CN104600251A - Lithium-sulfur battery positive electrode and preparation method thereof - Google Patents

Lithium-sulfur battery positive electrode and preparation method thereof Download PDF

Info

Publication number
CN104600251A
CN104600251A CN201410826024.2A CN201410826024A CN104600251A CN 104600251 A CN104600251 A CN 104600251A CN 201410826024 A CN201410826024 A CN 201410826024A CN 104600251 A CN104600251 A CN 104600251A
Authority
CN
China
Prior art keywords
positive electrode
lithium
preparation
sulphur
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410826024.2A
Other languages
Chinese (zh)
Inventor
张凯
覃富荣
方静
刘文文
于范
卢海
李强
李劼
赖延清
张治安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201410826024.2A priority Critical patent/CN104600251A/en
Publication of CN104600251A publication Critical patent/CN104600251A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Landscapes

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

Abstract

The invention discloses a lithium-sulfur battery positive electrode and a preparation method thereof. The preparation method comprises the steps of uniformly mixing a positive active substance, a conducting agent and a bonding agent to obtain a mixture, smearing the mixture on a current collector as an active substance layer, and drying the current collector to obtain a positive substrate; uniformly mixing a conducting agent, a bonding agent and a dispersing agent to obtain a conducting sizing agent, smearing the conducting sizing agent on the outer surface of the positive substrate as a protective layer, and drying the positive substrate to obtain the lithium-sulfur battery positive electrode. The preparation method is simple and easy to operate, easy to control and suitable for industrialized production; in the prepared lithium-sulfur battery positive electrode, the protective layer plays a role of a conducting, sulfur intercepting and electrode stabilizing structure, so that the capacity, multiplying power and cycling stability of a lithium-sulfur battery can be effectively improved, the thickness of the protective layer is easy to control, and the influence on the sulfur content of the positive electrode can be reduced as far as possible.

