CN104201339A - Battery positive-electrode as well as preparation method and application thereof in lithium-sulfur batteries - Google Patents

Battery positive-electrode as well as preparation method and application thereof in lithium-sulfur batteries Download PDF

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CN104201339A
CN104201339A CN201410478138.2A CN201410478138A CN104201339A CN 104201339 A CN104201339 A CN 104201339A CN 201410478138 A CN201410478138 A CN 201410478138A CN 104201339 A CN104201339 A CN 104201339A
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carbon
lithium
anode
sulphur
water
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CN104201339B (en
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赵金保
张义永
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Xiamen University
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Xiamen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a battery positive-electrode as well as a preparation method and application thereof in lithium-sulfur batteries. The battery positive-electrode is provided with a metal current collector, positive active materials and an adhesive, and the positive active materials coat the current collector through the adhesive and comprise a carbon-based /sulfur composite material and a conductive agent. The preparation method comprises the following steps: putting a carbon-based material in water for ultrasonic treatment to obtain a carbon-based material dispersion liquid; mixing and dispersing sulfur and sodium sulfide in water, and adding TX 100 to obtain yellow polysulphide dispersion liquid; adding the yellow polysulphide dispersion liquid into the carbon-based material dispersion liquid for ultrasonic treatment, and then adding hydrochloric acid to obtain carbon-based-sulfide mixing liquid; carrying out a water bath and vacuum filtration, drying and then heating to obtain the carbon-based /sulfur composite material; mixing the carbon-based /sulfur composite material with the conductive agent, and grinding to obtain positive active material powder; mixing the positive active material powder with the adhesive solution to prepare positive active material powder slurry with an adhesive coating, coating the positive active material powder slurry on the metal current collector, and drying to obtain the battery positive-electrode.

Description

Anode and preparation method thereof and application in lithium-sulfur cell
Technical field
The present invention relates to anode, especially relate to a kind of anode and preparation method thereof and application in lithium-sulfur cell.
Background technology
Elemental sulfur has the multiple advantages such as high energy density, abundant natural resources, cheap and environmental friendliness, is very good anode material for lithium-ion batteries of future generation, and this field is all study hotspot all the time.Compared with conventional lithium ion battery, theoretical capacity is that the sulphur of 1672 mAh/g is as positive active material, and to use theoretical capacity be that the lithium metal of 3860 mAh/g is as the lithium-sulfur rechargeable battery of negative electrode active material, there is very high energy density, and there are the potentiality of manufacturing little, the lightweight and secondary cell that demand increases day by day of volume.Be expected to especially become the device of high-energy-density energy storage and automobile power using elemental sulfur composite material as anodal lithium-sulphur (Li-S) secondary cell.
In lithium-sulfur cell, the oxidation/reduction reaction between lithium and sulphur can be expressed as following reaction process:
2Li+S 8(solid) → Li 2s 8(solution)
2Li+Li2S 8(solution) → 2Li 2s 4(solution)
2Li+Li 2s 4(solution) → 2Li 2s 2(solution)
2Li+Li 2s 2(solution) → 2Li 2s (solids of sedimentation)
Can find out from above-mentioned reaction process, in the redox reaction between lithium and sulphur, generate new product, i.e. many lithium sulfides.Known in above-mentioned reaction sulphur and discharging product thereof be all electronics and ion insulator, electronics and ion, in anodal transmission difficulty, cause room temperature electrochemical reaction dynamics speed very slow, electrode interior reaction is insufficient.Many lithium sulfides that reduction process produces are soluble in organic electrolyte solvent, cause the loss of active material.Increase along with discharging and recharging all numbers, anodal and negative terminal surface can generate the Li of electronic isolation gradually 2s sedimentary deposit, hinders on the one hand electric charge transmission, has changed on the other hand the interface of electrode/electrolyte, increases the internal resistance of cell, finally causes that Li-S secondary cell active material utilization is low, capacity attenuation is rapid, thereby has limited its development.How admittedly sulphur, improves conductivity, increases cyclical stability, is the important topic of lithium-sulfur cell research and development.
