CN105449175A - Carbon sulfur composite material for lithium-sulfur battery and preparation method and application for carbon sulfur composite material - Google Patents

Carbon sulfur composite material for lithium-sulfur battery and preparation method and application for carbon sulfur composite material Download PDF

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CN105449175A
CN105449175A CN201510784839.3A CN201510784839A CN105449175A CN 105449175 A CN105449175 A CN 105449175A CN 201510784839 A CN201510784839 A CN 201510784839A CN 105449175 A CN105449175 A CN 105449175A
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carbon
composite material
sulphur
lithium
sulfur
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智林杰
张云博
苗力孝
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National Center for Nanosccience and Technology China
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National Center for Nanosccience and Technology China
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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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Abstract

The invention provides a carbon sulfur composite material for a lithium-sulfur battery and a preparation method and an application for the carbon sulfur composite material. The carbon sulfur composite material is positioned between a positive electrode and a diaphragm of the lithium-sulfur battery. For solving the problems of severe circulation capacity degradation, low active substance conductivity and the like of the lithium-sulfur battery, the carbon sulfur composite material positioned between the positive electrode and the diaphragm is designed and prepared and is used for improving the electrochemical performance of the lithium-sulfur battery; the capability of the material for absorbing and holding polysulfide ions can be adjusted by controlling the content of sulfur in the carbon sulfur composite material to improve the utilization rate of sulfur so as to improve the charge-discharge capacity and the cycling performance of the lithium-sulfur battery; and in addition, the carbon sulfur composite material provided by the invention is simple and easy to implement the preparation process, and good for later industrial production and quite high in potential in actual applications.

Description

A kind of carbon sulphur composite material for lithium-sulfur cell and its production and use
Technical field
The present invention relates to electrochemical cell art field, be specifically related to a kind of carbon sulphur composite material and its production and use, particularly relate to a kind of carbon sulphur composite material for lithium-sulfur cell and its production and use.
Background technology
Lithium-sulfur cell is expected to the secondary cell becoming high-energy-density of future generation, because positive active material is elemental sulfur, its prices of raw and semifnished materials are cheap, environmentally friendly, has higher than current lithium-ion battery system 3-5 specific energy density doubly simultaneously.But, the many sulphions of the intermediate product dissolved in lithium-sulfur cell electrochemical reaction process are to the corrosion of lithium anode, and the sulphur of poorly conductive and lithium sulfide to result in circulating battery capacity attenuation in the problem that electrode surface is built up serious, coulombic efficiency is low, the defect that active material utilization is low, constrains the commercial applications of lithium-sulfur cell to a great extent.
For above problem, researchers have carried out a large amount of work improving lithium-sulfur cell performance, and in succession disclose many patent applications.Wherein, designing new battery structure is a kind of simple and easy method improving lithium-sulfur cell chemical property, and such as, ArumugamManthiram etc. introduce porous, electrically conductive intermediate layer between positive pole and barrier film, the effect of shuttling back and forth caused by polysulfide can be suppressed, improve the combination property of lithium-sulfur cell.But add pure carbon intermediate layer and will increase the quality of inert matter, reduce the specific energy density (SuYS of battery, ManthiramA.Lithium-sulphurbatterieswithamicroporouscarbo npaperasabifunctionalinterlayer, NatureCommunications, 2012,3:1166).Patent CN102185158A discloses a kind of lithium-sulfur cell with adsorption layer, proposes on barrier film, to apply one deck material with carbon element intermediate layer to adsorb polysulfide, improves lithium-sulfur cell chemical property.But, barrier film is coated with composite bed and easily causes battery short circuit, and at positive electrode surface coating composite bed, then easily destroy the original gap structure of electrode surface, the mode be simultaneously coated with inevitably introduces inert matter coating layer, the content of active material in battery is reduced, is unfavorable for the feature realizing lithium-sulfur cell high-energy-density density.In addition; patent CN103050667A discloses a kind of multilayered structure anode composite for lithium-sulfur rechargeable battery and preparation method; mention the method for method in lithium-sulphur cell positive electrode area load layer of conductive film of use sputtering; but the method is comparatively complicated; cost is higher, does not utilize scale volume production.
In sum, although existing method can improve the performance of lithium-sulfur cell to a certain extent, but by simple increase intermediate layer material or directly in positive electrode surface coating intermediate layer, all be the increase in the quality of the total inert matter of battery, the ratio of active material in battery can be reduced, be unfavorable for the feature realizing lithium-sulfur cell high-energy-density density; In discharge process, active sulfur dissolving must enter intermediate layer and make active material further loss in addition, makes battery capacity occur the rapid decay at initial stage.
Summary of the invention
For problems of the prior art, the invention provides a kind of carbon sulphur composite material for lithium-sulfur cell and its production and use.Described carbon sulphur composite material, between anode and barrier film, can improve the specific capacity of battery, high rate performance and cyclical stability effectively, and its preparation is simple, be beneficial to the suitability for industrialized production in later stage.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of carbon sulphur composite material for lithium-sulfur cell, and described carbon sulphur composite material is between anode and barrier film.