Description

A kind of lithium-sulphur cell positive electrode and preparation method thereof
Technical field
The present invention relates to lithium-sulfur cell technical field, be specifically related to a kind of lithium-sulphur cell positive electrode and preparation method thereof.
Background technology
Along with population, the growth of economy and the raising of people's living standard, demand for energy increases year by year, because fossil energy uses the environmental pollution caused also further serious.In order to reduce the dependence to fossil energy, the new energy technology based on regenerative resource is fast-developing and apply.Lithium-sulfur cell is as a kind of cheapness and have the rechargeable battery of high-energy-density (theoretical energy density of lithium-sulfur cell is up to 2600W h kg -1), be considered to one of battery system of following most attraction.But lithium-sulfur cell technology is also faced with much from the problem of materials and systems: first, the resistivity of active material sulphur is higher by (5 × 10 -30s cm -1, 25 DEG C); Secondly, can there is volumetric expansion in sulphur, cause sulfur electrode structural damage in cycle charge discharge electric process; Again, the polysulfide formed in cyclic process is easy to be dissolved in electrolyte, and electrode active material reduces gradually, and specific capacity reduces.These problems directly results in active material utilance reduce, cycle life reduce and capacity decline.
For solving the problem, a lot of scientific worker has carried out a lot of research in recent years, and in succession discloses many patents about lithium-sulfur cell.Wherein some method is absorbed in exploitation and is had nanostructure and sulphur composite material of good performance, is used for improving discharge capacity, service life cycle and current efficiency, but the sulfur content in composite material can significantly reduce mostly.Other methods then improve the utilance of active material by designing new cell arrangement, such as, [the Su Y S such as Arumugam Manthiram, Manthiram A. Lithium – sulphur batteries with a microporous carbon paper as a bifunctional interlayer. [J] Nature Communications, 2012, 3:1166.] between pole piece and barrier film, add a porous, electrically conductive interlayer, stop shuttling back and forth of polysulfide, reach the object improving lithium-sulfur cell chemical property, but the quality added increasing positive pole of interlayer, cause lower energy density, and the complicate fabrication process of interlayer, be unfavorable for that industrialization is produced, (application number is the Chinese patent application " a kind of lithium-sulfur cell with adsorption layer " that the building spring etc. propose: 201110092817.2) then direct one deck adsorption layer that applies on barrier film, reach the object that absorption polysulfide improves lithium-sulfur cell chemical property, but the method difficulty applying adsorption layer on barrier film is large, and battery short circuit may be caused.In addition, the Chinese patent application " a kind of multilayered structure anode composite for lithium-sulfur rechargeable battery and preparation method " (application number is: 201210538945.X) that Zhang Kai etc. propose is in traditional lithium-sulphur cell positive electrode surface sputtering layer of conductive film, object is the effect played conduction and cut sulphur, but the method is complicated, cost is higher.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming prior art existence, a kind of lithium-sulphur cell positive electrode and preparation method thereof is provided, this lithium-sulphur cell positive electrode effectively can improve the capacity of lithium-sulfur cell, multiplying power and cyclical stability, and operation is simple for its preparation method, be easy to control, be applicable to suitability for industrialized production.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A preparation method for lithium-sulphur cell positive electrode, mixes positive active material, conductive agent, binding agent as active material layer coating on a current collector, obtains positive electrode substrate after drying in dispersant; The electrocondution slurry be made up of conductive agent, binding agent and dispersant Homogeneous phase mixing is coated in the outer surface of positive electrode substrate as protective layer, after drying, obtains lithium-sulphur cell positive electrode.Active material layer preferably adopts the method for blade coating or spraying to be coated on collector.
Above-mentioned preparation method, preferably, the thickness of described protective layer is 150nm ~ 150 μm.
Above-mentioned preparation method, preferably, in described electrocondution slurry, the quality of conductive agent is 10 ~ 90% of conductive agent and binding agent gross mass, and the quality of dispersant is 45 ~ 95% of electrocondution slurry gross mass.
Above-mentioned preparation method, preferably, described conductive agent is one or more in conductive carbon black, acetylene black, graphite powder, porous charcoal ball, carbon nano-tube, carbon fiber, Graphene, biomass carbon; Described binding agent is one or more in polyvinyl alcohol, polytetrafluoroethylene, polyacrylic acid, carboxymethyl cellulose, TPO, polyvinylidene fluoride, Polyurethane, SBR rubber, Viton, Kynoar; Described dispersant is one or more in water, methyl alcohol, ethanol, isopropyl alcohol, oxolane, acetonitrile, dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE.