At present, in lithium-sulfur cell research, solid sulphur method mainly contains two kinds of Physical and chemical methods.Wherein, the solid sulphur method of physics is mainly used various porous carbon materials to adsorb element sulphur as matrix, partly overcomes the shortcoming of above-mentioned lithium-sulfur cell, and has obtained marked improvement.The characteristics such as size, pattern, porosity and the texture of various porous carbon materials have material impact to the chemical property of S-C composite material.The material with carbon element matrix that it has been generally acknowledged that loose structure in these S-C compounds has mainly played two kinds of effects: effectively adsorb element sulphur, and suppress polysulfide to the diffusion in organic electrolyte; Carbon framework greatly facilitates electric transmission simultaneously, thereby has promoted the redox reaction on electrode, and utilance and the cyclical stability of element sulphur are improved.
In addition, the solid sulphur method of chemistry is mainly synthetic various organosulfur compounds, utilizes S-C chemical bond to consolidate sulphur.In organosulfur compound molecule, main chain is conducting polymer skeleton, can improve the conductivity of material, reduces the consumption of conductive agent, and then is conducive to improve anodal specific capacity; The S-S key of energy storage is connected on polymer backbone as side chain, when electric discharge, skeleton is not degraded, dissolubility in organic electrolyte, much smaller than little molecule polysulfide, can ensure that anodal dimensional stability and most of sulphur are trapped in positive polar region, and cycle performance will strengthen to some extent.
But existing lithium-sulphur cell positive electrode and corresponding lithium-sulfur cell, in the requirement that still can not meet business application aspect active material utilization and circulating battery characteristic, have limited the large-scale application of lithium-sulfur cell.
Summary of the invention
The object of the invention is to the problems referred to above that exist for existing anode, provide one to there is satisfactory electrical conductivity and fine sulfur capturing capacity, can improve the utilance of active material sulphur, give the cycle performance of lithium-sulfur cell excellence, and its preparation technology anode simple to operation and preparation method thereof and application in lithium-sulfur cell.
Described anode is provided with metal collector, positive active material and binder, and described positive active material is coated in metal collector by binder, and described positive active material comprises carbon back/sulphur composite material, conductive agent;
At least one in the optional self-expanding graphite of described carbon-based material, Graphene, carbon nano-tube, mesoporous carbon, hollow carbon sphere, graphene oxide etc., preferably expanded graphite.
Described sulfur materials can be selected from sublimed sulfur simple substance (S 8), Li 2s n(n>=1), organosulfur compound, carbon sulphur polymer ((C 2s x) n, wherein the scope of x is 2.5～50, and n>=2) etc. at least one, preferably sublimed sulfur simple substance (S 8).
In described carbon back/sulphur composite material, by mass percentage, the content of carbon back can be 20%～50%, and the content of sulphur can be 50%～80%.
The metal of described metal collector can be selected from a kind of elemental metals of element or the alloy of at least 2 kinds of elements in Fe, Co, Ni, Cu, Zn, Ag, Pt, Au etc., preferable alloy copper or copper alloy.
Described binder can adopt poly-vinylidene fluoride (PVDF) etc.
Described conductive agent can adopt acetylene black etc.
The preparation method of described anode, comprises the following steps:
1) first prepare compound carbon back/sulphur composite material:
Carbon-based material is put into water, after ultrasonic carbon-based material dispersion liquid; Again sulphur and vulcanized sodium mixing are dispersed in water, add surfactant TX100, obtain yellow polysulfide dispersion liquid; Yellow polysulfide dispersion liquid is added in carbon-based material dispersion liquid, again ultrasonic after, add hydrochloric acid, obtain carbon back-sulfide mixed liquor, under water-bath, stir, vacuum filtration, heat treated again after oven dry, obtains carbon back/sulphur composite material;
2) preparation of anode:
By step 1) carbon back/sulphur composite material of making and conductive agent mix and grind and obtain positive electrode active material powder, again positive electrode active material powder and binder solution are mixed, preparation comprises the positive active material powdery pulp of binder coating, be coated in metal collector, dry except after desolventizing, obtain anode.
