CN105529464A - Lithium-sulfur battery - Google Patents
Lithium-sulfur battery Download PDFInfo
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- CN105529464A CN105529464A CN201610042581.4A CN201610042581A CN105529464A CN 105529464 A CN105529464 A CN 105529464A CN 201610042581 A CN201610042581 A CN 201610042581A CN 105529464 A CN105529464 A CN 105529464A
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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
- H01M4/58—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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- 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
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium-sulfur battery. The lithium-sulfur battery is composed of a positive electrode material coating a current collector, a diaphragm, an interlayer, an electrolyte and a negative electrode material, wherein the positive electrode material is composed of a carbon/sulfur active material, a conductive agent and a binder; the diaphragm is a polypropylene diaphragm; the interlayer is a carbon nano tube paper or a carbon nano tube paper acidized by nitric acid; and the negative electrode material is a metallic lithium piece. When a current density is 0.5C(1C=1675mA.g<-1>), a first specific discharge capacity is 1039.9 mAh.g<-1>; after circulating 50 circles, the specific discharge capacity is 674.1 mAh.g<-1>, and an attenuation rate is only 0.1%.
Description
Technical field
The application relates to electrochemical cell art field, particularly relates to a kind of lithium-sulfur cell.
Background technology
Along with electronics technology development day by day, be limited to the lithium ion battery of lower theoretical specific capacity, its energy density promotes difficulty, is difficult to meet growing demand, the novel secondary battery of market demand high-energy-density.Lithium-sulfur cell is using sulphur simple substance as positive pole, and lithium metal is negative pole.Its high theoretical specific capacity (1675mAhg
-1) derive from fracture and the restructuring of S-S key in ring-type sulphur eight molecule in its charge and discharge process, include the repeatedly redox reaction that elemental sulfur and lithium ion occur.The theoretical specific energy density of lithium-sulfur cell is up to 2600Whkg
-1, the energy density in actual production also reaches 500Whkg
-1, far above lithium ion battery (150Whkg
-1).In addition, it is extensive that lithium-sulfur cell has raw material sources, and with low cost, advantages of environment protection, is contemplated to the main force of future market, has been a great concern.
Lithium-sulfur cell is the one of lithium battery, ends and is still in the scientific research stage in 2013.Lithium-sulfur cell is using element sulphur as anode, and lithium metal is as a kind of lithium battery of negative pole.Specific capacity is up to 1675mAhg
-1, far away higher than the capacity (<150mAhg of the cobalt acid lithium battery of commercial extensive use
-1).And sulphur is a kind of environment amenable element, does not substantially pollute environment, it is the very promising lithium battery of one.
Lithium-sulfur cell is anode reactant matter with sulphur, take lithium as negative pole.During electric discharge, negative reaction is that lithium loses electronics and becomes lithium ion, and positive pole reaction generates sulfide for sulphur and lithium ion and electron reaction, and the electrical potential difference of positive pole and negative reaction is the discharge voltage that lithium-sulfur cell provides.Under applied voltage effect, the positive pole of lithium-sulfur cell and negative reaction counter movement, be charging process.Elemental sulfur according to unit mass becomes S completely
2-the electricity that can provide can show that the theoretical discharge specific discharge capacity of sulphur is 1675mAhg
-1, in like manner can show that the theoretical discharge specific discharge capacity of simple substance lithium is 3860mAhg
-1.The theoretical discharge voltage of lithium-sulfur cell is 2.287V, when sulphur and lithium complete reaction generate lithium sulfide (Li
2s), time, the theoretical discharge specific energy of corresponding lithium-sulfur cell is 2600Whkg
-1.
The commercialization process of lithium-sulfur cell is hampered by following significant deficiency: the poorly conductive of sulphur; Many lithium sulfide (the Li of the intermediate product-high-order of sulphur positive pole in discharge process
2s
n, 8>=n>=4) and be soluble in organic electrolyte and spontaneous spreading to negative pole, react with lithium metal, produce " effect of shuttling back and forth ".Tradition lithium-sulfur cell mainly uses liquid organic ethers electrolyte as electrolyte.Ethers electrolyte has ionic conductance and chemical stability is high; With the advantage such as lithium metal compatibility is good.But it is the main cause causing cycle performance difference that many sulphions are dissolved in ethers electrolyte.Ionic liquid at room temperature can reduce polysulfide and spread to cathode of lithium, significantly improves battery performance, but ionic liquid at room temperature synthesis technique is complicated, with high costs, is difficult to large-scale production.Although all solid state electrolyte overcomes " effect of shuttling back and forth ", be still limited to ionic conductance and conductivity that room temperature bends down.