Above-mentioned preparation method, preferably, described conductive agent, binding agent and dispersant make electrocondution slurry by one or more the mode Homogeneous phase mixing in physical grinding, mechanical ball milling, mechanical agitation.
Above-mentioned preparation method, preferably, the method that described electrocondution slurry is coated in the outer surface of positive electrode substrate is the one in knife coating, spread coating, spraying process, silk screen print method, rolling method, intaglio printing and laser printing method.
Above-mentioned preparation method, preferably, described collector is the one in aluminium foil, carbon film, aluminium net and nickel screen.Above-mentioned aluminium foil is preferably corrosive aluminum foil or covers carbon aluminium foil.
Above-mentioned preparation method, preferably, by weight percentage described active material layer comprise the positive active material of 50 ~ 90%, the conductive agent of 5 ~ 30% and 5 ~ 20% binding agent; Described positive active material be elemental sulfur, sulfide, containing one or more in sulfur compound.
Above-mentioned preparation method, preferably, described sulfide is one or more in inorganic sulphide, organic sulfur compound, sulfur-bearing complex, described is sulphur carbon composite containing sulfur compound, sulphur polymer composites, organic sulfur compound, one or more in metal sulfide and composite material thereof, and be 5% ~ 100% containing the mass percentage of sulphur in sulfur compound, wherein, carbon in sulphur carbon composite is porous carbon, carbon nano-tube, Graphene or carbon fiber, polymer in sulphur polymer composites is polyaniline, polypyrrole, polythiophene, poly-dopamine, one or more in polyethylene glycol oxide, metal sulfide is iron sulfide, nickel sulfide, cobalt sulfide, artificial gold, copper sulfide, one or more in titanium sulfide.In above-mentioned sulfur compound, the mass percentage of sulphur is preferably 5% ~ 95%; Sulphur carbon composite is preferably porous carbon-sulfur compound, carbon nano-tube-sulfur compound, graphene-sulfur compound or carbon fiber-sulfur compound; Sulphur polymer composites is preferably polyaniline-sulfur compound, polypyrrole-sulfur compound, polythiophene-sulfur compound.
The present invention also provides a kind of above-mentioned preparation method the lithium-sulphur cell positive electrode obtained.
Compared with prior art, the invention has the advantages that: the present invention applies the electrocondution slurry of one deck containing conductive agent, binding agent and dispersant on traditional positive pole plate of lithium-sulfur cell, protective layer is formed after electrocondution slurry drying, protective layer containing conductive agent plays conduction, cuts sulphur effect, not only further increase the conductivity of electrode, and polysulfide can be stoped in cyclic process to be dissolved in electrolyte, can suppress significantly " effect of shuttling back and forth "; Meanwhile, in protective layer, the caking property of bonding agent can also play the effect of stabilized electrodes structure; In addition, the protective layer that electrocondution slurry drying is formed afterwards is a kind of loose structure, is conducive to the infiltration of electrolyte.The features such as protective layer adopts coating method to be formed, and its scheme is simple, be easy to operation, has coating thickness controlled, and materials are few, and substantially do not change the quality of pole piece, thus total sulfur content can be improved as much as possible.The capacity that the battery utilizing lithium-sulphur cell positive electrode of the present invention to assemble has is high, the advantage such as multiplying power and good cycling stability.
In sum, the present invention be a kind of simple to operate, scheme is easy, be easy to control the method preparing the good lithium-sulphur cell positive electrode of chemical property.Lithium-sulphur cell positive electrode prepared by the method obviously can improve the specific discharge capacity of lithium-sulfur cell, high rate performance and cyclical stability.
Accompanying drawing explanation
Fig. 1 is the structural representation of lithium-sulphur cell positive electrode of the present invention.
Fig. 2 is the cycle performance curve chart of the lithium-sulphur cell positive electrode that embodiment 1 and comparative example obtain.
Marginal data:
1, collector; 2, active material layer; 3, protective layer.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Comparative example:
By elemental sulfur, conductive black and Kynoar in mass ratio for the amount of 7:2:1 is dispersed in 1-METHYLPYRROLIDONE (NMP), after carrying out sufficient mechanical agitation, blade coating is in aluminum foil current collector, and vacuumize 24h at the temperature of 60 DEG C, is directly compressed into the electrode slice that diameter is 10mm.
Using the electrode slice of above-mentioned preparation as positive pole, lithium sheet, as negative pole, is assembled into CR2025 button cell in the glove box being full of argon gas, is 25 DEG C in temperature, deboost is 1.7 ~ 3.0V, and charging and discharging currents density is carry out electrochemical property test under the condition of 0.5C.Test result as be positioned in Fig. 2 below curve shown in, can find out that battery first discharge specific capacity is 790mAh/g, 100 times circulation after specific capacity be 424mAh/g.