In step 1) in, the proportioning of described carbon-based material and water can be (25～50) mg: 100mL, and wherein, carbon-based material is calculated in mass, and water is calculated by volume; Described water can adopt deionized water; The described ultrasonic time can be 5h; The proportioning of described sulphur, vulcanized sodium, water, surfactant TX100 and hydrochloric acid can be (50～75) mg: (50～75) mg: 100mL: 10mL: 10mL, wherein, sulphur and vulcanized sodium are calculated in mass, and water, surfactant TX100 and hydrochloric acid are calculated by volume; Described water can adopt deionized water; It is 1% surfactant TX100 that described surfactant TX100 can adopt mass concentration; Described ultrasonic time again can be 1h; The temperature of described water-bath can be 70 DEG C, and the time of stirring can be 1h; The temperature of described oven dry can be 60 DEG C, and the temperature of described heat treated can be 155 DEG C, and the time of heat treated can be 4h; When carbon-based material adopts when expanded graphite, expanded graphite, under air atmosphere, is processed 10s at 800 DEG C and is obtained by expansible graphite in tube furnace.
In step 2) in, the mass ratio of described carbon back/sulphur composite material and conductive agent can be (60～90): (0～30), and wherein, conductive agent is not 0; Described dry condition can be in 60 DEG C of baking ovens vacuumize 10～24h; The described thickness being coated in metal collector can be 10～500 μ m.
Because the prepared anode of the present invention has very high active material utilization efficiency, excellent cycling performance, therefore described anode can be applied preparing in lithium-sulfur cell.
Described lithium-sulfur cell comprises pond body, negative pole, barrier film, electrolyte and described anode; Negative pole, barrier film and described anode are located in the body of pond, and described negative pole comprises negative electrode active material, described negative electrode active material be selected from lithium embed material, Zinc-lithium alloy material and lithium metal in one; Barrier film is located between negative pole and described anode, injects electrolyte in the body of pond.
Electrolyte between lithium-sulfur cell both positive and negative polarity mainly plays a part to carry out transmission charge by conductive lithium ion.Electrolyte need to have good wettability with electrode, and electrolyte lithium salt has good dissolubility and ionic conductivity therein, the important such as working temperature to battery, specific energy, cycle efficieny, security performance.And barrier film is wherein that the both positive and negative polarity active material of battery is separated, and avoids any electron stream between both positive and negative polarity directly to pass through, and avoids battery short circuit; Ion current by time resistance little as far as possible, in most lithium ion batteries, adopt apertured polymeric film at present.
Described electrolyte comprises electrolytic salt, organic solvent and additive, and described electrolytic salt can be selected from lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), lithium perchlorate (LiClO 4), trifluoromethanesulfonic acid lithium (CF 3sO 3li), two (trifluoromethyl) sulfimide lithium (LiN (S0 2cF 3) 2) etc. at least one; Described organic solvent can be selected from benzene, toluene, ethanol, isopropyl alcohol, N, dinethylformamide, N, N-dimethyl pyrrolidone, oxolane, dimethyl acetate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, ethyl carbonate, propyl carbonate, gamma-butyrolacton, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ether compound, crown compound, dimethoxy-ethane compound, at least one in DOX etc.; Described additive can be selected from SO 2, NOx, CO 2, at least one in vinylene carbonate, vinyl acetate, lithium carbonate, lithium nitrate etc.
Described barrier film can adopt polymer microporous film, the optional multilayer microporous film from polyethylene and microporous polypropylene membrane, polyethylene and polypropylene screen of described polymer microporous film, and above-mentioned material surface modification film afterwards, as ceramic powder (aluminium oxide, silica etc.) is coated in the composite ceramics barrier film on polyolefin.
For promoting lithium-sulfur cell performance, after lithium-sulfur cell, discharge and recharge activation preparing, comprise that early stage, some cycle periods first carried out the activation that discharges and recharges of small electric current density, treat metal collector or with the abundant chemical combination of active material sulphur after, then carry out the activation procedure that discharges and recharges compared with high current density charge-discharge test.
The present invention is by adopting metal collector and carbon-based material unlike the prior art, preferred metal collector has the solid sulphur effect of certain chemistry and preferred carbon-based material has the solid sulphur effect of certain physics and can form good conductive network, preferred metal collector and carbon-based material and positive active material element sulphur chemical combination, generate the reactive compound that discharges and recharges of high, the stable cycle performance of conductivity, element sulphur is fixed, improve the utilance of element sulphur, and made prepared lithium-sulfur cell there is excellent cycle performance.And this positive electrode and widely used negative material, barrier film, nonaqueous electrolytic solution etc. in lithium ion battery have been formed to high performance lithium ion battery, obtain achievement of the present invention.
