CN106684389A - Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof - Google Patents

Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof Download PDF

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CN106684389A
CN106684389A CN201611257681.5A CN201611257681A CN106684389A CN 106684389 A CN106684389 A CN 106684389A CN 201611257681 A CN201611257681 A CN 201611257681A CN 106684389 A CN106684389 A CN 106684389A
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sulphur
nano material
sulfur
lithium
graphene nano
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杨植
王璐
聂华贵
化五星
肖助兵
黄少铭
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Wenzhou University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a sulfur-nitrogen dual-doped graphene nano material. A preparation method of the sulfur-nitrogen dual-doped graphene nano material comprises the following steps: mixing a sulfur nitrogen precursor and graphene oxide to obtain a mixture I, adding the mixture I into ethanol, ultrasonically and uniformly dispersing, and drying at 40 to 90 DEG C, thus obtaining a composite of the graphene oxide and the sulfur nitrogen precursor; and standing the composite of the graphene oxide and the sulfur nitrogen precursor at a high temperature of 800 to 1000 DEG C for 1 to 5 hours under the protection of inert gas, then naturally cooling to the room temperature, and obtaining a final product. The preparation method is low in cost; by combining a two-dimensional structure of the graphene and doping-induced polarity active site, the conductivity of a positive electrode of a lithium sulfur battery is remarkably improved, the loss and reutilization of polysulfide are improved, and when the prepared sulfur nitrogen dual-doped graphene nano material is used as a multifunctional interlayer material to be applied to the lithium sulfur battery, the conductivity of the sulfur positive electrode and the completeness of a protection diaphragm under large current can be remarkably improved, and the applicability is high.

Description

Sulphur nitrogen codope graphene nano material and preparation method and application
(1) technical field
The present invention relates to nano materials research field, more particularly to a kind of sulphur nitrogen codope graphene nano material and its system Preparation Method with application, the sulphur nitrogen codope graphene nano material can as Multifunction sandwiched-type materials application in lithium-sulfur cell, Improve the effect such as its chemical property and protection barrier film to play.
(2) background technology
With the fast development of society, people increasingly increase to expire to the demand of high-energy-density, the battery of high stability The need for the aspect such as sufficient vehicle drive power and extensive energy stores.Lithium-sulfur cell is very high because of its theoretical energy density (1675mAh/g and 2600kWh/kg) receives much concern, and is recognized as active material using with low cost, environment-friendly sulphur To be the battery system of new generation of great potential.But the business of lithium-sulfur cell is practical to be needed to solve the problems, such as three below:(1) The poorly conductive (5 × 10 of sulphur-30S·cm-1), cause that the utilization rate of sulphur is relatively low and actual capacity is relatively low;(2) in charge and discharge process Because the mutual conversion of sulphur and solid discharge product causes electrode structure and pattern to change, and then influence circulating battery stability The problems such as;(3) in charge and discharge process, the polysulfide of generation can loss by dissolution in electrolyte, cause battery efficiency and capacity The problems such as decay.
For the problem that lithium-sulfur cell is present, from the lithium-sulfur cell appearance sixties in last century, it has been proposed that by sulphur and more empty The carbon materials such as carbon, CNT, Graphene are combined the loss of the insulating properties and sulphur that improve sulphur, the positive pole material as lithium-sulfur cell Material.But above-mentioned method effect in terms of the loss of polysulfide is improved is limited, and because of the non-polar open architecture of carbon material Or material preparation process it is complicated, realize that the reasons such as condition is cumbersome cause its meaning to be limited.Recent years, it has been found that in sulphur just Sandwich material is used between pole and barrier film, the chemical property of lithium-sulfur cell can be effectively improved.At present report sandwich material because To introduce the poor materials of electric conductivity such as such as aluminum oxide, carbon iron compound, them are have impact on to a certain extent improves lithium-sulfur cells The effect of chemical property.Additionally, in order to be able to meet its application at the aspect such as vehicle drive power and extensive energy stores, The large current discharging capability of lithium-sulfur cell still needs to improve, and this is accomplished by further improving its high rate performance.