Embodiment 1:
By elemental sulfur, conductive black and Kynoar in mass ratio for the amount of 7:2:1 is dispersed in 1-METHYLPYRROLIDONE (NMP), after carrying out sufficient mechanical agitation, blade coating is in aluminum foil current collector 1, at the temperature of 60 DEG C, vacuumize 24h, prepares the positive electrode substrate with active material layer 2.
The amount of conductive carbon black and Kynoar 8:2 is in mass ratio dispersed in 1-METHYLPYRROLIDONE (NMP); utilize mechanical agitation to mix and obtain electrocondution slurry; with hairbrush electrocondution slurry brushed gently and form protective layer 3 in the positive electrode substrate with active material layer 2; at the temperature of 60 DEG C after vacuumize; obtain lithium-sulphur cell positive electrode; as shown in Figure 1, wherein the thickness of protective layer 3 is 35 μm to its structure.And then be pressed into the electrode slice that diameter is 10mm.
Using the electrode slice of above-mentioned preparation as positive pole, using lithium sheet as negative pole, being assembled into CR2025 button cell in the glove box being full of argon gas, is 25 DEG C in temperature, deboost is 1.7 ~ 3.0V, and charging and discharging currents density is carry out electrochemical property test under the condition of 0.5C.Test result as be positioned in Fig. 2 top curve shown in, can find out that battery first discharge specific capacity is 1255mAh/g, after 100 circulations, specific capacity is 811mAh/g, compared to comparative example, after adopting the lithium-sulphur cell positive electrode of the present embodiment, significantly improve the specific discharge capacity of lithium-sulfur cell, high rate performance and cyclical stability.
Embodiment 2:
By elemental sulfur, conductive black and polyvinyl alcohol in mass ratio for the amount of 6:3:1 mixes, after carrying out sufficient mechanical agitation, blade coating is in aluminum foil current collector 1, and vacuumize 24h at the temperature of 70 DEG C, prepares the positive electrode substrate with active material layer 2.
The amount of conductive carbon black and Kynoar 7:3 is in mass ratio dispersed in 1-METHYLPYRROLIDONE (NMP); hand lapping is to Homogeneous phase mixing; obtain protective layer slurry; by protective layer slurry gently blade coating in the positive electrode substrate with active material layer 2, form protective layer 3; at the temperature of 80 DEG C after vacuumize; obtain lithium-sulphur cell positive electrode, wherein the thickness of protective layer 3 is 20 μm, and then is pressed into the electrode slice that diameter is 10mm.
Using the electrode slice of above-mentioned preparation as positive pole, using lithium sheet as negative pole, adopt the method in embodiment 1 to carry out electrochemical property test, recording battery first discharge specific capacity is 1231mAh/g, and after 100 circulations, specific capacity is 783mAh/g.
Embodiment 3:
By carbon nano-tube-sulphur composite material, conductive black and polyacrylic acid in mass ratio for the amount of 8:1:1 is dispersed in water, hand lapping is to mixing, blade coating is in aluminum foil current collector 1, and at the temperature of 100 DEG C, vacuumize 24h, prepares the positive electrode substrate with active material layer 2.
The amount being 6:4 in mass ratio by carbon nano-tube and Kynoar is dispersed in 1-METHYLPYRROLIDONE (NMP); hand lapping is to Homogeneous phase mixing; obtain protective layer slurry; with bubbler protective layer slurry is sprayed on gently in the positive electrode substrate with active material layer 2 and forms protective layer 3; at the temperature of 50 DEG C after vacuumize; obtain lithium-sulphur cell positive electrode, wherein the thickness of protective layer 3 is 15 μm, and then is pressed into the electrode slice that diameter is 10mm.
Using the electrode slice of above-mentioned preparation as positive pole, using lithium sheet as negative pole, adopt the method in embodiment 1 to carry out electrochemical property test, recording battery first discharge specific capacity is 1121mAh/g, and after 100 circulations, specific capacity is 763mAh/g.
Embodiment 4:
By sulphur-polyaniline composite material, cassava carbon and Kynoar in mass ratio for the amount of 5:3:2 is dispersed in 1-METHYLPYRROLIDONE (NMP), after carrying out sufficient mechanical agitation, blade coating is on carbon film collector 1, at the temperature of 70 DEG C, vacuumize 24h, prepares the positive electrode substrate with active material layer 2.
By carbon nano-tube and polyacrylic acid in mass ratio 8:2 measure and be dispersed in 1-METHYLPYRROLIDONE (NMP); hand lapping is to Homogeneous phase mixing; obtain protective layer slurry; by protective layer slurry gently blade coating in the positive electrode substrate with active material layer 2, form protective layer 3; at the temperature of 60 DEG C after vacuumize; obtain lithium-sulphur cell positive electrode, wherein the thickness of protective layer 3 is 80 μm, and then is pressed into the electrode slice that diameter is 10mm.
Using the electrode slice of above-mentioned preparation as positive pole, using lithium sheet as negative pole, adopt the method in embodiment 1 to carry out electrochemical property test, battery first discharge specific capacity is 1220mAh/g, and after 100 circulations, specific capacity is 781mAh/g.

