CN105742567A - Composite positive electrode of lithium sulfur battery, preparation method of composite positive electrode and lithium sulfur battery - Google Patents

Composite positive electrode of lithium sulfur battery, preparation method of composite positive electrode and lithium sulfur battery Download PDF

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Publication number
CN105742567A
CN105742567A CN201610270171.5A CN201610270171A CN105742567A CN 105742567 A CN105742567 A CN 105742567A CN 201610270171 A CN201610270171 A CN 201610270171A CN 105742567 A CN105742567 A CN 105742567A
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layer
lithium
carbon
sulfur
anode composite
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钱昕晔
沈湘黔
赵迪
杨晓龙
王善文
习小明
周友元
廖达前
黄承焕
姚山山
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC 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
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

A composite positive electrode of a lithium sulfur battery is formed by combining a diaphragm layer, a porous carbon layer and a carbon sulfur compound, wherein the porous carbon layer is arranged on one side of the diaphragm layer, and the carbon sulfur compound is arranged on the porous carbon layer. The preparation method comprises the following steps of adding the porous carbon, a conductive agent and an adhesive into an organic solvent to prepare paste, applying the paste onto one side of a diaphragm, and forming a porous carbon layer compound on one surface of the diaphragm layer; and adding the carbon sulfur compound, the conductive agent and the adhesive into the organic solvent to prepare paste, and applying the paste onto the porous carbon layer in the compound to obtain the composite positive electrode of the lithium sulfur battery. The lithium sulfur battery disclosed by the invention comprises the composite positive electrode of the lithium sulfur battery, a negative electrode and an electrolyte. By the lithium sulfur battery, the interface resistance can be reduced, the ionic conductivity and electron conductivity are improved, and the energy density, the cycle performance and the rate performance of the lithium sulfur battery are effectively improved.

Description

A kind of lithium-sulfur cell anode composite and preparation method thereof, lithium-sulfur cell
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of lithium-sulfur cell anode composite and preparation method thereof, lithium-sulfur cell.
Background technology
Along with developing rapidly of electric automobile and portable type electronic product, in the urgent need to developing the lithium ion battery of higher energy density.But by the restriction of the specific capacities such as tradition positive electrode such as cobalt acid lithium, LiMn2O4, its specific energy is difficult to be greatly improved again, thus it is imperative to develop new positive electrode.Lithium sulfur (Li-S) battery be with lithium be negative pole (theoretical specific capacity 3860mAh/g), sulfur be a kind of model electrochemical energy-storage system of positive pole (theoretical specific capacity 1675mAh/g), theoretical specific energy is up to 2600Wh/kg, commercial Li-ion battery much larger than present stage, and the rich reserves that sulfur is on earth, there is advantage cheap, low toxicity so that this system great commercial value.But sulfur there is also some problems in actual applications, first, its electrical conductivity is very low, is at room temperature about 5 × 10-30S/cm, must add conductive agent during as electrode material, thus the energy density of positive electrode can be reduced;Secondly, the many lithium sulfides of intermediate product of electrochemical reaction are soluble in electrolyte and produce " effect of shuttling back and forth ", reduce utilization rate and the cycle performance of sulfur, add ion migration resistance, simultaneously discharging product Li2S2And Li2S can deposit on sulfur electrode surface, forms solid electrolyte interface thin film (SEI), causes that utilization efficiency and cycle performance decline;Again, the volume that sulfur positive pole occurs in charge and discharge process acute variation repeatedly can cause battery structure unstable, causes cycle life and special capacity fade.