Brief description of the drawings
Fig. 1 is the SEM figure of embodiment 2 expanded graphites/sulphur composite material.
Fig. 2 is the TEM figure of embodiment 2 expanded graphites/sulphur composite material.
Fig. 3 is embodiment 2 electrode charge and discharge curves.
Fig. 4 is the charge/discharge cycle characteristics curve of embodiment 2 batteries.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described.
Embodiment 1
The expanded graphite of 20 mass parts (by expansible graphite in tube furnace, under air atmosphere, process 10s at 800 DEG C and obtain, lower with) is put into the beaker that fills 100mL deionized water, and ultrasonic 5h, obtains carbon-based material dispersion liquid; The vulcanized sodium of the sulphur of 80 mass parts and 80 mass parts is mixed and is dispersed in 100mL deionized water, add the surfactant TX100 of 10mL1%, obtain yellow polysulfide dispersion liquid; Under ultrasonic work, described yellow polysulfide dispersion liquid is slowly added in expanded graphite dispersion liquid, ultrasonic 1h, then adds 10mL concentrated hydrochloric acid (adopting commercially available concentrated hydrochloric acid), and room temperature lower magnetic force stirs 1h, obtains expanded graphite-polysulfide mixed liquor; In fume hood, expanded graphite-polysulfide mixed liquor is stirred to 1h under 70 DEG C of water-baths, then vacuum filtration, dries in 60 DEG C of vacuum drying ovens, then in 155 DEG C of vacuum drying ovens heat treated 2h, obtain expanded graphite-sulphur composite material.
Claim expanded graphite-sulphur composite material of 60 mass parts and the conductive agent acetylene black of 30 mass parts, and even by mortar ground and mixed, obtain positive electrode active material powder; The binder PVDF of 9 mass parts is dissolved in to the binder solution making in the solvent METHYLPYRROLIDONE of 91 mass parts; By the binder solution mix and blend 1h of the positive electrode active material powder of 90 mass parts and 111 mass parts or longer time, be prepared into the powdery pulp of the positive active material that comprises binder coating with solvent METHYLPYRROLIDONE; This powdery pulp is coated on Copper Foil collector with automatic coating machine, and in 60 DEG C of baking ovens, vacuumize 10～24h, except desolventizing, makes the anode pole piece for the lithium-sulfur cell of embodiment of the present invention embodiment 1.
Utilize this positive electrode and lithium anode, electrolyte LiTFSI-DOL/DME, and barrier film PP/PE/PP assemble lithium sulphur button cell in the glove box that is full of argon gas, and in battery test system the performance of test battery.
Embodiment 2
The expanded graphite of 25 mass parts is put into the beaker that fills 100mL deionized water, ultrasonic 5h, obtains carbon-based material dispersion liquid; The vulcanized sodium of the sulphur of 75 mass parts and 75 mass parts is mixed and is dispersed in 100mL deionized water, add the surfactant TX100 of 10mL1%, obtain yellow polysulfide dispersion liquid; Under ultrasonic work, described yellow polysulfide dispersion liquid is slowly added in expanded graphite dispersion liquid, ultrasonic 1h, then adds 10mL concentrated hydrochloric acid, and room temperature lower magnetic force stirs 1h, obtains expanded graphite-polysulfide mixed liquor; In fume hood, expanded graphite-polysulfide mixed liquor is stirred to 1h under 70 DEG C of water-baths, then vacuum filtration, dries in 60 DEG C of vacuum drying ovens, then in 155 DEG C of vacuum drying ovens heat treated 2h, obtain expanded graphite-sulphur composite material.
By preparing anodal and manufacture lithium-sulfur cell with the identical step described in embodiment 1.