Claims (10)

1. a preparation method for lithium-sulphur cell positive electrode, is characterized in that: positive active material, conductive agent, binding agent are mixed in dispersant as active material layer coating on a current collector, obtain positive electrode substrate after drying; The electrocondution slurry be made up of conductive agent, binding agent and dispersant Homogeneous phase mixing is coated in the outer surface of positive electrode substrate as protective layer, after drying, obtains lithium-sulphur cell positive electrode.
2. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: the thickness of described protective layer is 150 nm ~ 150 μm.
3. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: in described electrocondution slurry, the quality of conductive agent is 10 ~ 90% of conductive agent and binding agent gross mass, and the quality of dispersant is 45 ~ 95% of electrocondution slurry gross mass.
4. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: described conductive agent is one or more in conductive carbon black, acetylene black, graphite powder, porous charcoal ball, carbon nano-tube, carbon fiber, Graphene, biomass carbon; Described binding agent is one or more in polyvinyl alcohol, polytetrafluoroethylene, polyacrylic acid, carboxymethyl cellulose, TPO, polyvinylidene fluoride, Polyurethane, SBR rubber, Viton, Kynoar; Described dispersant is one or more in water, methyl alcohol, ethanol, isopropyl alcohol, oxolane, acetonitrile, dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE.
5. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: described conductive agent, binding agent and dispersant make electrocondution slurry by one or more the mode Homogeneous phase mixing in physical grinding, mechanical ball milling, mechanical agitation.
6. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: the method that described electrocondution slurry is coated in the outer surface of positive electrode substrate is the one in knife coating, spread coating, spraying process, silk screen print method, rolling method, intaglio printing and laser printing method.
7. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: described collector is the one in aluminium foil, carbon film, aluminium net and nickel screen.
8. the preparation method of lithium-sulphur cell positive electrode according to claim 1, is characterized in that: by weight percentage described active material layer comprise the positive active material of 50 ~ 90%, the conductive agent of 5 ~ 30% and 5 ~ 20% binding agent; Described positive active material be elemental sulfur, sulfide, containing one or more in sulfur compound.
9. the preparation method of lithium-sulphur cell positive electrode according to claim 8, is characterized in that: described sulfide is one or more in inorganic sulphide, organic sulfur compound, sulfur-bearing complex, described is sulphur carbon composite containing sulfur compound, sulphur polymer composites, organic sulfur compound, one or more in metal sulfide and composite material thereof, and be 5% ~ 100% containing the mass percentage of sulphur in sulfur compound, wherein, carbon in sulphur carbon composite is porous carbon, carbon nano-tube, Graphene or carbon fiber, polymer in sulphur polymer composites is polyaniline, polypyrrole, polythiophene, poly-dopamine, one or more in polyethylene glycol oxide, metal sulfide is iron sulfide, nickel sulfide, cobalt sulfide, artificial gold, copper sulfide, one or more in titanium sulfide.
10. the lithium-sulphur cell positive electrode that the preparation method according to any one of a claim 1 to 9 obtains.
CN201410826024.2A 2014-12-26 2014-12-26 Lithium-sulfur battery positive electrode and preparation method thereof Pending CN104600251A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410826024.2A CN104600251A (en) 2014-12-26 2014-12-26 Lithium-sulfur battery positive electrode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410826024.2A CN104600251A (en) 2014-12-26 2014-12-26 Lithium-sulfur battery positive electrode and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104600251A true CN104600251A (en) 2015-05-06

Family

ID=53125887

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410826024.2A Pending CN104600251A (en) 2014-12-26 2014-12-26 Lithium-sulfur battery positive electrode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104600251A (en)