Graphene since the report, because its good electric conductivity, unique two-dimension plane structure enjoy pro-gaze, lithium from Sub- battery, fuel cell equal energy source field realize commercial applications or obtain larger substantive breakthroughs.It is in lithium-sulfur cell Major part is confined to be combined with sulphur, but because of the non-polar surface characteristic and its two-dimensional structure of carbon, its host for being used for sulphur Material improvement is limited.Nitrogen, sulfur doping can be effectively improved the electric conductivity of carbon material and increase material surface polarity work site, and The problems such as shuttle that polysulfide in lithium-sulfur cell can be improved is lost in.
(3) content of the invention
The present invention be based on the unique two-dimensional structure of Graphene, propose a kind of sulphur nitrogen codope graphene nano material and its Preparation method and application.Sulphur nitrogen codope Graphene is used for lithium-sulfur cell sandwich material by the present invention first, and is coated in On traditional lithium sulfur battery anode material, improve lithium-sulphur cell positive electrode electric conductivity and polysulfide loss the problems such as, than The sulphur positive pole of interlayer and the sulphur positive pole of undoped p graphene interlayers are provided without, using the lithium-sulfur cell of the sulphur nitrogen codope Graphene Active material sulphur utilization rate and specific capacity significantly improve, the high rate performance battery up to 40C is achieved first, and followed under 8C Ring stablizes the cycle performance of 1000 circles, and confirms function of the sandwich material in barrier film protection first.
The present invention is adopted the following technical scheme that:
A kind of sulphur nitrogen codope graphene nano material, its preparation method is:
(1) by sulphur nitrogen presoma, graphene oxide in mass ratio 0.5~3:After 1 mixing, in addition ethanol, ultrasonic disperse Uniformly, then the compound of graphene oxide and sulphur nitrogen presoma is obtained in 40~90 DEG C of drying;
Described sulphur nitrogen presoma is thiocarbamide, amido thiocarbamide, sulphur nitrogen piperazine, methionine or cysteine;
Described graphene oxide is single-layer graphene oxide, few layer graphene oxide or multilayer graphene oxide;
The volumetric usage of the ethanol is calculated as 80~400mL/g, preferably 100~200mL/g with the quality of graphene oxide;
(2) under inert gas (such as argon gas) protection, by step (1) gained graphene oxide and the compound of sulphur nitrogen presoma 1~5h is kept at a high temperature of being placed in 800~1000 DEG C, room temperature (20~30 DEG C) is naturally cooled to afterwards, obtain described sulphur nitrogen Codope graphene nano material.
The specific surface area of obtained sulphur nitrogen codope graphene nano material of the invention is 100~350m2/g。
Described sulphur nitrogen codope graphene nano material can be as Multifunction sandwiched-type materials application in lithium-sulfur cell.Tool Body, the method for the application is:
Described sulphur nitrogen codope graphene nano material is pressed into feed liquid mass ratio 0.1~30:100 (preferably 1~5:100) Add in organic solvent, ultrasonic disperse is uniform, obtains solidliquid mixture slurry, it is brushed in lithium-sulphur cell positive electrode with spreader Surface (usual brushing thickness is 4~8um), is then vacuum dried, that is, realize and (make sulphur nitrogen codope graphene nano material It is multifunction clips layer material) lithium-sulphur cell positive electrode structure is integrated in, subsequently carry out battery assembling (described sulphur according to routine operation Nitrogen codope graphene nano material is integrated between lithium-sulphur cell positive electrode and barrier film) and performance test;
Described organic solvent is 1-METHYLPYRROLIDONE (NMP) or (S)-(+) -5- methylols -2-Pyrrolidone;
The material of the lithium-sulphur cell positive electrode is carbon black/sulphur, porous carbon/sulphur, Graphene/sulphur, CNT/sulphur, carbon fibre Dimension/sulphur or CMK-3/ sulphur;
Described sulphur nitrogen codope graphene nano material is integrated in after lithium-sulphur cell positive electrode structure, the sulphur nitrogen codope The mass percent that graphene nano material accounts for whole lithium-sulphur cell positive electrode is 0.2%~1% (the aluminium foil matter not including collector Amount);
Described sulphur nitrogen codope graphene nano material as multifunction clips layer material, wherein " multi-functional " is meant that Refer to:The interlayer possesses the high rate performance and cycle performance for improving and improving lithium-sulfur cell, safeguards the stability of positive pole and carries big electricity Flow down the characteristics such as the integrality of protection barrier film.