Carbon sulphur composite material of the present invention is between anode and barrier film, there is high electrolyte absorbability and hold capacity, be conducive to suppressing many sulphions in positive electrode to be diffused into electrolyte and negative pole, simultaneously, the conductive structure had and the good contact of positive pole ensure that the circulation of active material effectively utilizes, avoiding many sulphions in the deposition on positive electrode surface is gathered into dead sulphur, decreases the loss of active sulfur; Simultaneously compared to simple increase intermediate layer material or directly in positive electrode surface coating intermediate layer, the quality of the total inert matter of battery can not be increased too much, contribute to the high-energy-density density realizing lithium-sulfur cell.
In carbon sulphur composite material of the present invention, mass percentage shared by sulphur is 1-70wt%, such as 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt% or 70wt% etc., be preferably 1-40wt%.
In carbon sulphur composite material of the present invention, the content of sulphur can control, and by controlling the content of sulphur, the absorption of this composite material can be regulated and the ability of the polysulfide of recycling dissolving and sulphur content in the battery, and then the balance of battery high sulfur content and good circulation performance can be realized.
In the present invention, the thickness of described carbon sulphur composite material is 50nm-200 μm, such as 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm etc., be preferably 500nm-50 μm, more preferably 1 μm-20 μm.
The THICKNESS CONTROL of carbon sulphur composite material of the present invention is in suitable scope, its thickness is greater than maximum of the present invention, excessively can increase inert matter whole content in the battery, reduce the energy density of battery, its thickness is less than minimum value of the present invention, be then difficult to play restriction to the diffusion of many sulphions.
In the present invention, described carbon sulphur composite material is prepared by material with carbon element and sulphur class active material.
Preferably, described material with carbon element is carbon nano-tube, Graphene, the combination of any one or at least two kinds in carbon fiber or conductive black, described typical but non-limiting example has: carbon nano-tube, Graphene, carbon fiber, conductive black, the combination of carbon nano-tube and Graphene, the combination of carbon fiber and conductive black, the combination of carbon nano-tube and carbon fiber, the combination of Graphene and conductive black, carbon nano-tube, the combination of carbon fiber and conductive black carbon, nanotube, the combination of Graphene and conductive black, carbon nano-tube, Graphene, the combination etc. of carbon fiber and conductive black, be preferably in carbon nano-tube or Graphene any one.
Preferably, the thickness of described material with carbon element is 50nm-200 μm, such as 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm etc., be preferably 500nm-50 μm, more preferably 1 μm-20 μm.
Preferably, the void size of the network configuration of described material with carbon element is 1nm-10 μm, such as 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm etc., be preferably 1nm-500nm, more preferably 2nm-100nm.
Described material with carbon element has network configuration, the carbon sulphur composite material prepared also is network configuration, the space of network configuration has high electrolyte absorbability and hold capacity, contribute to sulphur and form concentration gradient, many sulphions in positive electrode are suppressed to be diffused in bulk solution and negative pole district, avoid in charging process, the deposition of many sulphions on positive electrode surface is also gathered into dead sulphur, reduces the loss of active sulfur; There is good conductive network simultaneously, can ensure that the sulphur class active material distributed wherein is recycled again effectively, thus improve the specific capacity of battery.
In the present invention, described carbon fiber is prepared by the combination of any one in high temperature cabonization biological substance, bacteria cellulose or organic fiber or at least two kinds, the typical but non-limiting example of described combination has: the combination of carbonization biological substance and bacteria cellulose, the combination of carbonization biological substance and organic fiber, the combination etc. of carbonization biological substance, bacteria cellulose and organic fiber, is preferably carbonization bacteria cellulose and prepares described carbon fiber.
Wherein, biological substance in described high temperature cabonization biological substance is preferably plant cellulose, the combination of any one or at least two kinds more preferably in bamboo fibre, cotton fiber or lignocellulosic, the typical but non-limiting example of described combination has: the combination of bamboo fibre and cotton fiber, the combination of cotton fiber and lignocellulosic, the combination etc. of bamboo fibre, cotton fiber and lignocellulosic.
Preferably, the temperature of described high temperature cabonization is greater than 800 DEG C, such as 800 DEG C, 820 DEG C, 840 DEG C, 860 DEG C, 880 DEG C, 900 DEG C or 920 DEG C etc.
Preferably, described carbon fiber is obtained by chemical vapour deposition technique (CVD) or template synthesis.
In the present invention, described conductive black is acetylene black, Supe-P, the combination of any one or at least two kinds in the black or porous, electrically conductive carbon of KB (section's qin), the typical but non-limiting example of described combination has: the combination of acetylene black and Supe-P, the combination of KB (section's qin) carbon and porous, electrically conductive carbon, the combination of acetylene black and KB (section's qin) carbon, the combination of Supe-P and porous, electrically conductive carbon, acetylene black, the combination of Supe-P and porous, electrically conductive carbon, acetylene black, the combination of KB (section's qin) carbon and porous, electrically conductive carbon, acetylene black, Supe-P, the combination etc. of KB (section's qin) carbon or porous, electrically conductive carbon.
In the present invention, described conductive black is preferably porous, electrically conductive carbon.