Along with the development of social city, technicalization, popularizing of humanity concept, and the formation of novel harmonious society, it is very important for designing a kind of lithium-sulfur cell slowing down effect of shuttling back and forth, high-performance and long service life.
Summary of the invention
the technical problem solved:the application provides a kind of lithium-sulfur cell, solve existing lithium-sulfur cell to produce and to shuttle back and forth reaction, many sulphions be dissolved in that ethers electrolyte causes that cycle performance is poor, complex process, with high costs, be difficult to large-scale production and be limited to the technical problems such as ionic conductance that room temperature bends down and conductivity.
The application is by the following technical solutions:
A kind of lithium-sulfur cell, described lithium-sulfur cell is by the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material composition, from left to right be followed successively by positive electrode, barrier film, interlayer, barrier film and negative material, electrolyte is in the middle of positive electrode and negative material, described positive electrode is by carbon/sulphur active material, conductive agent and binding agent composition, described carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is active carbon, mesoporous carbon, Graphene, carbon nano-tube, carbon black, one or more compositions in carbon nano-fiber or carbon ball, described conductive agent is acetylene black, one or more compositions in Graphene or carbon nano-tube, binding agent is Kynoar, polyvinylidene fluoride, one or more compositions in Pluronic F-127 or polyacrylic acid.The 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, in wherein carbon/sulphur active material, sulfur content is 70%, and barrier film is polypropylene diaphragm, and interlayer is the carbon nanotube paper of carbon nanotube paper or nitric acid acidifying, and negative material is metal lithium sheet.
As a preferred technical solution of the present invention: described carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, and wherein material with carbon element is active carbon, mesoporous carbon or carbon nano-fiber.
As a preferred technical solution of the present invention: described polypropylene diaphragm is microporous polypropylene membrane, described microporous polypropylene membrane adopts Celgard2400 polypropylene screen.
As a preferred technical solution of the present invention: the carbon nanotube paper preparation method of described nitric acid acidifying is that carbon nanotube paper is put into 6MHNO
3in, 90 DEG C of backflow 10h obtain the carbon nanotube paper of nitric acid acidifying.
As a preferred technical solution of the present invention: described conductive agent is acetylene black, Graphene or carbon nano-tube.
As a preferred technical solution of the present invention: described binding agent is Kynoar, polyvinylidene fluoride or Pluronic F-127.
As a preferred technical solution of the present invention: described collector is one or both compositions in the aluminium foil of aluminium foil or carbon coated.
As a preferred technical solution of the present invention: described solvent adopts METHYLPYRROLIDONE.
As a preferred technical solution of the present invention: described electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1.
beneficial effect
Described in the application, a kind of lithium-sulfur cell adopts above technical scheme compared with prior art, there is following technique effect: many lithium sulfides that 1, physics hinders lithium-sulfur cell electric discharge to produce spread to negative pole, slow down " effect of shuttling back and forth ", improve battery performance, extend the useful life of battery; 2, the cost of raw material is cheap, and production technology is easy, is applicable to large-scale industrial production; 3, the oxygen-containing functional group of the carbon nanotube paper surface graft of nitric acid acidifying can the many sulphions of chemisorbed, this chemisorption hinders many sulphions to spread to negative pole further, circulating battery good stability, electrolyte can be adsorbed preferably, serve as electrolyte basin, reduce the loss of electrolyte, solve the problem of electrolyte rapid wear; 4, at current density 0.5C(1C=1675mAg
-1) time, first discharge specific capacity is 1039.9mAhg
-1; 5, circulate after 250 circles, specific discharge capacity is 674.1mAhg
-1, attenuation rate only has 0.1%.
accompanying drawing illustrates:
Fig. 1 is conventional lithium-sulfur cell schematic diagram described in the application's comparative example 1.
Fig. 2 is lithium-sulfur cell schematic diagram described in the embodiment of the present application 1.
Fig. 3 is lithium-sulfur cell schematic diagram described in the embodiment of the present application 2.
Fig. 4 is conventional lithium-sulfur cell 0.5C cycle performance figure described in the application's comparative example 1.
Fig. 5 is lithium-sulfur cell 0.5C cycle performance figure described in the embodiment of the present application 1.
Fig. 6 is lithium-sulfur cell 0.5C cycle performance figure described in the embodiment of the present application 2.