The beneficial effects of the present invention are:
1st, the raw material sulphur nitrogen presoma and graphene oxide cost that preparation method of the present invention is used are relatively low;
2nd, the two-dimensional structure and doping for combining Graphene cause polarity work site, significantly improve lithium-sulphur cell positive electrode The loss of electric conductivity and polysulfide and recycling;
3rd, the interlayer that the method is obtained can significantly improve the electric conductivity of sulphur positive pole and barrier film is protected under high current Integrality;
4th, the method can pervasively with carbon black/sulphur, porous carbon/sulphur, Graphene/sulphur, CNT/sulphur, carbon fiber/ The composite positive poles such as sulphur, CMK-3/ sulphur are used in combination.
(4) illustrate
Fig. 1:The structural representation of the lithium-sulfur cell of brushing sulphur nitrogen codope graphene interlayers;
Fig. 2:Scribble sulphur nitrogen codope graphene interlayers, nitrogen-doped graphene interlayer, sulfur doping graphene interlayers, oxygen reduction Graphite alkene layer and original carbon nanotubes/charge and discharge platform curve of five kinds of the sulphur composite electrode under 0.5C current densities;
Fig. 3:Scribble sulphur nitrogen codope graphene interlayers, nitrogen-doped graphene interlayer, sulfur doping graphene interlayers, oxygen reduction Graphite alkene layer and original carbon nanotubes/five kinds of sulphur composite ac impedance measurement of electrode;
Fig. 4:A () is not used for the barrier film electron scanning micrograph of the fresh barrier film of lithium-sulfur cell circulation work;B () adopts The barrier film for (circulating 5 under the multiplying power of 15C to enclose) collection after circulation with the lithium-sulfur cell of sulphur nitrogen codope graphene interlayers is scanned Electron micrograph;
Fig. 5:Scribble sulphur nitrogen codope graphene interlayers, nitrogen-doped graphene interlayer, sulfur doping graphene interlayers, oxygen reduction The specific discharge capacity and cycle performance of graphite alkene layer and original carbon nanotubes/five kinds of sulphur composite electrode;
Fig. 6:Scribble sulphur nitrogen codope graphene interlayers, nitrogen-doped graphene interlayer, sulfur doping graphene interlayers, oxygen reduction Graphite alkene layer and original carbon nanotubes/five kinds of sulphur composite high rate performance of electrode.
(5) specific embodiment
The present invention is specifically described below by embodiment, is served only for being further described the present invention, no It is understood that to be limiting the scope of the present invention, person skilled in art can make according to the content of foregoing invention to the present invention Go out some nonessential modifications and adaptations.
Embodiment 1
A, prepare sulphur nitrogen codope graphene nano material
(1) thiocarbamide 600mg, graphene oxide 300mg are weighed, mixing is dissolved in 50mL ethanol, is stirred vigorously and ultrasound point Dissipate uniform, then dry mixing liquid in 80 DEG C of water-baths, obtain the compound of graphene oxide and thiocarbamide.
(2) under argon atmosphere protection, the compound of step (1) gained graphene oxide and thiocarbamide is placed at 900 DEG C 4h is kept, room temperature is naturally cooled to afterwards, obtain sulphur nitrogen codope graphene nano material.