In the last few years, academia and business circles are mainly through studying relevant positive electrode and electrolyte to improve electric conductivity and the utilization rate of sulfur, suppress the diffusion of polysulfide, and to the integrated design of barrier film and positive pole and the integral energy density attention rate of lithium-sulfur cell is not high.CN103490027A Chinese patent proposition use Porous barriers is carried on common diaphragm as the adsorption layer of polysulfide, suppress the diffusion of polysulfide further, but such a process increases the quality of lithium-sulfur cell septation and volume, actually likely reduce the volume energy density of lithium-sulfur cell, and the combination interface between Porous barriers and positive pole is not tight, easily increase interface resistance, reduce ionic conductance and electronic conductance.CN103972467A Chinese patent devises a kind of multi-layer compound structure being made up of the first graphene film layer, carbon/sulfur active material layer, the second graphene film layer and polymeric layer, achieve lithium-sulfur cell multicomponent integrated design, first graphene film layer is collector, and the second graphene film layer is polysulfide barrier layer.Graphene is substituted aluminium foil as collector by the multi-layer film structure of this similar sandwich structure, decreases the quality of electrode, and on barrier film, the Graphene of load can suppress the diffusion of polysulfide, improve the capacity of battery.But, the use cost of Graphene is also higher at present on the one hand, is unfavorable for extensive popularization and application;On the other hand, this multi-layer structure design actually and unrealized truly positive pole integration because Graphene modified diaphragm and Graphene collector remain two parts of separation, certain interface resistance after being assembled into battery, can be produced.
Summary of the invention
The technical problem to be solved is, overcomes deficiency of the prior art, it is provided that a kind of lithium-sulfur cell anode composite and preparation method thereof, lithium-sulfur cell.Barrier film, porous carbon layer (as upper strata collector and polysulfide physical barrier) and carbon-sulfur compound layer (as active material layer) are organically combined, it is achieved that positive pole integrated design truly.This anode composite is used for lithium-sulfur cell, can reduce interface resistance, increases ionic conductance and electronic conductance, is effectively improved the mass energy density of lithium-sulfur cell, volume energy density, cycle performance and high rate performance.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
A kind of lithium-sulfur cell anode composite, this anode composite is composited by membrane layer, porous carbon layer and carbon-sulfur compound layer, wherein porous carbon layer is arranged at the side of membrane layer, carbon-sulfur compound layer is arranged on porous carbon layer, forms the anode composite of membrane layer/porous carbon layer/carbon-sulfur compound layer three-decker.
Above-mentioned lithium-sulfur cell anode composite, it is preferred that the thickness of described porous carbon layer is 10 μm ~ 50 μm, the thickness of described carbon-sulfur compound layer is 40 μm ~ 200 μm.Porous carbon layer at this thickness range can effectively transmit ion and electronics and absorbed portion polysulfide;Carbon-sulfur compound layer is as active material layer, and integral thickness is thicker than porous carbon layer, it is possible to be effectively improved the energy density of positive pole.
Above-mentioned lithium-sulfur cell anode composite, it is preferred that described membrane layer one in polypropylene screen, polyethylene film, polypropylene screen is Celgard2400 more preferably.
Above-mentioned lithium-sulfur cell anode composite, it is preferred that described porous carbon layer is obtained by porous carbon, conductive agent and binding agent compound;Described carbon-sulfur compound layer is obtained by carbon-sulfur compound, conductive agent and binding agent compound, and described carbon-sulfur compound is obtained by porous carbon and elemental sulfur compound.It is furthermore preferred that at least one that described porous carbon is in Ketjen black, CNT, carbon nano-fiber, Graphene, fullerene, Cabot carbon black BP2000, activated carbon, described conductive agent is selected from white carbon black Super-P, and described binding agent is selected from Kynoar.
As a total inventive concept, the preparation method that the present invention also provides for above-mentioned lithium-sulfur cell anode composite, comprise the following steps:
(1) porous carbon, conductive agent and binding agent being joined mix homogeneously in organic solvent, make slurry, the rear flank that then slurry is uniformly coated on barrier film is dried again, obtains being formed with on a surface of membrane layer the complex of porous carbon layer;
(2) carbon-sulfur compound, conductive agent and binding agent are joined mix homogeneously in organic solvent, make slurry, then it is dried again after slurry being uniformly coated on the porous carbon layer in the complex that step (1) obtains, obtains described lithium-sulfur cell anode composite.