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105374982A (en) * 2015-12-11 2016-03-02 中国电子科技集团公司第十八研究所 Electrode structure of lithium sulfur battery and processing technology therefor
CN105720248A (en) * 2016-02-19 2016-06-29 钟玲珑 Preparation method for phosphorus-doped three-dimensional structured positive electrode material for lithium-sulfur battery
CN105789557A (en) * 2016-05-26 2016-07-20 厦门大学 Lithium-sulfur pole piece with function protection layer and preparation method and application thereof
CN106058150A (en) * 2016-08-15 2016-10-26 柔电(武汉)科技有限公司 Electrode of lithium sulfur battery and preparation method thereof
CN106207088A (en) * 2016-09-30 2016-12-07 上海空间电源研究所 A kind of lithium-sulphur cell positive electrode and preparation method thereof
WO2017053142A1 (en) * 2015-09-25 2017-03-30 Board Of Regents, The University Of Texas System Multi-layer carbon-sulfur cathodes
CN107359315A (en) * 2017-03-08 2017-11-17 常州大学 A kind of sulphur/new the lithium-sulfur battery composite anode material of amorphous curing nickel
CN107507958A (en) * 2017-07-17 2017-12-22 河南师范大学 A kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate
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
CN107848807A (en) * 2015-07-07 2018-03-27 罗伯特·博世有限公司 The silicon substrate compound with tri-bonded network for lithium ion battery
CN107887605A (en) * 2017-10-25 2018-04-06 天津赫维科技有限公司 One kind is based on active MnO2The preparation method of the lithium-sulphur cell positive electrode of catalysis
CN108666533A (en) * 2018-05-16 2018-10-16 清华大学深圳研究生院 A kind of preparation method and application of lithium-sulfur cell sulfur electrode
CN109004173A (en) * 2018-09-06 2018-12-14 西安建筑科技大学 A kind of lithium-sulphur cell positive electrode and its manufacturing method
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
CN109786119A (en) * 2019-01-23 2019-05-21 三峡大学 A kind of method of porous electrode and its conductive treatment
CN111029525A (en) * 2019-12-31 2020-04-17 四川绿鑫电源科技有限公司 Preparation method of positive pole piece of lithium-sulfur battery and product thereof
CN111477843A (en) * 2020-04-14 2020-07-31 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 3D printing positive electrode material, and preparation method and application thereof
CN111628166A (en) * 2020-06-04 2020-09-04 合肥工业大学 Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof
CN111628150A (en) * 2020-06-04 2020-09-04 合肥工业大学 Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof
CN112011026A (en) * 2020-08-21 2020-12-01 华南农业大学 Tung oil-based positive electrode binder for lithium-sulfur battery, positive electrode for lithium-sulfur battery and preparation method of positive electrode
CN112072067A (en) * 2020-09-18 2020-12-11 北京理工大学 Carbon-sulfur composite positive electrode for lithium-sulfur battery and preparation method thereof
CN112159523A (en) * 2020-10-13 2021-01-01 福州大学 Polyaniline/nickel disulfide/graphene nanofiber composite material and preparation method thereof
CN112382760A (en) * 2020-10-29 2021-02-19 厦门大学 Preparation method of aqueous conductive binder for positive electrode of lithium-sulfur battery
CN112701246A (en) * 2020-12-29 2021-04-23 珠海冠宇电池股份有限公司 Electrode sheet and battery
CN112928243A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Self-supporting nickel sulfide electrode and preparation and application thereof
CN113764624A (en) * 2021-09-17 2021-12-07 西安理工大学 Preparation method of high-performance lithium-sulfur battery positive plate with gradient structure
CN114023919A (en) * 2021-10-20 2022-02-08 中国科学院上海硅酸盐研究所 High-capacity sulfur positive electrode and lithium-sulfur battery containing same
CN114079038A (en) * 2020-08-12 2022-02-22 清华大学 High-sulfur-capacity lithium-sulfur battery positive electrode and preparation method thereof
CN114497550A (en) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
CN114744140A (en) * 2022-03-23 2022-07-12 广西大学 Method for preparing fibrous electrode by active printing

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100758383B1 (en) * 2006-07-20 2007-09-14 경상대학교산학협력단 Sulfur electrode coated with carbon for using in the li/s secondary battery
CN102185158A (en) * 2011-04-14 2011-09-14 武汉理工大学 Lithium sulfur battery provided with adsorption layer
CN103050667A (en) * 2012-12-13 2013-04-17 中南大学 Composite anode of multi-layer structure for lithium-sulfur rechargeable battery and preparation method
CN103515646A (en) * 2013-09-09 2014-01-15 中南大学 Lithium-sulfur battery with conductive adsorption layer, and application of conductive polymer film
CN103647104A (en) * 2013-12-18 2014-03-19 中国科学院上海硅酸盐研究所 Lithium-sulfur battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100758383B1 (en) * 2006-07-20 2007-09-14 경상대학교산학협력단 Sulfur electrode coated with carbon for using in the li/s secondary battery
CN102185158A (en) * 2011-04-14 2011-09-14 武汉理工大学 Lithium sulfur battery provided with adsorption layer
CN103050667A (en) * 2012-12-13 2013-04-17 中南大学 Composite anode of multi-layer structure for lithium-sulfur rechargeable battery and preparation method
CN103515646A (en) * 2013-09-09 2014-01-15 中南大学 Lithium-sulfur battery with conductive adsorption layer, and application of conductive polymer film
CN103647104A (en) * 2013-12-18 2014-03-19 中国科学院上海硅酸盐研究所 Lithium-sulfur battery