B, prepare lithium-sulfur rechargeable battery anode piece
By CNT (Nanjing Xian Feng Nono-material Science & Technology Ltd., 5g purity 95%, 0.5~2 micron of length, carboxylic Base content 3.86wt%, XFM06) 250mg, elemental sulfur 585mg be fully ground mixing, is dissolved in 8mL carbon disulfide, it is stirred vigorously And ultrasound, treat that carbon disulfide volatilization is clean, during mixture transfer put into baking oven, 155 DEG C are warming up to, constant temperature 20h, cooling obtains carbon Nanotube/sulphur composite positive pole, by thermogravimetric analysis test its actual sulfur content be 68%.
By obtained CNT/sulphur composite positive pole 160mg and acetylene black 23.53mg, Kynoar (PVDF) 11.76mg uniformly mixes, and stirring forms slurry in being dispersed in 45mL 1-METHYLPYRROLIDONEs (NMP) solution, then with 40 μ m-thicks Degree is coated in above aluminium foil, and tentatively lithium-sulfur rechargeable battery anode piece is obtained in vacuum drying at 60 DEG C.
C, sulphur nitrogen codope graphene nano material are integrated in lithium-sulphur cell positive electrode structure, and carry out the assembling of battery and survey Examination
By in sulphur nitrogen codope graphene nano material 50mg additions 3mL 1-METHYLPYRROLIDONEs obtained in step A, surpass Sound is uniformly dispersed, and obtains slurry, with the brushing of 6um thickness in lithium-sulfur rechargeable battery anode piece surface obtained in step B, at 60 DEG C Vacuum drying 12h.
Battery is assembled and test:
The active material that sulphur nitrogen codope graphene layer will be scribbled strikes out electrode slice.As a comparison, will be not coated with interlayer and The sulphur positive pole for only applying redox graphene also strikes out electrode slice.With metal lithium sheet as negative pole, electrolyte is addition 1% LiNO31M LiTFSI/DOL:DME (1: 1), is assembled into battery in the glove box full of argon gas.At room temperature, with 0.5C Current density carry out charge-discharge test, it is 1.5~3.0V that charging/discharging voltage is interval.
Fig. 1 is the structural representation of the lithium-sulfur cell with traditional lithium-sulfur cell of brushing sulphur nitrogen codope graphene interlayers.Survey Test result shows, scribbles sulphur nitrogen codope graphene interlayers, nitrogen-doped graphene interlayer, sulfur doping graphene interlayers, oxygen reduction Graphite alkene layer and original carbon nanotubes/five kinds of sulphur composite electrode under 0.5C current densities, voltage range be 1.5~ During 3.0V, the charge and discharge platform of the lithium-sulfur rechargeable battery of standard is all shown, as shown in Figure 2.Meanwhile, compare following for five kinds of electrodes Ring performance and high rate performance, as it can be seen in figures 5 and 6, discovery scribbles the later electrode performance of sulphur nitrogen codope graphene interlayers, with it He compares four kinds of electrodes, and the discharge capacity and cyclical stability of lithium-sulfur rechargeable battery have and increase substantially.Fig. 3 proves to have benefited from Preferable electric conductivity, the chemical property for scribbling sulphur nitrogen codope graphene interlayers electrode is better than other four kinds of electrodes, and Fig. 4 says Understand protecting effect of the sulphur nitrogen codope graphene interlayers to membrane integrity.
Embodiment 2
A, prepare sulphur nitrogen codope graphene nano material
(1) amido thiocarbamide 700mg, graphene oxide 330mg are weighed, mixing is dissolved in 70mL ethanol, is stirred vigorously and surpasses Sound is uniformly dispersed, and then dries mixing liquid in 80 DEG C of water-baths, obtains the compound of graphene oxide and amido thiocarbamide.
(2) under argon atmosphere protection, the compound of step (1) gained graphene oxide and amido thiocarbamide is placed in 850 4h is kept at DEG C, room temperature is naturally cooled to afterwards, obtain sulphur nitrogen codope graphene nano material.