Above-mentioned preparation method, it is preferred that described step (1) and in step (2), described organic solvent is selected from N-Methyl pyrrolidone, the mass ratio of binding agent and organic solvent is 1:20 ~ 80, and baking temperature is 45 DEG C-55 DEG C (most preferably 50 DEG C), and drying time is 4 ~ 8 hours;In described step (1), the mass ratio of porous carbon, conductive agent and binding agent is (7 ~ 8): (2 ~ 1): 1;In described step (2), the mass ratio of carbon-sulfur compound, conductive agent and binding agent is (7 ~ 8): (2 ~ 1): 1.
Above-mentioned preparation method, it is preferred that in described step (2), carbon-sulfur compound is prepared by following methods: mixed with elemental sulfur by porous carbon, through wet ball grinding, places into and carries out heat treatment in hermetic container after drying, obtain carbon-sulfur compound.It is furthermore preferred that the mass ratio of porous carbon and elemental sulfur is 1:1 ~ 5, the rotating speed of wet ball grinding is 400 ~ 1000r/min, and heat treatment temperature is 155 DEG C, and heat treatment time is 6 ~ 12 hours.
The present invention also provides for a kind of lithium-sulfur cell, including above-mentioned lithium-sulfur cell anode composite, negative pole and electrolyte.Negative pole is preferably metal lithium sheet, and electrolyte is preferably the mixed solution of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.
Present invention is characterized in that the present invention by being coated on the side of barrier film by porous carbon, again carbon-sulfur compound is coated on porous carbon layer, define and constituted three-layer composite structure by membrane layer, porous carbon layer and carbon-sulfur compound layer, achieve the integrated design of lithium-sulfur cell anode composite, the membrane layer decreasing porous carbon modified separates, with carbon sulfur anode composite, the interface resistance caused, increase ionic conductance and electronic conductance, wherein porous carbon layer plays upper strata collector and the effect of polysulfide physical barrier, and carbon-sulfur compound layer is active material layer.In general, upper strata collector generally plays lithium ion conducting passage and the effect of part electronic conduction, and lower floor's collector mainly plays the effect of electronic conduction, and lower floor's collector is necessary.But in the present invention, lower floor's collector can be removed, because the pattern of carbon sulfur composite positive pole is carbon cladding sulfur, such material with carbon element actually just serves the effect of electronic conduction at outer layer, and owing to upper strata afflux physical ability collects substantial amounts of lithium ion, these electronics and lithium ion can exchange immediately, so that electrochemical reaction is carried out rapidly.The present invention ensures that in the process of coating upper strata collector and carbon sulfur composite bed are combined closely, it is not easy to comes off, thus can guarantee that the integration of positive pole and barrier film, increases electronics and ionic conductance.The present invention also removes metal collector conventional in lithium-sulfur cell and (is generally aluminium foil, as lower floor's collector), simplify preparation technology, effectively reduce quality and the volume of positive pole, improve mass energy density and the volume energy density of lithium-sulfur cell;Porous carbon layer ensure that the transmission of ion and electronics on the one hand, effectively inhibits the effect of shuttling back and forth of polysulfide on the other hand, has relaxed the volumetric expansion in course of reaction, the specific capacity of lithium-sulfur cell, cycle performance and high rate performance are greatly improved.
Compared with prior art, it is an advantage of the current invention that:
(1) present invention eliminates aluminum foil current collector conventional in lithium-sulfur cell, simplify preparation technology, decrease quality and the volume of anode composite, it is possible to improve mass energy density and the volume energy density of lithium-sulfur cell.
(2) anode composite of the present invention is the three layers compact texture of membrane layer/porous carbon layer/carbon-sulfur compound layer, achieve the integrated design of lithium-sulfur cell anode composite, the membrane layer decreasing porous carbon modified separates, with carbon sulfur anode composite, the interface resistance caused, increase ionic conductance and electronic conductance, be conducive to the carrying out of electrochemical reaction.
(3) porous carbon layer in anode composite of the present invention both can as the upper strata collector of carbon-sulfur compound layer, can also as the physical barrier of polysulfide, ensure that the transmission of ion and electronics, inhibit the effect of shuttling back and forth of polysulfide, relax the volumetric expansion in course of reaction, the specific capacity of lithium-sulfur cell, cycle performance and high rate performance have been greatly improved.