Embodiment 3
The expanded graphite of 33 mass parts is put into the beaker that fills 100mL deionized water, ultrasonic 5h, obtains carbon-based material dispersion liquid; The vulcanized sodium of the sulphur of 66 mass parts and 66 mass parts is mixed and is dispersed in 100mL deionized water, add the surfactant TX100 of 10mL1%, obtain yellow polysulfide dispersion liquid; Under ultrasonic work, described yellow polysulfide dispersion liquid is slowly added in expanded graphite dispersion liquid, ultrasonic 1h, then adds 10mL concentrated hydrochloric acid, and room temperature lower magnetic force stirs 1h, obtains expanded graphite-polysulfide mixed liquor; In fume hood, expanded graphite-polysulfide mixed liquor is stirred to 1h under 70 DEG C of water-baths, then vacuum filtration, dries in 60 DEG C of vacuum drying ovens, then in 155 DEG C of vacuum drying ovens heat treated 2h, obtain expanded graphite-sulphur composite material.
By preparing anodal and manufacture lithium-sulfur cell with the identical step described in embodiment 1.
Embodiment 4
The expanded graphite of 50 mass parts is put into the beaker that fills 100mL deionized water, ultrasonic 5h, obtains carbon-based material dispersion liquid; The vulcanized sodium of the sulphur of 50 mass parts and 50 mass parts is mixed and is dispersed in 100mL deionized water, add the surfactant TX100 of 10mL1%, obtain yellow polysulfide dispersion liquid; Under ultrasonic work, described yellow polysulfide dispersion liquid is slowly added in expanded graphite dispersion liquid, ultrasonic 1h, then adds 10mL concentrated hydrochloric acid, and room temperature lower magnetic force stirs 1h, obtains expanded graphite-polysulfide mixed liquor; In fume hood, expanded graphite-polysulfide mixed liquor is stirred to 1h under 70 DEG C of water-baths, then vacuum filtration, dries in 60 DEG C of vacuum drying ovens, then in 155 DEG C of vacuum drying ovens heat treated 2h, obtain expanded graphite-sulphur composite material.
By preparing anodal and manufacture lithium-sulfur cell with the identical step described in embodiment 1.
At ambient temperature, the button lithium-sulfur cell charge-discharge performance of difference test evaluation embodiment 1-4.Charging and discharging currents density is all set to front 5 circulation 0.1C activation, encloses afterwards by 0.5C charge and discharge cycles 100, discharges and recharges cut-ff voltage and is limited to 1.0～3.0V.Utilization efficiency is defined as the lithium-sulfur cell specific discharge capacity and the elemental sulfur theory that detect and puts the percentage of specific capacitance (being 1672mAh/g).
Below the embodiment 2 of electrical property optimum is elaborated, to reach the further understanding to excellent properties of the present invention.Fig. 1 and Fig. 2 are SEM and the TEM figure of the expanded graphite/sulphur composite material in embodiment 2, from Fig. 1 and Fig. 2, can find out, expanded graphite has reached well and has peeled off after ultrasonic processing, form foamed three-dimensional net structure, build excellent three-dimensional conductive network, and sulphur is coated on to the inside uniformly, has reached the solid sulphur of good physics.Fig. 3 and Fig. 4 are lithium sulphur charging and discharging curve and the specific discharge capacity figure in embodiment 2.From Fig. 3 and Fig. 4, can find out, charged electrical flattens as 1.88V, and discharge voltage plateau is 1.71V.This lithium-sulfur cell has very high utilization efficiency and cyclical stability; When first circle electric discharge, in anode composite material, the utilance of sulphur is up to more than 93%, and unit sulphur weight discharge capacity is up to 1562mAh/g; In charge and discharge process, just more stable after specific discharge capacity activation, after circulating for hundreds of times under room temperature, unit sulphur weight discharge capacity can remain on 80% left and right of the theoretical specific discharge capacity of elemental sulfur (1672mAh/g), coulomb efficiency remains on 100% left and right, does not obviously overcharge phenomenon.

Claims (10)

1. anode, is characterized in that being provided with metal collector, positive active material and binder, and described positive active material is coated in metal collector by binder, and described positive active material comprises carbon back/sulphur composite material, conductive agent.
2. anode as claimed in claim 1, is characterized in that described carbon-based material is selected from least one in expanded graphite, Graphene, carbon nano-tube, mesoporous carbon, hollow carbon sphere, graphene oxide, preferably expanded graphite.