In the present invention, described sulphur class active material is the combination of any one or at least two kinds in elemental sulfur, lithium sulfide, over cure lithium or many sulphions, the typical but non-limiting example of described combination has: the combination of the combination of elemental sulfur and lithium sulfide, over cure lithium and many sulphions, the combination of elemental sulfur and over cure lithium, the combination of lithium sulfide and many sulphions, the combination of elemental sulfur, over cure lithium and many sulphions, the combination of lithium sulfide, over cure lithium and many sulphions, the combination etc. of elemental sulfur, lithium sulfide, over cure lithium and many sulphions;
Wherein, the chemical formula of described many sulphions is S n -, wherein 1<n<15, is preferably n=4-6.
Second aspect, the invention provides a kind of preparation method of carbon sulphur composite material as described in relation to the first aspect, described preparation method is solution in-situ compositing, fusion method, gel precipitation composite algorithm, the combination of any one or at least two kinds in Charging sulphur method or decompression Charging sulphur method, the typical but non-limiting example of described combination has: the combination of solution in-situ compositing and fusion method, the combination of gel precipitation composite algorithm and Charging sulphur method, the combination of solution in-situ compositing and decompression Charging sulphur method, solution in-situ compositing, the combination of fusion method and gel precipitation composite algorithm, fusion method, the combination of Charging sulphur method and decompression Charging sulphur method, solution in-situ compositing, fusion method, the combination of gel precipitation composite algorithm and Charging sulphur method, solution in-situ compositing, fusion method, the combination of Charging sulphur method and decompression Charging sulphur method, fusion method, gel precipitation composite algorithm, the combination of Charging sulphur method and decompression Charging sulphur method, solution in-situ compositing, fusion method, gel precipitation composite algorithm, the combination etc. of Charging sulphur method and decompression Charging sulphur method, is preferably solution in-situ compositing and/or fusion method, more preferably solution in-situ compositing.
The third aspect, the invention provides a kind of electrochemical energy storing device, and described electrochemical energy storing device comprises the above-mentioned carbon sulphur composite material of the present invention.
Compared with prior art, the present invention has following beneficial effect:
(1) space of carbon sulphur composite material network configuration of the present invention has high electrolyte absorbability and hold capacity, intermediate layer sulphur can form concentration gradient, many sulphions in positive electrode are suppressed to be diffused into electrolyte and negative pole, avoid in charging process, the deposition of many sulphions on positive electrode surface is also gathered into dead sulphur, reduces the loss of active sulfur;
(2) carbon sulphur composite material of the present invention has good conductive network, can ensure that the sulphur class active material distributed wherein is recycled again effectively, thus improve the specific capacity of battery, carbon sulphur composite material of the present invention is added between the positive pole and barrier film of lithium-sulfur cell, after under 1C multiplying power, charge and discharge cycles 300 is enclosed, the specific capacity of battery can up to 423mAhg -1, its capability retention is 84.9%, far above the 205mAhg not adding carbon sulphur composite material of the present invention -1with 33.5%; It is crucial that, by controlling the content of sulphur in this composite material, the absorption of carbon sulphur composite material can be regulated and the ability of the polysulfide of recycling dissolving and sulphur content in the battery, realizing the balance of battery high sulfur content and good circulation performance;
(3) carbon sulphur composite material preparation process of the present invention is simple, is beneficial to the suitability for industrialized production in later stage.
Accompanying drawing explanation
Fig. 1 carries out for adopting the carbon sulphur composite material prepared by embodiment 1 the lithium-sulfur cell cycle performance figure assembled;
Fig. 2 carries out for adopting the carbon sulphur composite material prepared by embodiment 3 the lithium-sulfur cell cycle performance figure assembled;
Fig. 3 is the lithium-sulfur cell cycle performance figure that comparative example 1 does not adopt carbon sulphur composite material to carry out assembling.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, below the present invention is described in more detail.But following embodiment is only simple and easy example of the present invention, and do not represent or limit the scope of the present invention, scope is as the criterion with claims.
Embodiment 1
After fully being cleaned in deionized water by bacteria cellulose, with liquid nitrogen by its snap frozen, with being placed on-50 DEG C, in the vacuum drying chamber of 20.0Pa, eliminate moisture.Subsequently, the bacteria cellulose aeroge of gained is placed in atmosphere tube type stove, with 5 DEG C of min under Ar gas shielded -1heating rate rise to 800 DEG C and carry out high temperature cabonization, with stove cooling after insulation 1h, prepare carbonization bacteria cellulose.