B, the assembling of battery and test
By commercial carbon blacks (Nanjing Xian Feng Nono-material Science & Technology Ltd., 100g particle diameters:30~45nm, XFI15) 150mg, elemental sulfur 350mg are fully ground mixing, are dissolved in 13mL carbon disulfide, are stirred vigorously and ultrasound, treat that carbon disulfide volatilizees Totally, in mixture transfer being put into baking oven, 155 DEG C are warming up to, constant temperature 18h, cooling obtains carbon black/sulphur composite positive pole, leads to Cross thermogravimetric analysis test its actual sulfur content be 65%.
, with embodiment 1, gained battery is carried out 50 times in 0.5C current densities for sulphur positive pole coating method and battery testing method Cycle charge-discharge.Compare and scribble sulphur nitrogen codope graphene layer electrode and original electrodes, capacity stabilization, 50 in the former cyclic process Capacity is maintained at 730mAh/g, efficiency for charge-discharge 99% or so after secondary circulation.The latter's decay is very fast, and capacity is maintained at 370mAh/g, efficiency for charge-discharge 88% or so.
Embodiment 3
A, prepare sulphur nitrogen codope graphene nano material
(1) methionine 650mg, graphene oxide 320mg are weighed, mixing is dissolved in 65mL ethanol, is stirred vigorously and surpasses Sound is uniformly dispersed, and then dries mixing liquid in 80 DEG C of water-baths, obtains the compound of graphene oxide and methionine.
(2) under argon atmosphere protection, the compound of step (1) gained graphene oxide and methionine is placed in 850 4h is kept at DEG C, room temperature is naturally cooled to afterwards, obtain sulphur nitrogen codope graphene nano material.
B, the assembling of battery and test
By business carbon fiber (Shang Hai Tuo Yang bio tech ltd, 1g, TAYC139875-1g) 150mg, elemental sulfur 350mg is fully ground mixing, is dissolved in 12mL carbon disulfide, is stirred vigorously and ultrasound, treats that carbon disulfide volatilization is clean, by mixture Transfer is put in baking oven, is warming up to 155 DEG C, and constant temperature 20h, cooling obtains carbon fiber/sulphur composite positive pole, is surveyed by thermogravimetric analysis Try its actual sulfur content be 62%.
, with embodiment 1, gained battery is carried out 50 times in 0.5C current densities for sulphur positive pole coating method and battery testing method Cycle charge-discharge.Compare and scribble sulphur nitrogen codope graphene layer electrode and original electrodes, capacity stabilization, 50 in the former cyclic process Capacity is maintained at 820mAh/g, efficiency for charge-discharge 99% or so after secondary circulation.The latter's decay is very fast, and capacity is maintained at 490mAh/g, efficiency for charge-discharge 92% or so.
Embodiment 4
A, prepare sulphur nitrogen codope graphene nano material
(1) cysteine 650mg, graphene oxide 310mg are weighed, mixing is dissolved in 60mL ethanol, is stirred vigorously and surpasses Sound is uniformly dispersed, and then dries mixing liquid in 80 DEG C of water-baths, obtains the compound of graphene oxide and cysteine.
(2) under argon atmosphere protection, the compound of step (1) gained graphene oxide and cysteine is placed in 900 4h is kept at DEG C, room temperature is naturally cooled to afterwards, obtain sulphur nitrogen codope graphene nano material.
B, the assembling of battery and test
By business porous carbon (Nanjing Xian Feng Nono-material Science & Technology Ltd., 5g, SSA:~600m2/ g, XFP05) 120mg, elemental sulfur 280mg are fully ground mixing, are dissolved in 12mL carbon disulfide, are stirred vigorously and ultrasound, treat that carbon disulfide volatilizees Totally, in mixture transfer being put into baking oven, 155 DEG C are warming up to, constant temperature 16h, cooling obtains porous carbon/sulphur composite positive pole, By thermogravimetric analysis test its actual sulfur content be 64%.