(4) barrier film, porous carbon and carbon-sulfur compound have been carried out integrated compound by the present invention, and the lithium-sulfur cell anode composite obtained is flexible, has good mechanical performance, it is possible to be used for preparing flexible battery.
(5) preparation method of anode composite of the present invention is simple, easily-controllable, it is possible to preparation low cost, high power, long-life lithium-sulfur cell, has great application prospect.
Accompanying drawing explanation
Fig. 1 is lithium-sulfur cell anode composite structural representation of the present invention.
Fig. 2 uses anode composite of the present invention to assemble the lithium-sulfur cell structural representation formed.
Fig. 3 is the lithium-sulfur cell for preparing of the embodiment of the present invention 1 cycle performance curve chart under 1C.
Fig. 4 is the high rate performance curve chart of the lithium-sulfur cell that the embodiment of the present invention 1 prepares.
Detailed description of the invention
As shown in Figure 1, the lithium-sulfur cell anode composite of the present invention is composited by three layers, it is followed successively by carbon-sulfur compound layer, porous carbon layer and membrane layer from the bottom to top, the thickness of porous carbon layer is 10 μm ~ 50 μm, the thickness of carbon-sulfur compound layer is 40 μm ~ 200 μm, wherein porous carbon layer plays the effect of upper strata collector and physical barrier, and carbon-sulfur compound layer is active material layer.This anode composite is used to assemble the lithium-sulfur cell structural representation formed as in figure 2 it is shown, include this anode composite, electrolyte, metal lithium sheet (negative pole), load and battery case.
Embodiment 1
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by Celgard2400 membrane layer, Ketjen black layer and Ketjen black-sulfur compound layer, wherein Ketjen black layer is arranged at the side of Celgard2400 membrane layer, Ketjen black-sulfur compound layer is arranged on Ketjen black layer, forms the anode composite of Celgard2400 membrane layer/Ketjen black layer/Ketjen black-sulfur compound layer three-decker.Wherein, the thickness of Ketjen black layer is 10 μm, and the thickness of Ketjen black-sulfur compound layer is 50 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of Celgard2400 barrier film, dry 4 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of Celgard2400 membrane layer the complex of Ketjen black layer, the thickness recording Ketjen black layer with micrometer is 10 μm;
(2) Ketjen black and elemental sulfur are mixed according to mass ratio 1:3, carrying out wet ball grinding in high speed ball mill, rotational speed of ball-mill is 800r/min, and Ball-milling Time is 6h, after drying the powder obtained is put into hermetic container heat treatment 10 hours at 155 DEG C, obtain Ketjen black-sulfur compound;It is that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the Ketjen black layer in the complex that step (1) obtains, dry 4 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording Ketjen black-sulfur compound layer with micrometer is 50 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and test result is as it is shown on figure 3, it can be seen that first discharge specific capacity is 1069mAh/g, after circulating 100 times, the specific discharge capacity of battery still reaches 950mAh/g, and coulombic efficiency is more than 90%;The high rate performance curve of lithium-sulfur cell is tested as shown in Figure 4, it can be seen that when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1250mAh/g.
Embodiment 2
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by Celgard2400 membrane layer, carbon nanotube layer and CNT-sulfur compound layer, wherein carbon nanotube layer is arranged at the side of Celgard2400 membrane layer, CNT-sulfur compound layer is arranged on carbon nanotube layer, forms the anode composite of Celgard2400 membrane layer/carbon nanotube layer/CNT-sulfur compound layer three-decker.Wherein, the thickness of carbon nanotube layer is 20 μm, and the thickness of CNT-sulfur compound layer is 80 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by CNT, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of Celgard2400 barrier film, dry 5 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of Celgard2400 membrane layer the complex of carbon nanotube layer, the thickness recording carbon nanotube layer with micrometer is 20 μm;
(2) CNT and elemental sulfur are mixed according to mass ratio 1:2, carrying out wet ball grinding in high speed ball mill, rotational speed of ball-mill is 600r/min, and Ball-milling Time is 6h, after drying the powder obtained is put into hermetic container heat treatment 12 hours at 155 DEG C, obtain CNT-sulfur compound;It is that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by CNT-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the carbon nanotube layer in the complex that step (1) obtains, dry 5 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording CNT-sulfur compound layer with micrometer is 80 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1019mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 910mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1217mAh/g.