Magnificent for the life of different quality sulphur content is not dissolved in carbon disulfide solution, prepares concentration and be respectively 20mgmL -1, 15mgmL -1, 8mgmL -1, 5mgmL -1and 0.5mgmL -1the carbon disulfide solution of sulphur.Carbonization bacteria cellulose is immersed in the solution of variable concentrations, take out after soaking 1h and dry in ventilating kitchen, and be placed in baking oven, at 155 DEG C, constant temperature keeps 12h, prepares sulfur content and is respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Carbon sulphur composite material obtained above is adopted to assemble lithium sulphur button cell, by elemental sulfur, conductive black and Kynoar in mass ratio for 7.5:1.5:1 joins in 1-METHYLPYRROLIDONE (NMP), carry out sufficient mechanical agitation, mix rear blade coating in aluminum foil current collector, vacuumize 24h at the temperature of 60 DEG C, prepares the positive pole that test uses.Be negative pole by the metal lithium sheet that 2mm is thick.LiTFSI/ (DME+DOL) solution of electrolyte to be concentration be 1M, the LiNO containing 1wt% 3additive.In the glove box being full of argon gas, be assembled into CR2025 button cell, carbon sulphur composite material is placed between positive pole and barrier film.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test, its test result is as shown in Figure 1.As can be seen from Figure 1, add sulfur content and be respectively 70wt%, after the carbon sulphur composite material of 56wt%, 40wt%, 20wt% and 1wt%, battery is respectively 448mAhg at the specific discharge capacity of the 300th circulation -1, 543mAhg -1, 686mAhg -1, 889mAhg -1and 1046mAhg -1, capability retention is respectively 80.8%, 90.3%, 78.0%, 84.9% and 57.0%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 325mAhg -1, 356mAhg -1, 394mAhg -1, 423mAhg -1and 397mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 20wt%.
Embodiment 2
1g lignocellulosic is dispersed in the TEMPO (0.016g) of 100mL and the aqueous solution of NaBr (0.016g).The aqueous solution of the NaClO of a 12wt% of another preparation, and add HCl solution, its pH value is adjusted to 10.In the dispersion liquid of lignocellulosic, add a certain amount of NaClO solution, make NaClO and cellulosic ratio be 3mmolNaClO:1g cellulose.Gained solution is at room temperature stirred, and by NaOH solution, pH value is controlled 10.The cellulose oxidation reaction of TEMPO regulation and control terminates when NaOH is no longer consumed.Subsequently, after the cellulose deionized water of oxidation is cleaned up by the mode of suction filtration, be scattered in water.Vacuum filtration is carried out to the dispersion liquid of oxycellulose, prepares lignocellulosic film.The lignocellulosic film of gained is placed in atmosphere tube type stove, with 5 DEG C of min under Ar gas shielded -1heating rate rise to 800 DEG C and carry out high temperature cabonization, with stove cooling after insulation 1h, prepare carbonized woody fiber element.
Be not dissolved in carbon disulfide solution by magnificent for the life of different quality sulphur content, preparing concentration is 20mgmL -1, 15mgmL -1, 8mgmL -1, 5mgmL -1and 0.5mgmL -1the carbon disulfide solution of sulphur.Carbonized woody fiber element is immersed in the solution of variable concentrations, takes out airing in ventilating kitchen after soaking 1h, and be placed in baking oven, keep 12h at 155 DEG C of constant temperature, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Carbon sulphur composite material obtained above is adopted to assemble lithium sulphur button cell, by elemental sulfur, conductive black and Kynoar in mass ratio for 7.5:1.5:1 joins in 1-METHYLPYRROLIDONE (NMP), carry out sufficient mechanical agitation, mix rear blade coating in aluminum foil current collector, vacuumize 24h at the temperature of 60 DEG C, prepares the positive pole that test uses.Be negative pole by the metal lithium sheet that 2mm is thick.LiTFSI/ (DME+DOL) solution of electrolyte to be concentration be 1M, the LiNO containing 1wt% 3additive.In the glove box being full of argon gas, be assembled into CR2025 button cell, carbon sulphur composite material is placed between positive pole and barrier film.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test.Add sulfur content and be respectively 70wt%, after the carbon sulphur composite material of 56wt%, 40wt%, 20wt% and 1wt%, battery is respectively 460mAhg at the specific discharge capacity of the 300th circulation -1, 627mAhg -1, 698mAhg -1, 977mAhg -1and 1012mAhg -1, capability retention is respectively 58.2%, 70.5%, 76.5%, 82.4% and 82.8%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 334mAhg -1, 410mAhg -1, 401mAhg -1, 415mAhg -1and 385mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 20wt%.
Embodiment 3
Multi-walled carbon nano-tubes is added the concentrated sulfuric acid and red fuming nitric acid (RFNA) volume ratio is in the aqueous solution of 3:1, under 80 DEG C of conditions, add hot reflux 12h be oxidized.Subsequently, with deionized water, suspension is diluted and eccentric cleaning, and final product is carried out ultrasonic disperse in a certain amount of deionized water, obtain carbon nano tube dispersion liquid.
By vulcanized sodium (Na 2s) be dissolved in deionized water, after forming solution, add sublimed sulfur, control Na 2the mol ratio of S and sublimed sulfur is 1:3, and at room temperature stirs 2h.Subsequently, acetic acid (CH is slowly added 3cOOH) to pH=3, reaction generates sulfur granules precipitation.After centrifugal taking-up precipitation, by washed with de-ionized water three times, and with ultrasonic disperse, obtain sulphur suspension-turbid liquid.