, with embodiment 1, gained battery is carried out 50 times in 0.5C current densities for sulphur positive pole coating method and battery testing method Cycle charge-discharge.Compare and scribble sulphur nitrogen codope graphene layer electrode and original electrodes, capacity stabilization, 50 in the former cyclic process Capacity is maintained at 900mAh/g, efficiency for charge-discharge 98% or so after secondary circulation.The latter's decay is very fast, and capacity is maintained at 495mAh/g, efficiency for charge-discharge 91% or so.
Embodiment 5
A, prepare sulphur nitrogen codope graphene nano material
(1) sulphur nitrogen piperazine 700mg, graphene oxide 350mg are weighed, mixing is dissolved in 70mL ethanol, is stirred vigorously and ultrasound It is uniformly dispersed, then dries mixing liquid in 80 DEG C of water-baths, obtains the compound of graphene oxide and sulphur nitrogen piperazine.
(2) under argon atmosphere protection, the compound of step (1) gained graphene oxide and sulphur nitrogen piperazine is placed in 950 DEG C Lower holding 4h, naturally cools to room temperature afterwards, obtains sulphur nitrogen codope graphene nano material.
B, the assembling of battery and test
By CMK-3 (Nanjing Xian Feng nanosecond science and technology Materials Co., Ltd, 5g, D:3.8~4nm, SSA:900m2/ g, XFP03) 120mg, elemental sulfur 280mg are fully ground mixing, are dissolved in 13mL carbon disulfide, are stirred vigorously and ultrasound, treat that carbon disulfide volatilizees Totally, in mixture transfer being put into baking oven, 155 DEG C are warming up to, constant temperature 24h, cooling obtains CMK-3/ sulphur composite positive poles, leads to Cross thermogravimetric analysis test its actual sulfur content be 53.1%.
, with embodiment 1, gained battery is carried out 50 times in 0.5C current densities for sulphur positive pole coating method and battery testing method Cycle charge-discharge.Compare and scribble sulphur nitrogen codope graphene layer electrode and original electrodes, capacity stabilization, 50 in the former cyclic process Capacity is maintained at 910mAh/g, efficiency for charge-discharge 99% or so after secondary circulation.The latter's decay is very fast, and capacity is maintained at 720mAh/g, efficiency for charge-discharge 92% or so.
Obviously, above-described embodiment is used for the purpose of the citing that clearly explanation technical solution of the present invention is done, and not right The restriction of implementation method.To those of ordinary skill in the art, other can also be made not on the basis of the above description With the change or variation of form.There is no need and unable to be exhaustive to all of implementation method.And thus extend out it is aobvious And the change that is clear to or change still in protection scope of the present invention.

Claims (7)

1. a kind of sulphur nitrogen codope graphene nano material, it is characterised in that described sulphur nitrogen codope graphene nano material It is prepared as follows obtaining:
(1) by sulphur nitrogen presoma, graphene oxide in mass ratio 0.5~3:After 1 mixing, add in ethanol, ultrasonic disperse is uniform, Then in 40~90 DEG C of drying, the compound of graphene oxide and sulphur nitrogen presoma is obtained;
Described sulphur nitrogen presoma is thiocarbamide, amido thiocarbamide, sulphur nitrogen piperazine, methionine or cysteine;
(2) under inert gas shielding, the compound of step (1) gained graphene oxide and sulphur nitrogen presoma is placed in 800~ 1~5h is kept at a high temperature of 1000 DEG C, room temperature is naturally cooled to afterwards, obtain described sulphur nitrogen codope graphene nano material Material.
2. sulphur nitrogen codope graphene nano material as claimed in claim 1, it is characterised in that in step (1), described oxygen Graphite alkene is single-layer graphene oxide, few layer graphene oxide or multilayer graphene oxide.
3. sulphur nitrogen codope graphene nano material as claimed in claim 1, it is characterised in that in step (1), the ethanol Volumetric usage 80~400mL/g is calculated as with the quality of graphene oxide.