Fig. 7 is lithium-sulfur cell 1C cycle performance figure described in the embodiment of the present application 3.
Embodiment
Set forth content of the present invention in further detail by the following examples.
Comparative example 1:
As shown in Figure 1, a kind of lithium-sulfur cell, be made up of the positive electrode applied on a current collector, barrier film, electrolyte and negative material, described positive electrode is made up of carbon/sulphur active material, conductive agent and binding agent, carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is active carbon, sulfur content 70%; Conductive agent is acetylene black, binding agent is Kynoar, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, take METHYLPYRROLIDONE as solvent, be coated on after stirring in current collector aluminum foil, then dry 12h in the vacuum drying chamber of 60 DEG C, solvent evaporated, makes positive electrode.
Negative material adopts metal lithium sheet, and barrier film adopts microporous polypropylene membrane Celgard2400, and electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3/ DOL+DME, described DOL+DME are dioxolanes and glycol dimethyl ether, volume ratio 1:1, assemble the conventional lithium-sulfur cell of 2016 type comparative examples 1 in the vacuum drying chamber being full of hydrogen, and in battery test system the performance of test battery.
As shown in Figure 4, conventional lithium-sulfur cell is along with the process of electric discharge, and sulphur simple substance is transformed into the many lithium sulfides being soluble in electrolyte, and to the diffusion of negative pole lithium, many lithium sulfides and the negative pole lithium of high price react; In charging process, many lithium sulfides at a low price get back to positive pole, and this " effect of shuttling back and forth " causes the cyclical stability of lithium-sulfur cell difference.Be 1.7-3.0V at voltage range, during current density 0.5C, first discharge specific capacity is 1084.9mAhg
-1, after circulation 250 circle, specific discharge capacity is 142.4mAhg
-1, often enclosing attenuation rate is 0.3%.
Embodiment 1:
As shown in Figure 2, a kind of lithium-sulfur cell, be made up of the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material, described positive electrode is made up of carbon/sulphur active material, conductive agent and binding agent, carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is active carbon, sulfur content 70%; Conductive agent is acetylene black, binding agent is Kynoar, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, take METHYLPYRROLIDONE as solvent, be coated on after stirring in current collector aluminum foil, then dry 12h in the vacuum drying chamber of 60 DEG C, solvent evaporated, makes positive electrode.
Negative material adopts metal lithium sheet, and barrier film adopts microporous polypropylene membrane Celgard2400, and interlayer adopts carbon nanotube paper, and electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1, assembles the lithium-sulfur cell of 2016 type embodiments 1 in the vacuum drying chamber being full of hydrogen, and in battery test system the performance of test battery.
As shown in Figure 5, carbon nanotube paper interlayer can adsorb electrolyte preferably, serves as electrolyte basin, reduces the loss of electrolyte; Carbon nanotube paper interlayer can hinder many lithium sulfides of lithium-sulfur cell electric discharge generation to spread to negative pole by physics, reduces the generation of " effect of shuttling back and forth ".Be 1.7-3.0V at voltage range, during current density 0.5C, first discharge specific capacity is 1028.0mAhg
-1, after circulation 250 circle, specific discharge capacity is 568.9mAhg
-1, often enclosing attenuation rate is 0.2%.
Embodiment 2:
As shown in Figure 3, a kind of lithium-sulfur cell, be made up of the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material, described positive electrode is made up of carbon/sulphur active material, conductive agent and binding agent, carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is active carbon, sulfur content 70%; Conductive agent is acetylene black, binding agent is Kynoar, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, take METHYLPYRROLIDONE as solvent, be coated on after stirring in current collector aluminum foil, then dry 12h in the vacuum drying chamber of 60 DEG C, solvent evaporated, makes positive electrode.
Negative material adopts metal lithium sheet, and barrier film adopts microporous polypropylene membrane Celgard2400, and interlayer adopts the carbon nanotube paper of nitric acid acidifying, and carbon nanotube paper is put into 6MHNO
3in, 90 DEG C of backflow 10h obtain the carbon nanotube paper of nitric acid acidifying, and electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1, assembles the lithium-sulfur cell of 2016 type embodiments 2 in the vacuum drying chamber being full of hydrogen, and in battery test system the performance of test battery.