Carbon nano tube dispersion liquid and sulphur suspension-turbid liquid are respectively 30:70 by carbon sulphur mass ratio, 44:56,60:40,80:20 and 99:1 mixes, and vacuum filtration is carried out to mixed liquor, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Adopt the above carbon sulphur composite material obtained, be assembled into lithium sulphur button cell in the same manner as in Example 1 and carry out electrochemical property test.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test, its result is as shown in Figure 2.As can be seen from Figure 2, add sulfur content and be respectively 70wt%, after the carbon sulphur composite material of 56wt%, 40wt%, 20wt% and 1wt%, battery is respectively 432mAhg at the specific discharge capacity of the 300th circulation -1, 469mAhg -1, 600mAhg -1, 793mAhg -1and 1012mAhg -1, capability retention is respectively 82.7%, 75.5%, 76.8%, 69.6% and 51.2%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 313mAhg -1, 307mAhg -1, 345mAhg -1, 377mAhg -1and 384mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 1wt%.
Embodiment 4
Multi-walled carbon nano-tubes is added the concentrated sulfuric acid and red fuming nitric acid (RFNA) volume ratio is in the aqueous solution of 3:1, under 80 DEG C of conditions, add hot reflux 12h be oxidized.Subsequently, with deionized water, suspension is diluted and eccentric cleaning, and final product is carried out ultrasonic disperse in a certain amount of deionized water, obtain carbon nano tube dispersion liquid.Add a certain amount of acetylene black subsequently, the mass ratio of carbon nano-tube and acetylene black controls as 5:1, and carries out the ultrasonic disperse of 1h.
By vulcanized sodium (Na 2s) be dissolved in deionized water, after forming solution, add sublimed sulfur, control Na 2the mol ratio of S and sublimed sulfur is 1:3, and at room temperature stirs 2h.Subsequently, acetic acid (CH is slowly added 3cOOH) to pH=3, reaction generates sulfur granules precipitation.After centrifugal taking-up precipitation, by washed with de-ionized water three times, and with ultrasonic disperse, obtain sulphur suspension-turbid liquid.
The mixed liquor of carbon nano-tube, acetylene black and sulphur suspension-turbid liquid are respectively 30:70 by carbon sulphur mass ratio, 44:56,60:40,80:20 and 99:1 mixes, and vacuum filtration is carried out to mixed liquor, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Adopt the above carbon sulphur composite material prepared, be assembled into lithium sulphur button cell in the same manner as in Example 1 and carry out electrochemical property test.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test.Adding sulfur content is after the carbon sulphur composite material of 70wt%, 56wt%, 40wt%, 20wt% and 1wt%, and battery is respectively 466mAhg at the specific discharge capacity of the 300th circulation -1, 470mAhg -1, 580mAhg -1, 805mAhg -1and 1020mAhg -1, capability retention is respectively 81.7%, 80.2%, 70.0%, 69.5% and 60.1%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 338mAhg -1, 308mAhg -1, 334mAhg -1, 382mAhg -1and 388mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 1wt%.
Embodiment 5
Multi-walled carbon nano-tubes is added the concentrated sulfuric acid and red fuming nitric acid (RFNA) volume ratio is in the aqueous solution of 3:1, under 80 DEG C of conditions, add hot reflux 12h be oxidized.Subsequently, with deionized water, suspension is diluted and eccentric cleaning, and final product is carried out ultrasonic disperse in a certain amount of deionized water, obtain carbon nano tube dispersion liquid.Add a certain amount of CMK-3 ordered mesopore carbon subsequently, the mass ratio of carbon nano-tube and ordered mesopore carbon controls as 5:1, and carries out the ultrasonic disperse of 1h.
By vulcanized sodium (Na 2s) be dissolved in deionized water, after forming solution, add sublimed sulfur, control Na 2the mol ratio of S and sublimed sulfur is 1:3, and at room temperature stirs 2h.Subsequently, acetic acid (CH is slowly added 3cOOH) to pH=3, reaction generates sulfur granules precipitation.After centrifugal taking-up precipitation, by washed with de-ionized water three times, and with ultrasonic disperse, obtain sulphur suspension-turbid liquid.
The mixed liquor of carbon nano-tube, ordered mesopore carbon and sulphur suspension-turbid liquid are respectively 30:70 by carbon sulphur mass ratio, 44:56,60:40,80:20 and 99:1 mixes, and vacuum filtration is carried out to mixed liquor, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Adopt the above carbon sulphur composite material prepared, be assembled into lithium sulphur button cell in the same manner as in Example 1 and carry out electrochemical property test.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test.Add sulfur content and be respectively 70wt%, after the carbon sulphur composite material of 56wt%, 40wt%, 20wt% and 1wt%, battery is respectively 429mAhg at the specific discharge capacity of the 300th circulation -1, 489mAhg -1, 591mAhg -1, 794mAhg -1and 1029mAhg -1, capability retention is respectively 85.4%, 78.3%, 75.1%, 68.8% and 66.5%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 311mAhg -1, 320mAhg -1, 340mAhg -1, 377mAhg -1and 391mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 1wt%.
Embodiment 6
First take 5g natural flake graphite, in the beaker of 500mL, add the concentrated sulfuric acid 200g of 98%, subsequently graphite and the concentrated sulfuric acid are mixed to join in beaker, stir under condition of ice bath and spend the night.Keep ice bath temperature at about 0 DEG C afterwards, add 15g potassium permanganate powder lentamente, stirring reaction 4h; Bath temperature is risen to 35 DEG C, continue stirring reaction 2h; Add the deionized water of 200mL at 1000mL beaker, with glass bar by reaction mixed dispersion liquid slowly drainage enter in water, and control temperature agitating heating 30min below 95 DEG C, prepares graphite oxide.