3. anode as claimed in claim 1, is characterized in that described sulfur materials is selected from sublimed sulfur simple substance (S 8), Li 2s n, organosulfur compound, carbon sulphur polymer (C 2s x) nin at least one, at Li 2s nin, n>=1; At (C 2s x) nin, the scope of x is 2.5～50, and n>=2; Preferably sublimed sulfur simple substance (S 8).
4. anode as claimed in claim 1, is characterized in that in described carbon back/sulphur composite material that by mass percentage, the content of carbon back is 20%～50%, and the content of sulphur is 50%～80%.
5. anode as claimed in claim 1, is characterized in that the metal of described metal collector is selected from the elemental metals of a kind of element in Fe, Co, Ni, Cu, Zn, Ag, Pt, Au or the alloy of at least 2 kinds of elements, preferable alloy copper or copper alloy.
6. anode as claimed in claim 1, is characterized in that described binder adopts poly-vinylidene fluoride; Described conductive agent can adopt acetylene black.
7. the preparation method of anode as claimed in claim 1, is characterized in that comprising the following steps:
1) first prepare compound carbon back/sulphur composite material:
Carbon-based material is put into water, after ultrasonic carbon-based material dispersion liquid; Again sulphur and vulcanized sodium mixing are dispersed in water, add surfactant TX100, obtain yellow polysulfide dispersion liquid; Yellow polysulfide dispersion liquid is added in carbon-based material dispersion liquid, again ultrasonic after, add hydrochloric acid, obtain carbon back-sulfide mixed liquor, under water-bath, stir, vacuum filtration, heat treated again after oven dry, obtains carbon back/sulphur composite material;
2) preparation of anode:
By step 1) carbon back/sulphur composite material of making and conductive agent mix and grind and obtain positive electrode active material powder, again positive electrode active material powder and binder solution are mixed, preparation comprises the positive active material powdery pulp of binder coating, be coated in metal collector, dry except after desolventizing, obtain anode.
8. the preparation method of anode as claimed in claim 7, is characterized in that in step 1) in, the proportioning of described carbon-based material and water is (25～50) mg: 100mL, and wherein, carbon-based material is calculated in mass, and water is calculated by volume; Described water can adopt deionized water; The described ultrasonic time can be 5h; The proportioning of described sulphur, vulcanized sodium, water, surfactant TX100 and hydrochloric acid can be (50～75) mg: (50～75) mg: 100mL: 10mL: 10mL, wherein, sulphur and vulcanized sodium are calculated in mass, and water, surfactant TX100 and hydrochloric acid are calculated by volume; Described water can adopt deionized water; It is 1% surfactant TX100 that described surfactant TX100 can adopt mass concentration; Described ultrasonic time again can be 1h; The temperature of described water-bath can be 70 DEG C, and the time of stirring can be 1h; The temperature of described oven dry can be 60 DEG C, and the temperature of described heat treated can be 155 DEG C, and the time of heat treated can be 4h; When carbon-based material adopts when expanded graphite, expanded graphite, under air atmosphere, is processed 10s at 800 DEG C and is obtained by expansible graphite in tube furnace.
9. the preparation method of anode as claimed in claim 7, is characterized in that in step 2) in, the mass ratio of described carbon back/sulphur composite material and conductive agent is (60～90): (0～30), and wherein, conductive agent is not 0; Described dry condition can be in 60 DEG C of baking ovens vacuumize 10～24h; The described thickness being coated in metal collector can be 10～500 μ m.