As shown in Figure 6, the carbon nanotube paper of nitric acid acidifying can adsorb electrolyte preferably, serves as electrolyte basin, reduces the loss of electrolyte; Can also many lithium sulfides of lithium-sulfur cell electric discharge generation be hindered to spread to negative pole by physics, reduce the generation of " effect of shuttling back and forth ", the oxygen-containing functional group of its surface graft can the many sulphions of chemisorbed, this chemisorption hinders many sulphions to spread to negative pole further, improves lithium-sulfur cell cyclical stability greatly.Be 1.7-3.0V at voltage range, during current density 0.5C, first discharge specific capacity is 1039.9mAhg
-1, after circulation 250 circle, specific discharge capacity is 674.1mAhg
-1, often enclosing attenuation rate is 0.1%
Embodiment 3:
A kind of lithium-sulfur cell, be made up of the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material, described positive electrode is made up of carbon/sulphur active material, conductive agent and binding agent, carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is active carbon, sulfur content 70%; Conductive agent is acetylene black, binding agent is Kynoar, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, take METHYLPYRROLIDONE as solvent, be coated on after stirring in current collector aluminum foil, then dry 12h in the vacuum drying chamber of 60 DEG C, solvent evaporated, makes positive electrode.
Negative material adopts metal lithium sheet, and barrier film adopts microporous polypropylene membrane Celgard2400, and interlayer adopts the carbon nanotube paper of nitric acid acidifying, and carbon nanotube paper is put into 6MHNO
3in, 90 DEG C of backflow 10h obtain the carbon nanotube paper of nitric acid acidifying, and electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1, assembles the lithium-sulfur cell of 2016 type embodiments 3 in the vacuum drying chamber being full of hydrogen, and in battery test system the performance of test battery.
As shown in Figure 7, the carbon nanotube paper of nitric acid acidifying can adsorb electrolyte preferably, serves as electrolyte basin, reduces the loss of electrolyte; Can also many lithium sulfides of lithium-sulfur cell electric discharge generation be hindered to spread to negative pole by physics, reduce the generation of " effect of shuttling back and forth ", the oxygen-containing functional group of its surface graft can the many sulphions of chemisorbed, this chemisorption hinders many sulphions to spread to negative pole further, improves lithium-sulfur cell cyclical stability greatly.Be 1.7-3.0V at voltage range, during current density 1C, first discharge specific capacity is 682.7mAhg
-1, after circulation 400 circle, specific discharge capacity is 453.9mAhg
-1, often enclosing attenuation rate is 0.1%, and coulombic efficiency is up to 99%.
Embodiment 4:
A kind of lithium-sulfur cell, be made up of the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material, described positive electrode is made up of carbon/sulphur active material, conductive agent and binding agent, carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is mesoporous carbon, sulfur content 70%; Conductive agent is Graphene, binding agent is polyvinylidene fluoride, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, take METHYLPYRROLIDONE as solvent, be coated on after stirring in current collector aluminum foil, then dry 12h in the vacuum drying chamber of 60 DEG C, solvent evaporated, makes positive electrode.
Negative material adopts metal lithium sheet, and barrier film adopts microporous polypropylene membrane Celgard2400, and interlayer adopts the carbon nanotube paper of nitric acid acidifying, and carbon nanotube paper is put into 6MHNO
3in, 90 DEG C of backflow 10h obtain the carbon nanotube paper of nitric acid acidifying, and electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1, assembles the lithium-sulfur cell of 2016 type embodiments 4 in the vacuum drying chamber being full of hydrogen.
The carbon nanotube paper of nitric acid acidifying can adsorb electrolyte preferably, serves as electrolyte basin, reduces the loss of electrolyte; Can also many lithium sulfides of lithium-sulfur cell electric discharge generation be hindered to spread to negative pole by physics, reduce the generation of " effect of shuttling back and forth ", the oxygen-containing functional group of its surface graft can the many sulphions of chemisorbed, this chemisorption hinders many sulphions to spread to negative pole further, improves lithium-sulfur cell cyclical stability greatly.
Embodiment 5:
A kind of lithium-sulfur cell, be made up of the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material, described positive electrode is made up of carbon/sulphur active material, conductive agent and binding agent, carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is carbon nano-fiber, sulfur content 70%; Conductive agent is carbon nano-tube, binding agent is Pluronic F-127, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, take METHYLPYRROLIDONE as solvent, be coated on after stirring on the aluminium foil of carbon coated, then dry 12h in the vacuum drying chamber of 60 DEG C, solvent evaporated, makes positive electrode.