The cleaning of graphite oxide and dispersion: with deionized water reactant liquor released and rarely after 800mL, add the aqueous hydrogen peroxide solution that 5mL solubility is 30%, and filter while hot, afterwards with 5% watery hydrochloric acid and deionized water repeatedly carry out eccentric cleaning, and final product is carried out ultrasonic disperse in a certain amount of deionized water, form graphene oxide dispersion.Subsequently, prepare graphene oxide membrane by the mode of vacuum filtration, and carry out 800 DEG C of carbonizations under an argon atmosphere, finally prepare graphene film.
Magnificent for the life of different quality sulphur content is not dissolved in carbon disulfide solution, prepares concentration and be respectively 30mgmL -1, 25mgmL -1, 18mgmL -1, 12mgmL -1and 4mgmL -1the carbon disulfide solution of sulphur.The composite membrane of Graphene and acetylene black is immersed in the solution of variable concentrations, takes out airing in ventilating kitchen after soaking 1h, and be placed in baking oven, keep 12h at 155 DEG C of constant temperature, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Adopt the above carbon sulphur composite material prepared, be assembled into lithium sulphur button cell in the same manner as in Example 1 and carry out electrochemical property test.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test.Add sulfur content and be respectively 70wt%, after the carbon sulphur composite material of 56wt%, 40wt%, 20wt% and 1wt%, battery is respectively 400mAhg at the specific discharge capacity of the 300th circulation -1, 458mAhg -1, 600mAhg -1, 716mAhg -1and 842mAhg -1, capability retention is respectively 80.2%, 80.3%, 79.6%, 74.3% and 57.6%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 290mAhg -1, 300mAhg -1, 345mAhg -1, 340mAhg -1and 320mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 40wt%.
Embodiment 7
First take 5g natural flake graphite, in the beaker of 500mL, add the concentrated sulfuric acid 200g of 98%, subsequently graphite and the concentrated sulfuric acid are mixed to join in beaker, stir under condition of ice bath and spend the night.Keep ice bath temperature at about 0 DEG C afterwards, add 15g potassium permanganate powder lentamente, stirring reaction 4h; Bath temperature is risen to 35 DEG C, continue stirring reaction 2h; Add the deionized water of 200mL at 1000mL beaker, with glass bar by reaction mixed dispersion liquid slowly drainage enter in water, and control temperature agitating heating 30min below 95 DEG C, prepares graphite oxide.
The cleaning of graphite oxide and dispersion: with deionized water reactant liquor released and rarely after 800mL, add the aqueous hydrogen peroxide solution that 5mL concentration is 30%, and filter while hot, afterwards with 5% watery hydrochloric acid and deionized water repeatedly carry out eccentric cleaning, and final product is carried out ultrasonic disperse in a certain amount of deionized water, form graphene oxide dispersion.Add a certain amount of acetylene black subsequently, the mass ratio of graphene oxide and acetylene black controls as 5:1, and carries out the ultrasonic disperse of 1h.Subsequently, prepared the composite membrane of graphene oxide and acetylene black by the mode of vacuum filtration, and carry out 800 DEG C of carbonizations under an argon atmosphere, finally prepare the composite membrane of Graphene and acetylene black.
Magnificent for the life of different quality sulphur content is not dissolved in carbon disulfide solution, prepares concentration and be respectively 25mgmL -1, 18mgmL -1, 12mgmL -1, 8mgmL -1and 1mgmL -1the carbon disulfide solution of sulphur.The composite membrane of Graphene and acetylene black is immersed in the solution of variable concentrations, takes out airing in ventilating kitchen after soaking 1h, and be placed in baking oven, keep 12h at 155 DEG C of constant temperature, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Adopt the above carbon sulphur composite material prepared, be assembled into lithium sulphur button cell in the same manner as in Example 1 and carry out electrochemical property test.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test, add sulfur content and be respectively 70wt%, 56wt%, 40wt%, after the carbon sulphur composite material of 20wt% and 1wt%, battery is respectively 421mAhg at the specific discharge capacity of the 300th circulation -1, 450mAhg -1, 617mAhg -1, 768mAhg -1and 947mAhg -1, capability retention is respectively 80.4%, 80.2%, 75.6%, 58.6% and 59.1%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 305mAhg -1, 294mAhg -1, 355mAhg -1, 365mAhg -1and 360mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 20wt%.
Embodiment 8
First take 5g natural flake graphite, in the beaker of 500mL, add the concentrated sulfuric acid 200g of 98%, subsequently graphite and the concentrated sulfuric acid are mixed to join in beaker, stir under condition of ice bath and spend the night.Keep ice bath temperature at about 0 DEG C afterwards, add 15g potassium permanganate powder lentamente, stirring reaction 4h; Bath temperature is risen to 35 DEG C, continue stirring reaction 2h; Add the deionized water of 200mL at 1000mL beaker, with glass bar by reaction mixed dispersion liquid slowly drainage enter in water, and control temperature agitating heating 30min below 95 DEG C, prepares graphite oxide.
