through the following technical solutions:
A kind of sulphur/carbon composite, is filled with nano-sulfur in the duct of the material with carbon element in described sulphur/carbon composite equably, form nano-sulfur particle/carbon composite, and in this sulphur/carbon composite, the mass percent of sulphur is 50% ~ 90%.
A preparation method for sulphur/carbon composite, mainly comprises the following steps:
Step 1: under normal temperature, mixes certain density ammonium sulfide solution by a certain percentage with elemental sulfur, stirs, and leaves standstill 0.5 ~ 2h, obtains the ammonium polysulfide solution ((NH clarified 4) 2sx (x=2 ~ 6)).
Step 2: a certain proportion of surfactant and material with carbon element are added in ammonium polysulfide solution successively, stirs; Be placed on 60 ~ 150W sonic oscillation, 0.5 ~ 2h in ultrasonic cleaner, and be placed in magnetic stirring apparatus and stir with certain rotating speed, be heated to 80 ~ 120 DEG C, ammonium polysulfide ((NH 4) 2sx (x=2 ~ 6)) nano-sulfur of decomposition generation is by in-situ deposition in material with carbon element duct, and through isolated by filtration or centrifugation, at 60 ~ 110 DEG C of temperature, vacuumize obtains sulphur/carbon composite.
The mass concentration of ammonium sulfide solution used in step 1 is 17 ~ 99%.
In step 1, described ammonium sulfide and the mol ratio of elemental sulfur are 1 ~ 5.
In step 1, described elemental sulfur is from one or more in sublimed sulfur, sedimentation sulphur, refining sulphur.
In step 2, surfactant used and material with carbon element mass percent are 1 ~ 20%.
In step 2, surfactant used is one or more in polyethylene glycol (PEG), softex kw (CTAB), neopelex (SDBS), Triton X-100 (TritonX-100).
In step 2, described material with carbon element is one or more in active carbon, mesoporous carbon, carbon black, carbon fiber, carbon nano-tube, charcoal-aero gel, Graphene.
In step 2, in described sulphur/carbon composite, sulphur mass percent is 50% ~ 90%, is filled with nano-sulfur particle uniformly in the hole of the material with carbon element in described sulphur/carbon composite, forms nano-sulfur particle/carbon composite.
Using sulphur/carbon composite of finally obtaining positive electrode as lithium-sulfur cell.
The present invention utilizes elemental sulfur under normal temperature to be dissolved in ammonium sulfide solution can generate ammonium polysulfide ((NH 4) 2sx (x=2 ~ 6)) solution, ammonium polysulfide heating can decomposite this principle of elemental sulfur.Reaction equation is: (x-1) S+ (NH 4) 2s=(NH 4) 2sx, (NH 4) 2sx=2NH 3+ H 2s+ (x-1) S.Adopt inorganic solvent ammonium sulfide in situ deposition method, by adding surfactant, material with carbon element is dispersed in ammonium polysulfide solution fully, under Ultrasound-assisted effect, heat resolve, easier in-situ deposition in material with carbon element duct, is prepared carbon sulfur granules combination sulphur/carbon composite closely by the sulphur generated.
Sulphur/carbon composite disclosed by the invention and preparation method thereof, has the following advantages:
(1) the present invention adopts ammonium polysulfide Direct Resolution to generate the in situ deposition method of sulphur to prepare sulphur/carbon composite, enter in the duct of porous carbon by the ultrasonic ammonium polysulfide solution that makes, ammonium polysulfide heat resolve generate nano-sulfur by in-situ deposition in the duct of porous carbon, thus the combination making carbon sulfur granules in the composite material prepared closely, decrease the solution loss of active material in lithium-sulfur cell to a certain extent and inhibit effect of shuttling back and forth.
(2) the present invention adopts ammonium polysulfide solution decomposition generation sulphur in situ deposition method to prepare sulphur/carbon composite, and sulfur content is high and controlled, can obtain the different sulphur/carbon composite of sulfur content by the material with carbon element controlled in raw material from elemental sulfur ratio.
(3) ammonia that in the present invention, ammonium polysulfide decomposition produces and hydrogen sulfide gas are easy to generate ammonium sulfide in industrialized condenser circulating device, and can be recycled, cost-saving, whole process contamination is little.
(4) the present invention adopts the sulphur source that ammonium sulfide solution is low by purity, particle is large to dissolve purification, generate ammonium polysulfide solution, ammonium polysulfide decomposes the highly purified nano-sulfur of generation, sulphur/carbon composite the impurity content of preparation is low, nano-sulfur particles size in sulphur/carbon composite is little, easily be embedded in the duct of porous carbon, make the combination of carbon sulfur granules closely.