Negative material adopts metal lithium sheet, and barrier film adopts microporous polypropylene membrane Celgard2400, and interlayer adopts the carbon nanotube paper of nitric acid acidifying, and carbon nanotube paper is put into 6MHNO
3in, 90 DEG C of backflow 10h obtain the carbon nanotube paper of nitric acid acidifying, and electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1, assembles the lithium-sulfur cell of 2016 type embodiments 5 in the vacuum drying chamber being full of hydrogen.
The carbon nanotube paper of nitric acid acidifying can adsorb electrolyte preferably, serves as electrolyte basin, reduces the loss of electrolyte; Can also many lithium sulfides of lithium-sulfur cell electric discharge generation be hindered to spread to negative pole by physics, reduce the generation of " effect of shuttling back and forth ", the oxygen-containing functional group of its surface graft can the many sulphions of chemisorbed, this chemisorption hinders many sulphions to spread to negative pole further, improves lithium-sulfur cell cyclical stability greatly.
With positive electrode, barrier film, interlayer and negative material assembling Novel lithium sulphur battery system, this carbon nanotube paper interlayer can adsorb ethers electrolyte, serves as electrolyte hold-up tank and suppresses it to consume, and forms the lithium-sulfur cell of sandwich structure; Due to the physical barrier of interlayer, many lithium sulfides that electric discharge is formed can not cross over rapidly membrane contacts negative pole lithium sheet, slow down effect of shuttling back and forth, thus improve the stability of lithium-sulfur cell system itself.By nitric acid acidifying carbon nanotube paper, at its surface graft oxygen-containing functional group, these functional groups can the many sulphions of chemisorbed, the further stability of raising lithium-sulfur cell.The lithium-sulfur cell of this sandwich structure slow down " effect of shuttling back and forth " and occurs while guarantee lithium ion efficiently conducts, and is expected to this type of novel energy-storing system industrialization.
Above-described embodiment is just for setting forth content of the present invention, instead of restriction, and any change therefore in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (9)
1. a lithium-sulfur cell, it is characterized in that: described lithium-sulfur cell is by the positive electrode applied on a current collector, barrier film, interlayer, electrolyte and negative material composition, from left to right be followed successively by positive electrode, barrier film, interlayer, barrier film and negative material, electrolyte is in the middle of positive electrode and negative material, described positive electrode is by carbon/sulphur active material, conductive agent and binding agent composition, described carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, wherein material with carbon element is active carbon, mesoporous carbon, Graphene, carbon nano-tube, carbon black, one or more compositions in carbon nano-fiber or carbon ball, described conductive agent is acetylene black, one or more compositions in Graphene or carbon nano-tube, binding agent is Kynoar, polyvinylidene fluoride, one or more compositions in Pluronic F-127 or polyacrylic acid, the 7:2:1 mixing in mass ratio of described carbon/sulphur active material, conductive agent and binding agent, in wherein carbon/sulphur active material, sulfur content is 70%, and barrier film is polypropylene diaphragm, and interlayer is the carbon nanotube paper of carbon nanotube paper or nitric acid acidifying, and negative material is metal lithium sheet.
2. lithium-sulfur cell according to claim 1, is characterized in that: described carbon/sulphur active material is the compound of sulfur-bearing active material and material with carbon element, and wherein material with carbon element is active carbon, mesoporous carbon or carbon nano-fiber.
3. lithium-sulfur cell according to claim 1, is characterized in that: described polypropylene diaphragm is microporous polypropylene membrane, and described microporous polypropylene membrane adopts Celgard2400 polypropylene screen.
4. lithium-sulfur cell according to claim 1, is characterized in that: the carbon nanotube paper preparation method of described nitric acid acidifying is that carbon nanotube paper is put into 6MHNO
3in, 90 DEG C of backflow 10h obtain the carbon nanotube paper of nitric acid acidifying.
5. lithium-sulfur cell according to claim 1, is characterized in that: described conductive agent is acetylene black, Graphene or carbon nano-tube.
6. lithium-sulfur cell according to claim 1, is characterized in that: described binding agent is Kynoar, polyvinylidene fluoride or Pluronic F-127.
7. lithium-sulfur cell according to claim 1, is characterized in that: described collector is one or both compositions in the aluminium foil of aluminium foil or carbon coated.
8. lithium-sulfur cell according to claim 1, is characterized in that: described solvent adopts METHYLPYRROLIDONE.