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107848807A (en) * 2015-07-07 2018-03-27 罗伯特·博世有限公司 The silicon substrate compound with tri-bonded network for lithium ion battery
WO2017053142A1 (en) * 2015-09-25 2017-03-30 Board Of Regents, The University Of Texas System Multi-layer carbon-sulfur cathodes
CN105374982A (en) * 2015-12-11 2016-03-02 中国电子科技集团公司第十八研究所 Electrode structure of lithium sulfur battery and processing technology therefor
CN105720248A (en) * 2016-02-19 2016-06-29 钟玲珑 Preparation method for phosphorus-doped three-dimensional structured positive electrode material for lithium-sulfur battery
CN105720248B (en) * 2016-02-19 2018-08-10 深圳市佩成科技有限责任公司 A kind of preparation method of phosphorus doping three-dimensional structure lithium sulfur battery anode material
CN105789557A (en) * 2016-05-26 2016-07-20 厦门大学 Lithium-sulfur pole piece with function protection layer and preparation method and application thereof
CN106058150A (en) * 2016-08-15 2016-10-26 柔电(武汉)科技有限公司 Electrode of lithium sulfur battery and preparation method thereof
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
CN106207088A (en) * 2016-09-30 2016-12-07 上海空间电源研究所 A kind of lithium-sulphur cell positive electrode and preparation method thereof
CN106207088B (en) * 2016-09-30 2019-05-03 上海空间电源研究所 A kind of lithium-sulphur cell positive electrode and preparation method thereof
CN107359315A (en) * 2017-03-08 2017-11-17 常州大学 A kind of sulphur/new the lithium-sulfur battery composite anode material of amorphous curing nickel
CN107507958A (en) * 2017-07-17 2017-12-22 河南师范大学 A kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate
CN107507958B (en) * 2017-07-17 2021-09-10 河南师范大学 In-situ powder coating and polar plate preparation integrated method for lithium-sulfur battery
CN107887605B (en) * 2017-10-25 2021-09-28 天津赫维科技有限公司 Based on active MnO2Preparation method of catalytic lithium-sulfur battery positive electrode
CN107887605A (en) * 2017-10-25 2018-04-06 天津赫维科技有限公司 One kind is based on active MnO2The preparation method of the lithium-sulphur cell positive electrode of catalysis
CN108666533A (en) * 2018-05-16 2018-10-16 清华大学深圳研究生院 A kind of preparation method and application of lithium-sulfur cell sulfur electrode
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
CN109004173A (en) * 2018-09-06 2018-12-14 西安建筑科技大学 A kind of lithium-sulphur cell positive electrode and its manufacturing method
CN109004173B (en) * 2018-09-06 2020-12-25 西安建筑科技大学 Lithium-sulfur battery positive electrode and manufacturing method thereof
CN109786119A (en) * 2019-01-23 2019-05-21 三峡大学 A kind of method of porous electrode and its conductive treatment
CN112928243A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Self-supporting nickel sulfide electrode and preparation and application thereof
CN111029525A (en) * 2019-12-31 2020-04-17 四川绿鑫电源科技有限公司 Preparation method of positive pole piece of lithium-sulfur battery and product thereof
CN111477843B (en) * 2020-04-14 2022-09-20 江西省纳米技术研究院 3D printing positive electrode material, and preparation method and application thereof
CN111477843A (en) * 2020-04-14 2020-07-31 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 3D printing positive electrode material, and preparation method and application thereof
CN111628150A (en) * 2020-06-04 2020-09-04 合肥工业大学 Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof
CN111628150B (en) * 2020-06-04 2021-10-08 合肥工业大学 Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof
CN111628166A (en) * 2020-06-04 2020-09-04 合肥工业大学 Three-dimensional lithium sulfide electrode for lithium-sulfur battery and preparation method thereof
CN114079038A (en) * 2020-08-12 2022-02-22 清华大学 High-sulfur-capacity lithium-sulfur battery positive electrode and preparation method thereof
CN114079038B (en) * 2020-08-12 2023-09-26 清华大学 High-sulfur-load lithium-sulfur battery positive electrode and preparation method thereof
CN112011026A (en) * 2020-08-21 2020-12-01 华南农业大学 Tung oil-based positive electrode binder for lithium-sulfur battery, positive electrode for lithium-sulfur battery and preparation method of positive electrode
CN112011026B (en) * 2020-08-21 2021-05-07 华南农业大学 Tung oil-based positive electrode binder for lithium-sulfur battery, positive electrode for lithium-sulfur battery and preparation method of positive electrode
CN112072067A (en) * 2020-09-18 2020-12-11 北京理工大学 Carbon-sulfur composite positive electrode for lithium-sulfur battery and preparation method thereof
CN112159523A (en) * 2020-10-13 2021-01-01 福州大学 Polyaniline/nickel disulfide/graphene nanofiber composite material and preparation method thereof
CN112159523B (en) * 2020-10-13 2021-10-29 福州大学 Polyaniline/nickel disulfide/graphene nanofiber composite material and preparation method thereof
CN114497550A (en) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery
CN112382760A (en) * 2020-10-29 2021-02-19 厦门大学 Preparation method of aqueous conductive binder for positive electrode of lithium-sulfur battery
CN112701246A (en) * 2020-12-29 2021-04-23 珠海冠宇电池股份有限公司 Electrode sheet and battery
CN113764624A (en) * 2021-09-17 2021-12-07 西安理工大学 Preparation method of high-performance lithium-sulfur battery positive plate with gradient structure
CN114023919A (en) * 2021-10-20 2022-02-08 中国科学院上海硅酸盐研究所 High-capacity sulfur positive electrode and lithium-sulfur battery containing same
CN114023919B (en) * 2021-10-20 2023-08-08 中国科学院上海硅酸盐研究所 High-load sulfur positive electrode and lithium sulfur battery containing high-load sulfur positive electrode
CN114744140B (en) * 2022-03-23 2023-06-23 广西大学 Method for preparing fibrous electrode by active printing
CN114744140A (en) * 2022-03-23 2022-07-12 广西大学 Method for preparing fibrous electrode by active printing