Embodiment 3
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by Celgard2400 membrane layer, graphene layer and Ketjen black-sulfur compound layer, wherein graphene layer is arranged at the side of Celgard2400 membrane layer, Ketjen black-sulfur compound layer is arranged on graphene layer, forms the anode composite of Celgard2400 membrane layer/graphene layer/Ketjen black-sulfur compound layer three-decker.Wherein, the thickness of graphene layer is 10 μm, and the thickness of Ketjen black-sulfur compound layer is 70 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by Graphene, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:60 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of Celgard2400 barrier film, dry 6 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of Celgard2400 membrane layer the complex of graphene layer, the thickness recording graphene layer with micrometer is 10 μm;
(2) Ketjen black and elemental sulfur are mixed according to mass ratio 1:4, carrying out wet ball grinding in high speed ball mill, rotational speed of ball-mill is 800r/min, and Ball-milling Time is 6h, after drying the powder obtained is put into hermetic container heat treatment 10 hours at 155 DEG C, obtain Ketjen black-sulfur compound;It is that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the graphene layer in the complex that step (1) obtains, dry 6 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording Ketjen black-sulfur compound layer with micrometer is 70 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1124mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 995mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1340mAh/g.
Embodiment 4
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by Celgard2400 membrane layer, carbon nano-fiber layer and carbon nano-fiber-sulfur compound layer, wherein carbon nano-fiber layer is arranged at the side of polypropylene screen membrane layer, carbon nano-fiber-sulfur compound layer is arranged on carbon nano-fiber layer, forms the anode composite of Celgard2400 membrane layer/carbon nano-fiber layer/carbon nano-fiber sulfur compound layer three-decker.Wherein, the thickness of carbon nano-fiber layer is 20 μm, and the thickness of carbon nano-fiber-sulfur compound layer is 80 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by carbon nano-fiber, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:60 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of polypropylene diaphragm, dry 7 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of Celgard2400 membrane layer the complex of carbon nano-fiber layer, the thickness recording carbon nano-fiber layer with micrometer is 20 μm;
(2) carbon nano-fiber and elemental sulfur are mixed according to mass ratio 1:2.5, high speed ball mill carries out wet ball grinding, rotational speed of ball-mill is 900r/min, Ball-milling Time is 8h, after drying the powder obtained is put into hermetic container heat treatment 12 hours at 155 DEG C, obtain carbon nano-fiber-sulfur compound;It is that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by carbon nano-fiber-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:60 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the carbon nano-fiber layer in the complex that step (1) obtains, dry 7 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording carbon nano-fiber-sulfur compound layer with micrometer is 80 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1040mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 890mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1180mAh/g.
Embodiment 5
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by polyethylene film membrane layer, carbon nanotube layer and graphene-sulfur composite layer, wherein carbon nanotube layer is arranged at the side of polyethylene film membrane layer, graphene-sulfur composite layer is arranged on carbon nanotube layer, forms the anode composite of polyethylene film membrane layer/carbon nanotube layer/graphene-sulfur composite layer three-decker.Wherein, the thickness of carbon nanotube layer is 15 μm, and the thickness of CNT-sulfur compound layer is 80 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by CNT, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of polyethylene diagrams, dry 8 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of polyethylene film membrane layer the complex of carbon nanotube layer, the thickness recording carbon nanotube layer with micrometer is 15 μm;
(2) Graphene and elemental sulfur are mixed according to mass ratio 1:5, carrying out wet ball grinding in high speed ball mill, rotational speed of ball-mill is 1000r/min, and Ball-milling Time is 10h, after drying the powder obtained is put into hermetic container heat treatment 12 hours at 155 DEG C, obtain graphene-sulfur complex;It is that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by CNT-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:60 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the carbon nanotube layer in the complex that step (1) obtains, dry 8 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording graphene-sulfur composite layer with micrometer is 80 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1165mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 1050mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1420mAh/g.