(5) the ammonium sulfide low price of the present invention's employing, can be recycled; And whole preparation technology is simple, the time is short, and energy consumption is low, repeatable strong, is easy to industrially implement and produce in enormous quantities.
In sum, preparation technology of the present invention is simple; Cost is low; Time is short; Energy consumption is low; Sulfur content is high and controlled; The ammonia that decomposition produces and hydrogen sulfide gas are easy in circulating device, generate ammonium sulfide and recycle, and whole technical process is pollution-free; Repeatable strong; Be easy to large-scale production.The sulphur carbon composite of preparation is a kind of desirable positive material for lithium-sulfur battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the sulphur/carbon composite prepared by embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the sulphur/carbon composite prepared by embodiment 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of the sulphur/carbon composite prepared by embodiment 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of the sulphur/carbon composite prepared by embodiment 5;
Fig. 5 is the scanning electron microscope (SEM) photograph of the sulphur/carbon composite prepared by embodiment 6.
Lithium-sulfur cell 50 discharge capacity curve charts that Fig. 6 is is positive pole with the sulphur/carbon composite prepared by embodiment 1;
Lithium-sulfur cell 50 discharge capacity curve charts of Fig. 7 to be sulphur/carbon composite prepared by embodiment 3 be positive pole;
Lithium-sulfur cell 50 discharge capacity curve charts of Fig. 8 to be sulphur/carbon composite prepared by embodiment 4 be positive pole;
Lithium-sulfur cell 50 discharge capacity curve charts of Fig. 9 to be sulphur/carbon composite prepared by embodiment 5 be positive pole;
Lithium-sulfur cell 50 discharge capacity curve charts of Figure 10 to be sulphur/carbon composite prepared by embodiment 6 be positive pole.
Figure 11 is the thermogravimetric curve figure of the sulphur/carbon composite obtained by embodiment 1.
Can find out that from the scanning electron microscope (SEM) photograph of accompanying drawing 1-5 the composite material sulphur carbon dispersion of preparation is relatively more even, sulphur and carbon combine closely.
Lithium-sulfur cell 50 discharge capacity curve charts that accompanying drawing 6 is is positive pole with the sulphur/absorbent charcoal composite material prepared by embodiment 1, first discharge specific capacity is 1210mAh/g, is greater than 550mAh/g after 50 circulations;
Lithium-sulfur cell 50 discharge capacity curve charts of accompanying drawing 7 to be sulphur/Carbon Black Composites prepared by embodiment 3 be positive pole, first discharge specific capacity is 980mAh/g, is greater than 500mAh/g after 50 circulations;
Lithium-sulfur cell 50 discharge capacity curve charts of accompanying drawing 8 to be sulphur/graphene composite materials prepared by embodiment 4 be positive pole, first discharge specific capacity is 1270mAh/g, is greater than 800mAh/g after 50 circulations;
Lithium-sulfur cell 50 discharge capacity curve charts of accompanying drawing 9 to be sulphur/carbon fibre composites prepared by embodiment 5 be positive pole, first discharge specific capacity is 1320mAh/g, is greater than 650mAh/g after 50 circulations;
Lithium-sulfur cell 50 discharge capacity curve charts of accompanying drawing 10 to be sulphur/carbon nano tube compound materials prepared by embodiment 6 be positive pole, first discharge specific capacity is 1050mAh/g, is greater than 600mAh/g after 50 circulations.Prepared sulphur/carbon composite is the cycle performance that the lithium-sulfur cell of positive pole all shows high first discharge specific capacity and becomes reconciled.
Accompanying drawing 11 is thermogravimetric curves of the sulphur/carbon composite prepared by embodiment 1.Thermogravimetric curve ordinate is sulphur mass percentage, and abscissa is the temperature of heating.Can find out that sulphur mass percentage is 79.6% from the thermogravimetric curve of accompanying drawing 11, sulfur content is high and consistent with the sulphur material with carbon element ratio added in embodiment, and sulfur content is easy to control as can be seen here.
Embodiment
Below in conjunction with embodiment, the present invention will be further described in detail, but can not be regarded as the restriction to protection scope of the present invention.
Embodiment 1:
At normal temperatures, the mass concentration to 17g be 20% ammonium sulfide solution add 3.2g sublimed sulfur, generate ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.08g surfactant polyethylene octyl phenyl ether and 0.8g active carbon is added successively, stir 2h, after stirring, this mixed liquor is placed in ultrasonic cleaner and carries out sonic oscillation 1h with the power of 150W, and be placed in magnetic stirring apparatus and stir with certain rotating speed, be heated to 95 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated, in absorbent charcoal material duct, then by isolated by filtration, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite distilled water is washed till neutrality, then vacuumize at 80 DEG C, obtains sulphur/carbon composite that sulfur-bearing mass percent is 79.6%.