4. sulphur nitrogen codope graphene nano material as claimed in claim 1, it is characterised in that in step (1), the ethanol Volumetric usage 100~200mL/g is calculated as with the quality of graphene oxide.
5. sulphur nitrogen codope graphene nano material as claimed in claim 1 as multifunction clips layer material in lithium-sulfur cell Application.
6. sulphur nitrogen codope graphene nano material as claimed in claim 5 as multifunction clips layer material in lithium-sulfur cell Application, it is characterised in that the method for the application is:
Described sulphur nitrogen codope graphene nano material is pressed into feed liquid mass ratio 0.1~30:In 100 addition organic solvents, surpass Sound is uniformly dispersed, and obtains solidliquid mixture slurry, and it is brushed on lithium-sulphur cell positive electrode surface with spreader, and then vacuum is done It is dry, that is, realize and sulphur nitrogen codope graphene nano material is integrated in lithium-sulphur cell positive electrode structure, subsequently according to routine operation Carry out battery assembling and performance test;
Described organic solvent is 1-METHYLPYRROLIDONE or (S)-(+) -5- methylols -2-Pyrrolidone;
The material of the lithium-sulphur cell positive electrode is carbon black/sulphur, porous carbon/sulphur, Graphene/sulphur, CNT/sulphur, carbon fiber/sulphur Or CMK-3/ sulphur;
Described sulphur nitrogen codope graphene nano material is integrated in after lithium-sulphur cell positive electrode structure, the sulphur nitrogen codope graphite The mass percent that alkene nano material accounts for whole lithium-sulphur cell positive electrode is 0.2%~1%.
7. sulphur nitrogen codope graphene nano material as claimed in claim 6 as multifunction clips layer material in lithium-sulfur cell Application, it is characterised in that described sulphur nitrogen codope graphene nano material press feed liquid mass ratio 1~5:100 additions are organic In solvent.
CN201611257681.5A 2016-12-30 2016-12-30 Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof Pending CN106684389A (en)

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CN110790262A (en) * 2019-10-31 2020-02-14 西北工业大学 Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method
CN111155146A (en) * 2019-12-26 2020-05-15 浙江大学 Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material
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CN114792797A (en) * 2022-03-25 2022-07-26 西交利物浦大学 Preparation method of sulfydryl modified MXene-sulfur composite material and lithium-sulfur battery thereof

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CN109713313A (en) * 2018-12-29 2019-05-03 珠海光宇电池有限公司 A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell
CN110790262B (en) * 2019-10-31 2022-11-04 西北工业大学 Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method
CN110790262A (en) * 2019-10-31 2020-02-14 西北工业大学 Preparation method for preparing nitrogen-sulfur double-doped graphene negative electrode material by low-temperature molten salt method
CN111155146A (en) * 2019-12-26 2020-05-15 浙江大学 Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material
CN111403711A (en) * 2020-03-26 2020-07-10 内蒙古杉杉科技有限公司 Sulfur-nitrogen co-doped graphene loaded nano-silicon three-dimensional electrode material and preparation method thereof
CN111403711B (en) * 2020-03-26 2023-03-14 内蒙古杉杉科技有限公司 Sulfur-nitrogen co-doped graphene loaded nano-silicon three-dimensional electrode material and preparation method thereof
WO2022035172A1 (en) * 2020-08-10 2022-02-17 주식회사 엘지에너지솔루션 Anode coating for lithium secondary battery, manufacturing method therefor, and anode and lithium secondary battery, each including same coating
CN112093796A (en) * 2020-09-24 2020-12-18 江苏江南烯元石墨烯科技有限公司 Preparation method of sulfur-nitrogen doped graphene material
CN113097470A (en) * 2021-03-29 2021-07-09 长春理工大学 Nitrogen-sulfur-containing co-doped graphene cobalt-copper-silicon hydrogen storage composite material and preparation method thereof
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