Embodiment 6
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by polyethylene film membrane layer, Cabot carbon black BP2000 layer and Cabot carbon black BP2000-sulfur compound layer, wherein Cabot carbon black BP2000 layer is arranged at the side of polyethylene film membrane layer, Cabot carbon black BP2000-sulfur compound layer is arranged on Cabot carbon black BP2000 layer, forms the anode composite of polyethylene film membrane layer/Cabot carbon black BP2000 layer/Cabot carbon black BP2000-sulfur compound layer three-decker.Wherein, the thickness of Cabot carbon black BP2000 layer is 10 μm, and the thickness of Cabot carbon black BP2000-sulfur compound layer is 40 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 8:1:1 joins mix homogeneously in N-Methyl pyrrolidone by Cabot carbon black BP2000, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of polyethylene film barrier film, dry 5 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of polyethylene diagrams layer the complex of Cabot carbon black BP2000 layer, the thickness recording Cabot carbon black BP2000 layer with micrometer is 10 μm;
(2) Cabot carbon black BP2000 and elemental sulfur are mixed according to mass ratio 1:3.5, high speed ball mill carries out wet ball grinding, rotational speed of ball-mill is 800r/min, Ball-milling Time is 9h, after drying the powder obtained is put into hermetic container heat treatment 12 hours at 155 DEG C, obtain Cabot carbon black BP2000-sulfur compound;It is that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by Cabot carbon black BP2000-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the Cabot carbon black BP2000 layer in the complex that step (1) obtains, dry 5 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording Cabot carbon black BP2000-sulfur compound layer with micrometer is 40 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1040mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 910mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1197mAh/g.
Embodiment 7
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by polyethylene film membrane layer, Ketjen black layer and CNT-sulfur compound layer, wherein Ketjen black layer is arranged at the side of polyethylene film membrane layer, CNT-sulfur compound layer is arranged on Ketjen black layer, forms the anode composite of polyethylene film membrane layer/Ketjen black layer/CNT-sulfur compound layer three-decker.Wherein, the thickness of Ketjen black layer is 20 μm, and the thickness of CNT-sulfur compound layer is 80 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7.5:1.5:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of polyethylene diagrams, dry 6 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of polyethylene film membrane layer the complex of Ketjen black layer, the thickness recording Ketjen black layer with micrometer is 20 μm;
(2) CNT and elemental sulfur are mixed according to mass ratio 1:4.5, high speed ball mill carries out wet ball grinding, rotational speed of ball-mill is 800r/min, Ball-milling Time is 8h, after drying the powder obtained is put into hermetic container heat treatment 12 hours at 155 DEG C, obtain CNT-sulfur compound;It is that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by CNT-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the Ketjen black layer in the complex that step (1) obtains, dry 6 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording CNT-sulfur compound layer with micrometer is 80 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1115mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 970mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, fills
When discharge-rate is 0.1C, the first discharge specific capacity of battery reaches 1297mAh/g.
Embodiment 8
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by Celgard2400 membrane layer, Ketjen black layer and CNT-sulfur compound layer, wherein Ketjen black layer is arranged at the side of Celgard2400 membrane layer, CNT-sulfur compound layer is arranged on Ketjen black layer, forms the anode composite of Celgard2400 membrane layer/Ketjen black layer/CNT-sulfur compound layer three-decker.Wherein, the thickness of Ketjen black layer is 20 μm, and the thickness of CNT-sulfur compound layer is 110 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7.5:1.5:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of Celgard2400 barrier film, dry 8 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of Celgard2400 membrane layer the complex of Ketjen black layer, the thickness recording Ketjen black layer with micrometer is 20 μm;
(2) CNT and elemental sulfur are mixed according to mass ratio 1:4, carrying out wet ball grinding in high speed ball mill, rotational speed of ball-mill is 700r/min, and Ball-milling Time is 8h, after drying the powder obtained is put into hermetic container heat treatment 12 hours at 155 DEG C, obtain CNT-sulfur compound;It is that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by CNT-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the Ketjen black layer in the complex that step (1) obtains, dry 8 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording CNT-sulfur compound layer with micrometer is 110 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1075mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 960mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1244mAh/g.