The electrochemical property test of sulphur/carbon composite:
Prepare electrode slice and button cell: by the sulphur/carbon composite obtained by embodiment 1, binding agent (PVDF), conductive black 7:1:2 Homogeneous phase mixing in mass ratio, appropriate 1-METHYLPYRROLIDONE (NMP) is dripped wherein as solvent after mixing, then uniform sizing material is ground into, be coated in aluminum foil current collector, vacuumize 12 hours at 60 DEG C.The electrode slice that diameter is 10mm is struck out after drying.Then with this electrode slice for positive pole, take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2025 button cell, under room temperature (25 DEG C), carry out constant current charge-discharge test with 0.2C, first discharge specific capacity is 1210mAh/g, is greater than 550mAh/g after 50 circulations.
Embodiment 2:
At normal temperatures, the mass concentration to 17g is add 3.2g sublimed sulfur in the ammonium sulfide solution of 20%, generates ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.32g surfactant polyethylene and 3.2g active carbon is added successively, stir 1h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic of 100W vibration 1h, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated, in material with carbon element duct, then by centrifugation, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite ethanol is washed till neutrality, then vacuumize at 70 DEG C, obtains sulphur/carbon composite.
Embodiment 3:
At normal temperatures, the mass concentration to 6.8g is add 3.2g sedimentation sulphur in the ammonium sulfide solution of 20%, generates ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.21g surfactant polyethylene and 1.37g carbon black is added successively, stir 1h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic of 60W vibration 1h, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 120 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated is in material with carbon element duct, and isolated by filtration, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite distilled water is washed till neutrality, then vacuumize at 80 DEG C, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
By the carbon obtained by embodiment 3/sulphur composite material, binding agent (PVDF), conductive black 7:1:2 Homogeneous phase mixing in mass ratio, appropriate solvent N-methyl pyrilidone (NMP) is dripped wherein after mixing, then uniform sizing material is ground into, be coated in aluminum foil current collector, vacuumize 12 hours at 60 DEG C.The electrode slice that diameter is 10mm is struck out after drying.Then with this electrode slice for positive pole, take metal lithium sheet as negative pole, CR2025 button cell is assembled in the glove box being full of argon gas, constant current charge-discharge test is carried out with 0.2C under room temperature (25 DEG C), first discharge specific capacity is 980mAh/g, be greater than 500mAh/g after 50 circulations, 50 discharge capacity curves as shown in Figure 7.。
Embodiment 4:
At normal temperatures, the mass concentration to 22.7g is add 3.2g sedimentation sulphur in the ammonium sulfide solution of 30%, generates ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.16g surfactant softex kw and 3.2g Graphene is added successively, stir 0.5h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic of 60W vibration 1h, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated is in material with carbon element duct, and isolated by filtration, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite distilled water is washed till neutrality, vacuumize at 60 DEG C, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
Prepare electrode slice and button cell: by the carbon obtained by embodiment 4/sulphur composite material, binding agent (PVDF), conductive black 7:1:2 Homogeneous phase mixing in mass ratio, appropriate solvent N-methyl pyrilidone (NMP) is dripped wherein after mixing, then be coated in after being ground into uniform sizing material in aluminum foil current collector, vacuumize 12 hours at 60 DEG C.The electrode slice that diameter is 10mm is struck out after drying.Then with this electrode slice for positive pole, take metal lithium sheet as negative pole, CR2025 button cell is assembled in the glove box being full of argon gas, constant current charge-discharge test is carried out with 0.2C in room temperature (25 DEG C), first discharge specific capacity is 1270mAh/g, be greater than 800mAh/g after 50 circulations, 50 discharge capacity curves as shown in Figure 8.
Embodiment 5:
At normal temperatures, the mass concentration to 22.7g is add 3.2g in the ammonium sulfide solution of 30% to refine sulphur, generates ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.07g surfactant softex kw (CTAB) and 0.36 carbon fiber is added successively, stir 1h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic of 150W vibration 1h, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated is in material with carbon element duct, and isolated by filtration, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite distilled water is washed till neutrality, vacuumize at 90 DEG C, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
By the sulphur/carbon composite obtained by embodiment 5, binding agent (PVDF), conductive black 7:1:2 Homogeneous phase mixing in mass ratio, appropriate solvent N-methyl pyrilidone (NMP) is dripped wherein after mixing, then be coated in after being ground into uniform sizing material in aluminum foil current collector, vacuumize 12 hours at 60 DEG C.The electrode slice that diameter is 10mm is struck out after drying.Then with this electrode slice for positive pole, take metal lithium sheet as negative pole, CR2025 button cell is assembled in the glove box being full of argon gas, constant current charge-discharge test is carried out with 0.2C in room temperature (25 DEG C), first discharge specific capacity is 1320mAh/g, be greater than 650mAh/g after 50 circulations, 50 discharge capacity curves as shown in Figure 9.