10. as described in as arbitrary in claim 1～6, anode is applied preparing in lithium-sulfur cell; Described lithium-sulfur cell comprises pond body, negative pole, barrier film, electrolyte and described anode; Negative pole, barrier film and described anode are located in the body of pond, and described negative pole comprises negative electrode active material, described negative electrode active material be selected from lithium embed material, Zinc-lithium alloy material and lithium metal in one; Barrier film is located between negative pole and described anode, injects electrolyte in the body of pond;
Described electrolyte can comprise electrolytic salt, organic solvent and additive, and described electrolytic salt can be selected from lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethanesulfonic acid lithium, at least one in two (trifluoromethyl) sulfimide lithium; Described organic solvent can be selected from benzene, toluene, ethanol, isopropyl alcohol, N, dinethylformamide, N, N-dimethyl pyrrolidone, oxolane, dimethyl acetate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, ethyl carbonate, propyl carbonate, gamma-butyrolacton, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ether compound, crown compound, dimethoxy-ethane compound, at least one in DOX; Described additive can be selected from SO 2, NOx, CO 2, at least one in vinylene carbonate, vinyl acetate, lithium carbonate, lithium nitrate;
Described barrier film can adopt polymer microporous film, the optional multilayer microporous film from polyethylene and microporous polypropylene membrane, polyethylene and polypropylene screen of described polymer microporous film, and above-mentioned material surface modification film afterwards, film after described above-mentioned material surface modification can be selected from ceramic powder and be coated in the composite ceramics barrier film on polyolefin, the optional self-alumina ceramic powder of described ceramic powder or silicon oxide ceramics powder.
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104600247A (en) * 2014-12-31 2015-05-06 山东玉皇新能源科技有限公司 Sulfur-carbon composite positive electrode material for lithium-sulfur battery and preparation method of sulfur-carbon composite positive electrode material
CN104900846A (en) * 2015-05-21 2015-09-09 张涉 Preparation method of polysulfide hydroxylated grapheme nano-composite (lithium ion rechargeable battery)
CN105576193A (en) * 2015-12-21 2016-05-11 张志平 Multi-layer carbon-sulfur composite positive electrode structure of aluminum ion battery and preparation method of multi-layer carbon-sulfur composite positive electrode structure of aluminum ion battery
CN105591078A (en) * 2015-12-21 2016-05-18 昆明理工大学 Mixed ion liquid Al/C-S secondary battery and preparation method
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CN108780917A (en) * 2016-03-04 2018-11-09 博比特电池有限公司 Rechargeable sode cell unit for high energy density cells
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CN110098396A (en) * 2019-05-06 2019-08-06 广东工业大学 A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery
CN110137572A (en) * 2019-05-30 2019-08-16 大连理工大学 A kind of application of terthienyl as lithium-sulfur cell electrolysis additive
CN110416510A (en) * 2019-07-18 2019-11-05 孙群 A kind of sulfenyl absorption electrically conductive carrier material based on lithium-sulphur cell positive electrode
CN111065600A (en) * 2017-10-30 2020-04-24 株式会社Lg化学 Sulfur-carbon composite material and preparation method thereof
CN111063867A (en) * 2018-10-16 2020-04-24 中南大学 Metal thio compound @ S composite material, preparation thereof and application thereof in lithium-sulfur battery
CN111653781A (en) * 2020-06-10 2020-09-11 中航锂电技术研究院有限公司 Positive electrode material, diaphragm, lithium-sulfur battery and preparation method thereof
CN111653729A (en) * 2020-05-20 2020-09-11 佛山科学技术学院 Lithium-sulfur battery composite positive electrode and preparation method thereof
CN112204771A (en) * 2018-09-19 2021-01-08 株式会社Lg化学 Method for manufacturing sulfur-carbon composite, sulfur-carbon composite manufactured thereby, positive electrode comprising the sulfur-carbon composite, and lithium secondary battery comprising the positive electrode
CN112687953A (en) * 2020-12-24 2021-04-20 中国电子新能源（武汉）研究院有限责任公司 Secondary battery electrolyte, preparation method thereof and battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002329495A (en) * 2001-05-01 2002-11-15 Matsushita Electric Ind Co Ltd Lithium secondary battery and production process thereof
CN102082260A (en) * 2011-01-07 2011-06-01 中国地质大学（武汉） Preparation method of positive composite material of lithium battery
WO2013049663A1 (en) * 2011-09-30 2013-04-04 The Regents Of The University Of California Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002329495A (en) * 2001-05-01 2002-11-15 Matsushita Electric Ind Co Ltd Lithium secondary battery and production process thereof
CN102082260A (en) * 2011-01-07 2011-06-01 中国地质大学（武汉） Preparation method of positive composite material of lithium battery
WO2013049663A1 (en) * 2011-09-30 2013-04-04 The Regents Of The University Of California Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

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