Similar Documents

Publication Publication Date Title
CN104600251A (en) Lithium-sulfur battery positive electrode and preparation method thereof
CN103346293B (en) Lithium ion battery cathode material and its preparation method, lithium ion battery
CN102324493B (en) There is thick electrode of good electrical chemical property and preparation method thereof
CN103219491B (en) Copper sulfide anode and preparation method thereof
Liu et al. Biomass-derived Activated Carbon for Rechargeable Lithium-Sulfur Batteries.
CN103390752B (en) Graphene-based matrix material, its preparation method and the application in lithium-sulfur cell thereof
CN104269515A (en) Negative electrode piece of lithium ion battery, preparation method of negative electrode piece and lithium ion battery
CN103700859A (en) Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material
CN108682820B (en) Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery
CN103811731A (en) Graphene-sulfur composite electrode material, preparation method and application thereof
CN102104140A (en) Power battery electrode and manufacturing method thereof
CN104362294B (en) A kind of porous sulphur positive pole for lithium-sulfur cell, its preparation method and lithium-sulfur cell
CN104347881A (en) Preparation method and applications of battery graphene-base current collector
CN102496707A (en) Preparation method of nano-grade-carbon-clad spinel lithium titanate battery cathode material
CN108630890A (en) A kind of multi-layer electrode structure and preparation method thereof for lithium-sulfur cell
Li et al. High-performance supercapacitor carbon electrode fabricated by large-scale roll-to-roll micro-gravure printing
Fan et al. Application of stabilized lithium metal powder and hard carbon in anode of lithium–sulfur battery
CN103915602A (en) New lithium sulfur battery positive electrode and lithium sulfur battery comprising new lithium sulfur battery positive electrode
CN112614703B (en) Negative electrode material of ionic capacitor and preparation method and application thereof
WO2018059180A1 (en) High-power, high-energy chemical power supply and preparation method therefor
CN109950549A (en) A kind of lithium ion battery collector and preparation method thereof
CN108258209A (en) A kind of carbide/carbon nano tube/graphene carries sulphur composite material and preparation method and application
Wang et al. Electrochemical stability of optimized Si/C composites anode for lithium-ion batteries
CN109859951A (en) A kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof
CN108923060A (en) A kind of solid state lithium battery and preparation method of modifying interface

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150506