Embodiment 6:
At normal temperatures, the mass concentration to 7.56g is add 3.2g in the ammonium sulfide solution of 30% to refine sulphur, generates ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.08g surfactant sodium dodecyl base benzene sulfonic acid sodium salt (SDBS) and 0.8g carbon nano-tube is added successively, stir 2h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic of 150W vibration 1h, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated is in material with carbon element duct, and centrifugation, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite distilled water is washed till neutrality, vacuumize at 90 DEG C, obtains sulphur/carbon composite.
The electrochemical property test of sulphur/carbon composite:
By the sulphur/carbon composite obtained by embodiment 6, binding agent (PVDF), conductive black 7:1:2 Homogeneous phase mixing in mass ratio, appropriate solvent (NMP) is dripped wherein after mixing, then be coated in after being ground into uniform sizing material in aluminum foil current collector, vacuumize 12 hours at 60 DEG C.The electrode slice that diameter is 10mm is struck out after drying.Take metal lithium sheet as negative pole, CR2025 button cell is assembled in the glove box being full of argon gas, constant current charge-discharge test is carried out with 0.2C in room temperature (25 DEG C), first discharge specific capacity is 1050mAh/g, be greater than 600mAh/g after 50 circulations, 50 discharge capacity curves as shown in Figure 10.
Embodiment 7:
At normal temperatures, the mass concentration to 17g is add the mixture 4.6g that simple substance sulfur content is 70% in the ammonium sulfide solution of 20%, and after reaction, centrifugation, gets clarification ammonium polysulfide solution; Then in ammonium polysulfide solution, 0.1g surfactant polyethylene octyl phenyl ether (TritonX-100) and 2.13g charcoal-aero gel is added successively, stir 2h, after stirring, this mixed liquor is placed in ultrasonic cleaner with the power ultrasonic of 120W vibration 1h, and be placed in magnetic stirring apparatus and stir with certain rotating speed, and be heated to 95 DEG C, the sulphur in-situ deposition that ammonium polysulfide heat resolve is generated is in material with carbon element duct, and isolated by filtration, obtains sulphur/carbon composite and filtrate; The sulphur obtained/carbon composite distilled water is washed till neutrality, vacuumize at 90 DEG C, obtains sulphur/carbon composite.

Claims (9)

1. a preparation method for sulphur/carbon composite, is characterized in that, described preparation method comprises the following steps:
Step 1: at normal temperatures, mixes ammonium sulfide solution with elemental sulfur, obtains the ammonium polysulfide solution ((NH clarified after stirring after leaving standstill 0.5 ~ 2h 4) 2sx (x=2 ~ 6));
Step 2: add surfactant and material with carbon element in the ammonium polysulfide solution of clarification obtained in step 1, sonic oscillation 0.5 ~ 2h in ultrasonic cleaner is placed on after stirring, and be placed in magnetic stirring apparatus and stir with certain rotating speed, be heated to 80 ~ 120 DEG C, then be separated, obtain sulphur/carbon composite and raffinate, by the sulphur/carbon composite vacuumize at 60 ~ 110 DEG C of temperature obtained.
2. the preparation method of sulphur/carbon composite according to claim 1, is characterized in that, the mass concentration of ammonium sulfide solution used in step 1 is 17 ~ 99%.
3. the preparation method of sulphur/carbon composite according to claim 1 and 2, is characterized in that: the mol ratio of the ammonium sulfide described in step 1 and elemental sulfur is 1 ~ 5.
4. the preparation method of sulphur/carbon composite according to claim 1, is characterized in that: the elemental sulfur described in step 1 is selected from one or more in sublimed sulfur, sedimentation sulphur, refining sulphur.
5. the preparation method of the sulphur/carbon composite according to claim 1 or 4, is characterized in that: the surfactant added in step 2 is one or more in polyethylene glycol (PEG), softex kw (CTAB), neopelex (SDBS), Triton X-100 (TritonX-100).
6. the preparation method of sulphur/carbon composite according to claim 5, is characterized in that: the surfactant added in step 2 and the mass percent of material with carbon element are 1 ~ 20%.
7. the preparation method of sulphur/carbon composite according to claim 6, is characterized in that: the material with carbon element added in step 2 is selected from one or more in active carbon, mesoporous carbon, carbon black, carbon fiber, carbon nano-tube, charcoal-aero gel, Graphene.
8. the preparation method of sulphur/carbon composite according to claim 1, is characterized in that: the mode of the separation in step 2 is isolated by filtration or centrifugation.
9. the preparation method of the sulphur/carbon composite according to claim 1 or 8, is characterized in that: obtained sulphur/carbon composite is as the positive electrode of lithium-sulfur cell.
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