9. lithium-sulfur cell according to claim 1, is characterized in that: described electrolyte adopts 1molL
-1liTFSI and 0.1molL
-1liNO
3be dissolved in the ether of DOL+DME two kinds mixing, described DOL+DME is dioxolanes and glycol dimethyl ether, volume ratio 1:1.
Priority Applications (1)
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| CN106450191A (en) * | 2016-10-11 | 2017-02-22 | 天津工业大学 | Positive electrode material of lithium-sulfur battery |
| CN106920913A (en) * | 2017-05-03 | 2017-07-04 | 厦门大学 | A kind of application of monolithic type Bipolar Membrane in lithium-sulfur cell |
| WO2018006557A1 (en) * | 2016-07-06 | 2018-01-11 | The Hong Kong University Of Science And Technology | Tunable and scalable synthesis of hierarchical porous nanocarbon/sulfur composite cathodes |
| CN107785523A (en) * | 2016-08-31 | 2018-03-09 | 清华大学 | Lithium-sulfur cell barrier film and lithium-sulfur cell |
| CN107845774A (en) * | 2016-09-21 | 2018-03-27 | 中国科学院大连化学物理研究所 | Self-supporting porous electrode preparation method and its electrode and application |
| CN109103491A (en) * | 2018-09-03 | 2018-12-28 | 江西克莱威纳米碳材料有限公司 | A kind of lithium-sulfur cell interlayer and preparation method thereof and a kind of lithium-sulfur cell |
| CN109256564A (en) * | 2018-09-10 | 2019-01-22 | 江西克莱威纳米碳材料有限公司 | Carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell |
| CN109873121A (en) * | 2019-03-07 | 2019-06-11 | 上海电气集团股份有限公司 | A kind of preparation method of high-energy density lithium sulphur electrode material for 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 |
| CN110729438A (en) * | 2018-07-17 | 2020-01-24 | 南京理工大学 | Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof |
| CN110911682A (en) * | 2019-11-06 | 2020-03-24 | 华南理工大学 | Electrode of lithium-sulfur battery and preparation method and application thereof |
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| WO2018006557A1 (en) * | 2016-07-06 | 2018-01-11 | The Hong Kong University Of Science And Technology | Tunable and scalable synthesis of hierarchical porous nanocarbon/sulfur composite cathodes |
| CN107785523A (en) * | 2016-08-31 | 2018-03-09 | 清华大学 | Lithium-sulfur cell barrier film and lithium-sulfur cell |
| CN107785523B (en) * | 2016-08-31 | 2019-12-03 | 清华大学 | Lithium-sulfur cell diaphragm and lithium-sulfur cell |
| CN107845774A (en) * | 2016-09-21 | 2018-03-27 | 中国科学院大连化学物理研究所 | Self-supporting porous electrode preparation method and its electrode and application |
| CN106450191A (en) * | 2016-10-11 | 2017-02-22 | 天津工业大学 | Positive electrode material of lithium-sulfur battery |
| CN106920913A (en) * | 2017-05-03 | 2017-07-04 | 厦门大学 | A kind of application of monolithic type Bipolar Membrane in lithium-sulfur cell |
| CN110729438B (en) * | 2018-07-17 | 2022-11-01 | 南京理工大学 | Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof |
| CN110729438A (en) * | 2018-07-17 | 2020-01-24 | 南京理工大学 | Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof |
| CN109103491A (en) * | 2018-09-03 | 2018-12-28 | 江西克莱威纳米碳材料有限公司 | A kind of lithium-sulfur cell interlayer and preparation method thereof and a kind of lithium-sulfur cell |
| CN109256564A (en) * | 2018-09-10 | 2019-01-22 | 江西克莱威纳米碳材料有限公司 | Carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell |
| CN109256564B (en) * | 2018-09-10 | 2021-07-09 | 江西克莱威纳米碳材料有限公司 | Carbon nanotube-graphite composite material, lithium-sulfur battery positive electrode material and lithium-sulfur battery |
| CN111224046A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Application of composite membrane in lithium-sulfur battery |
| CN111224046B (en) * | 2018-11-26 | 2023-04-18 | 中国科学院大连化学物理研究所 | Application of composite membrane in lithium-sulfur battery |
| CN109873121A (en) * | 2019-03-07 | 2019-06-11 | 上海电气集团股份有限公司 | A kind of preparation method of high-energy density lithium sulphur electrode material for 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 |
| CN110911682A (en) * | 2019-11-06 | 2020-03-24 | 华南理工大学 | Electrode of lithium-sulfur battery and preparation method and application thereof |
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