The cleaning of graphite oxide and dispersion: with deionized water reactant liquor released and rarely after 800mL, add the aqueous hydrogen peroxide solution that 5mL concentration is 30%, and filter while hot, afterwards with 5% watery hydrochloric acid and deionized water repeatedly carry out eccentric cleaning, and final product is carried out ultrasonic disperse in a certain amount of deionized water, form graphene oxide dispersion.Add a certain amount of CMK-3 ordered mesopore carbon subsequently, the mass ratio of graphene oxide and ordered mesopore carbon controls as 5:1.Subsequently, prepared the composite membrane of graphene oxide and ordered mesopore carbon by the mode of vacuum filtration, and carry out 800 DEG C of carbonizations under an argon atmosphere, finally prepare the composite membrane of Graphene and ordered mesopore carbon.
Magnificent for the life of different quality sulphur content is not dissolved in carbon disulfide solution, prepares concentration and be respectively 25mgmL -1, 18mgmL -1, 12mgmL -1, 8mgmL -1and 1mgmL -1the carbon disulfide solution of sulphur.The composite membrane of Graphene and acetylene black is immersed in the solution of variable concentrations, takes out airing in ventilating kitchen after soaking 1h, and be placed in baking oven, keep 12h at 155 DEG C of constant temperature, prepare sulfur content and be respectively 70wt%, 56wt%, the carbon sulphur composite material of 40wt%, 20wt% and 1wt%.
Adopt the above carbon sulphur composite material prepared, be assembled into lithium sulphur button cell in the same manner as in Example 1 and carry out electrochemical property test.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test, adding sulfur content is 70wt%, 56wt%, 40wt%, after the carbon sulphur composite material of 20wt% and 1wt%, battery is respectively 434mAhg at the specific discharge capacity of the 300th circulation -1, 534mAhg -1, 654mAhg -1, 842mAhg -1and 1082mAhg -1, capability retention is respectively 82.1%, 81.6%, 79.6%, 67.2% and 51.8%, all has good cycle performance.According to considering of sulfur content and circulating battery specific capacity, calculate the specific capacity calculated according to positive pole and intermediate layer gross mass and be followed successively by 315mAhg -1, 350mAhg -1, 376mAhg -1, 400mAhg -1and 411mAhg -1, the optimal result thus in this group embodiment is add the battery that sulfur content is the carbon sulphur composite material of 1wt%.
Comparative example 1
By elemental sulfur, conductive black and Kynoar in mass ratio for 7.5:1.5:1 joins in 1-METHYLPYRROLIDONE (NMP), carry out sufficient mechanical agitation, mix rear blade coating in aluminum foil current collector, vacuumize 24h at the temperature of 60 DEG C, prepares the positive pole that test uses.Be negative pole by the metal lithium sheet that 2mm is thick.LiTFSI/ (DME+DOL) solution of electrolyte to be concentration be 1M, the LiNO containing 1wt% 3additive.CR2025 button cell is assembled in the glove box being full of argon gas.Probe temperature is 25 DEG C, and voltage window is 1.8V-2.8V.Battery charge and discharge under 0.1C multiplying power circulates 2 times, after under 0.5C multiplying power charge and discharge circulate and activate for 5 times, after under 1C multiplying power charge and discharge cycles 300 times, carry out cyclical stability test.As shown in Figure 3, the Capacity fading of this comparative example is serious, only has 273mAhg at the capacity of the 300th circulation time for test result -1, capability retention is respectively 33.5%, and calculating the specific capacity calculated according to anode sizing agent gross mass is 205mAhg -1.
The concentration that this comparative example difference from Example 1 of comparative example 2 is only to prepare the carbon disulfide solution of sulphur in the raw material of carbon sulphur composite material is 0.1mgmL -1and 25mgmL -1, all the other raw materials and raw material dosage and preparation method all identical with embodiment 1 with condition, prepare the carbon sulphur composite material that sulfur content is respectively 0.5wt% and 76wt%.
The carbon sulphur composite material prepared is put between the positive pole of battery and barrier film, and the specific discharge capacity of the 300th circulation is respectively 1050mAhg -1and 352mAhg -1, capability retention is respectively 89.9% and 43.5%.According to considering of sulfur content and circulating battery specific capacity, the specific capacity calculated according to positive pole and intermediate layer gross mass is followed successively by 393mAhg -1and 266mAhg -1.
Compare by embodiment 1-8 can find out with comparative example 1, carbon sulphur composite material of the present invention is placed between anode and barrier film, effectively can improve specific capacity and the capability retention of battery, after under 1C multiplying power, charge and discharge cycles 300 is enclosed, the specific capacity of battery can up to 423mAhg -1, its capability retention is 84.9%, far above the 205mAhg not adding carbon sulphur composite material of the present invention -1with 33.5%, improve overall specific capacity and the cycle performance of battery.
Can be found out by embodiment 1-8, when material with carbon element is constant, by controlling the content of sulphur in carbon sulphur composite material, carbon sulphur composite material can be regulated to adsorb and recycle the ability of polysulfide and sulphur content in the battery of dissolving, realizing the balance of battery high sulfur content and good circulation performance; Simultaneously in carbon sulphur composite material, when the content of sulphur is constant, when changing material with carbon element, the specific capacity of battery can be different with capability retention, this illustrates by the synergy between material with carbon element and sulphur class active material, could obtain the carbon sulphur composite material of excellent performance.