Embodiment 9
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by polyethylene film membrane layer, graphene layer and Ketjen black-sulfur compound layer, wherein graphene layer is arranged at the side of polyethylene film membrane layer, Ketjen black-sulfur compound layer is arranged on graphene layer, forms the anode composite of polyethylene film membrane layer/graphene layer/Ketjen black-sulfur compound layer three-decker.Wherein, the thickness of graphene layer is 30 μm, and the thickness of CNT-sulfur compound layer is 150 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by Graphene, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:45 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of polyethylene diagrams, dry 6 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of polyethylene film membrane layer the complex of graphene layer, the thickness recording graphene layer with micrometer is 30 μm;
(2) Ketjen black and elemental sulfur are mixed according to mass ratio 1:3.5, high speed ball mill carries out wet ball grinding, rotational speed of ball-mill is 900r/min, Ball-milling Time is 10h, after drying the powder obtained is put into hermetic container heat treatment 10 hours at 155 DEG C, obtain CNT-sulfur compound;It is that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black-sulfur compound, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the graphene layer in the complex that step (1) obtains, dry 6 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording Ketjen black-sulfur compound layer with micrometer is 150 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1200mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 1010mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1370mAh/g.
Embodiment 10
A kind of lithium-sulfur cell anode composite of the present invention, this anode composite is composited by Celgard2400 membrane layer, Ketjen black layer and graphene-sulfur composite layer, wherein Ketjen black layer is arranged at the side of Celgard2400 membrane layer, graphene-sulfur composite layer is arranged on Ketjen black layer, forms the anode composite of Celgard2400 membrane layer/Ketjen black layer/graphene-sulfur composite layer three-decker.Wherein, the thickness of Ketjen black layer is 35 μm, and the thickness of graphene-sulfur composite layer is 180 μm.
The preparation method of the lithium-sulfur cell anode composite of the present embodiment, comprises the following steps:
(1) being that 7.5:1.5:1 joins mix homogeneously in N-Methyl pyrrolidone by Ketjen black, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:50 with the mass ratio of N-Methyl pyrrolidone;Then the slurry obtained is uniformly coated on the side of Celgard2400 barrier film, dry 7 hours at 50 DEG C in air dry oven subsequently, obtaining being formed with on a surface of Celgard2400 membrane layer the complex of Ketjen black layer, the thickness recording Ketjen black layer with micrometer is 35 μm;
(2) Graphene and elemental sulfur are mixed according to mass ratio 1:4, carrying out wet ball grinding in high speed ball mill, rotational speed of ball-mill is 850r/min, and Ball-milling Time is 7h, after drying the powder obtained is put into hermetic container heat treatment 10 hours at 155 DEG C, obtain graphene-sulfur complex;It is that 7:2:1 joins mix homogeneously in N-Methyl pyrrolidone by graphene-sulfur complex, white carbon black Super-P and Kynoar according to mass ratio, make slurry, wherein Kynoar is 1:40 with the mass ratio of N-Methyl pyrrolidone, then the slurry obtained is uniformly coated on the Ketjen black layer in the complex that step (1) obtains, dry 7 hours at 50 DEG C in air dry oven subsequently, obtaining the lithium-sulfur cell anode composite of the present invention, the thickness recording graphene-sulfur composite layer with micrometer is 180 μm.
The lithium-sulfur cell anode composite, negative pole (metal lithium sheet) and the electrolyte that are prepared by the present embodiment are assembled into lithium-sulfur cell, and electrolyte is the mixture of bis trifluoromethyl sulfonic acid Asia amide lithium, lithium nitrate, DOX and glycol dimethyl ether.The lithium-sulfur cell prepared is circulated performance test under 1C, and first discharge specific capacity is 1190mAh/g, and after circulating 100 times, the specific discharge capacity of battery still reaches 1000mAh/g, and coulombic efficiency is more than 90%;The high rate performance test result of lithium-sulfur cell shows, when charge-discharge magnification is 0.1C, the first discharge specific capacity of battery reaches 1225mAh/g.