Compare by embodiment 1 can find out with comparative example 2, when in carbon sulphur composite material, the content of sulphur is too much, also the overall performance of carbon sulphur composite material can be affected, and sulphur whole content in the battery time very few, can be reduced, therefore only have and the amount ranges of each composition is limited within the scope of the invention, could cooperatively interact well between each component, synergy, obtains the carbon sulphur composite material of high comprehensive performance.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. for a carbon sulphur composite material for lithium-sulfur cell, it is characterized in that, described carbon sulphur composite material is between anode and barrier film.
2. carbon sulphur composite material according to claim 1, is characterized in that, in described carbon sulphur composite material, the mass percentage shared by sulphur is 1-70wt%, is preferably 1-40wt%.
3. carbon sulphur composite material according to claim 1 and 2, is characterized in that, the thickness of described carbon sulphur composite material is 50nm-200 μm, is preferably 500nm-50 μm, more preferably 1 μm-20 μm.
4. the carbon sulphur composite material according to any one of claim 1-3, is characterized in that, described carbon sulphur composite material is prepared by material with carbon element and sulphur class active material.
5. carbon sulphur composite material according to claim 4, is characterized in that, described material with carbon element is the combination of any one or at least two kinds in carbon nano-tube, Graphene, carbon fiber or conductive black, is preferably any one in carbon nano-tube or Graphene;
Preferably, the thickness of described material with carbon element is 50nm-200 μm, is preferably 500nm-50 μm, more preferably 1 μm-20 μm;
Preferably, the void size of the network configuration of described material with carbon element is 1nm-10 μm, is preferably 1nm-500nm, more preferably 2nm-100nm.
6. carbon sulphur composite material according to claim 5, it is characterized in that, described carbon fiber is prepared by the combination of any one in high temperature cabonization biological substance, bacteria cellulose or organic fiber or at least two kinds, prepare preferably by carbonization bacteria cellulose, wherein, biological substance in described high temperature cabonization biological substance is preferably plant cellulose, the combination of any one or at least two kinds more preferably in bamboo fibre, cotton fiber or lignocellulosic;
Preferably, the temperature of described high temperature cabonization is greater than 800 DEG C;
Preferably, described carbon fiber is obtained by chemical vapour deposition technique or template synthesis.
7. carbon sulphur composite material according to claim 5, is characterized in that, described conductive black is the combination of any one or at least two kinds in the black or porous, electrically conductive carbon of acetylene black, Supe-P, KB (section's qin), is preferably porous, electrically conductive carbon.
8. carbon sulphur composite material according to claim 4, is characterized in that, described sulphur class active material is the combination of any one or at least two kinds in elemental sulfur, lithium sulfide, over cure lithium or many sulphions;
Preferably, the chemical formula of described many sulphions is S n -, wherein 1<n<15, is preferably n=4-6.
9. the preparation method of the carbon sulphur composite material according to any one of claim 1-8, it is characterized in that, described preparation method is the combination of any one or at least two kinds in solution in-situ compositing, fusion method, gel precipitation composite algorithm, Charging sulphur method or decompression Charging sulphur method, be preferably solution in-situ compositing and/or fusion method, more preferably solution in-situ compositing.
10. an electrochemical energy storing device, is characterized in that, described electrochemical energy storing device comprises the carbon sulphur composite material according to any one of claim 1-8.
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CN109285993A (en) * 2017-07-19 2019-01-29 中国科学院过程工程研究所 A kind of sulphur carbon flexible electrode material and its preparation method and application
CN107946569A (en) * 2017-11-18 2018-04-20 桂林电子科技大学 A kind of N doping ordered mesopore carbon sulfur materials and its preparation method and application
CN109962222A (en) * 2019-03-04 2019-07-02 杭州电子科技大学 A method of lithium sulfur battery anode material is prepared using bacteria cellulose aquagel
CN110212180A (en) * 2019-05-22 2019-09-06 杭州电子科技大学 A kind of preparation method and lithium-sulfur cell of lithium sulfide self-supporting carbon ball/carbon nano-fiber composite material
CN110416479A (en) * 2019-07-31 2019-11-05 东华大学 A kind of multichannel carbide wood interlayer and its preparation and application with orientation
CN110371950A (en) * 2019-08-12 2019-10-25 苏州大学 A kind of preparation method of hollow carbon material
CN110371950B (en) * 2019-08-12 2023-06-23 苏州大学 Preparation method of hollow carbon material
CN110600739A (en) * 2019-08-22 2019-12-20 浙江工业大学 Preparation method of metal lithium negative electrode protection layer material
CN112142034A (en) * 2020-09-27 2020-12-29 武汉理工大学 Preparation method of sulfur/carbon aerogel composite material
CN112928255A (en) * 2021-01-25 2021-06-08 合肥工业大学 Lithium-sulfur battery composite positive electrode material and preparation method and application thereof
CN112928255B (en) * 2021-01-25 2022-05-06 合肥工业大学 Lithium-sulfur battery composite positive electrode material and preparation method and application thereof

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