Claims (10)

1. a lithium-sulfur cell anode composite, it is characterized in that, this anode composite is composited by membrane layer, porous carbon layer and carbon-sulfur compound layer, wherein porous carbon layer is arranged at the side of membrane layer, carbon-sulfur compound layer is arranged on porous carbon layer, forms the anode composite of membrane layer/porous carbon layer/carbon-sulfur compound layer three-decker.
2. lithium-sulfur cell anode composite as claimed in claim 1, it is characterised in that the thickness of described porous carbon layer is 10 μm ~ 50 μm, and the thickness of described carbon-sulfur compound layer is 40 μm ~ 200 μm.
3. lithium-sulfur cell anode composite as claimed in claim 1, it is characterised in that described membrane layer one in polyethylene film, polypropylene screen.
4. lithium-sulfur cell anode composite as claimed in claim 1, it is characterised in that described porous carbon layer is obtained by porous carbon, conductive agent and binding agent compound;Described carbon-sulfur compound layer is obtained by carbon-sulfur compound, conductive agent and binding agent compound, and described carbon-sulfur compound is obtained by porous carbon and elemental sulfur compound.
5. lithium-sulfur cell anode composite as claimed in claim 4, it is characterized in that, described porous carbon at least one in Ketjen black, CNT, carbon nano-fiber, Graphene, fullerene, Cabot carbon black BP2000, activated carbon, described conductive agent is selected from white carbon black Super-P, and described binding agent is selected from Kynoar.
6. the preparation method of the lithium-sulfur cell anode composite as according to any one of claim 1 ~ 5, it is characterised in that comprise the following steps:
(1) porous carbon, conductive agent and binding agent being joined mix homogeneously in organic solvent, make slurry, the rear flank that then slurry is uniformly coated on barrier film is dried again, obtains being formed with on a surface of membrane layer the complex of porous carbon layer;
(2) carbon-sulfur compound, conductive agent and binding agent are joined mix homogeneously in organic solvent, make slurry, then it is dried again after slurry being uniformly coated on the porous carbon layer in the complex that step (1) obtains, obtains described lithium-sulfur cell anode composite.
7. preparation method as claimed in claim 6, it is characterized in that, in described step (1) and step (2), described organic solvent is selected from N-Methyl pyrrolidone, the mass ratio of binding agent and organic solvent is 1:20 ~ 80, baking temperature is 45 DEG C-55 DEG C, and drying time is 4 ~ 8 hours;In described step (1), the mass ratio of porous carbon, conductive agent and binding agent is (7 ~ 8): (2 ~ 1): 1;In described step (2), the mass ratio of carbon-sulfur compound, conductive agent and binding agent is (7 ~ 8): (2 ~ 1): 1.
8. preparation method as claimed in claim 6, it is characterized in that, in described step (2), carbon-sulfur compound is prepared by following methods: mixed with elemental sulfur by porous carbon, through wet ball grinding, place into hermetic container carries out heat treatment after drying, obtain carbon-sulfur compound.
9. preparation method as claimed in claim 8, it is characterised in that the mass ratio of porous carbon and elemental sulfur is 1:1 ~ 5, and the rotating speed of wet ball grinding is 400 ~ 1000r/min, and heat treatment temperature is 155 DEG C, and heat treatment time is 6 ~ 12 hours.
10. a lithium-sulfur cell, it is characterised in that include the lithium-sulfur cell anode composite according to any one of claim 1 ~ 5, negative pole and electrolyte.
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US10644290B2 (en) 2016-11-29 2020-05-05 Lg Chem, Ltd. Separator including laser-induced carbonized graphene layer and lithium-sulfur battery including the same
CN108963325A (en) * 2018-08-14 2018-12-07 桑德集团有限公司 Soft bag lithium ionic cell and preparation method thereof and electrical equipment
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CN110911682A (en) * 2019-11-06 2020-03-24 华南理工大学 Electrode of lithium-sulfur battery and preparation method and application thereof
CN112072067A (en) * 2020-09-18 2020-12-11 北京理工大学 Carbon-sulfur composite positive electrode for lithium-sulfur battery and preparation method thereof

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