CN105261721B - A kind of asymmetry diaphragm and the application in lithium-sulfur rechargeable battery - Google Patents
A kind of asymmetry diaphragm and the application in lithium-sulfur rechargeable battery Download PDFInfo
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- CN105261721B CN105261721B CN201510542932.3A CN201510542932A CN105261721B CN 105261721 B CN105261721 B CN 105261721B CN 201510542932 A CN201510542932 A CN 201510542932A CN 105261721 B CN105261721 B CN 105261721B
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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
- 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
- H01M50/431—Inorganic material
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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
- 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
- H01M50/411—Organic 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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Abstract
The invention belongs to electrochemical technology fields, and in particular to a kind of asymmetry diaphragm and the application in lithium-sulfur rechargeable battery.The asymmetry diaphragm is made of macromolecule matrix layer with conductive carbon layer；The conductive carbon layer is bonded on macromolecule matrix layer；The conductive carbon layer main body is carbon material, by binding agent adhesion or carbon material from adhesion.When applied to lithium-sulfur rechargeable battery, the conductive carbon layer is contacted with composite sulfur anode；Macromolecule matrix level is contacted to cathode with lithium metal.The present invention forms asymmetric diaphragm using electric conductivity, high-specific surface area speciality and the high molecular adhesive of carbon material, positive electrode active material utilization can be effectively promoted under relatively low conductive layer additive amount and inhibits polysulfide migration, and then promote the positive electrode capacity and cyclical stability of battery.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of asymmetry diaphragm and answering in lithium-sulfur rechargeable battery
With.
Background technology
With the development of being constantly progressive for modern science and technology, especially electronics industry, modern society is for electron stored energy
The demand of equipment is increasing.On the other hand, emerging in large numbers with environmental pollution and traditional fossil energy exhaustion etc. problem, stores up
Energy technology is gradually by the more and more extensive concern of people.
What the use of Ni-MH battery and lithium ion battery had successfully pushed including mobile phone, electric vehicle a series of has
The development and use of the electronics, electrical equipment of social change.But due to there is larger limitation in energy density, it
Cannot fully meet social technology development demand.And lithium-sulfur cell is as a kind of model electrochemical system, because its
High theoretical energy density and relatively low cost receive the extensive concern of educational circles and industrial circle in recent years, and are expected to substitute
Existing lithium ion battery.
In lithium-sulfur cell, sulphur is a kind of positive electrode with high theoretical specific capacity, and theoretical capacity is reachable
1672mAh/g, the theoretical energy density with the battery system of cathode of lithium composition is up to 2600Wh/kg.In addition, sulphur anode also has
Many advantages, such as inexpensive, nontoxic.But the intermediate product (polysulfide) that lithium-sulfur cell generates in charge and discharge process is easy
It dissolves, spread in the electrolytic solution, and then active material is caused to be detached from positive conductive network；Further, since polysulfide and cathode
Reaction and the disproportionated reaction in electrolyte, active material can be deposited in cathode, diaphragm and positive electrode surface, formed active matter
Matter inert layer.On the one hand this utilization rate for greatly reducing active material, not only reduces positive electrode capacity, also speeds up lithium-sulfur cell
Performance degradation limits the raising of anode sulphur load capacity；On the other hand also due to inert layer is formed, ion transmission channel is blocked
Plug, the internal resistance of cell increase, a series of problems, such as causing battery failure, generate heat.This how is solved to deposit for a long time in lithium-sulfur cell
" migration effect " and " inertia effect layer ", further promoted lithium-sulfur cell positive electrode capacity and cyclical stability, to push
Its practicalization has great value.
At present, the numerous studies based on lithium-sulfur cell concentrate on positive electrode side, and main means include carrying out anode
The structure design of sulphur/carbon composite and preparation improve the utilization rate of anode sulfur materials by improving electric conductivity and pore-size distribution,
And the dissolving diffusion attempted to polysulfide carries out a degree of inhibition.Such as：Nazar etc. passes through sulphur and ordered mesopore carbon
It is compound, using the migration of ordered mesoporous pore canals limitation polysulfide, obtain electrode material (the Ji XL, et of superior performance
al.Nat.Mater.2009；8(6):500-6.)；Wang Jiulin etc. is by by sulphur and the compound part realized to sulphur of polyacrylonitrile
Curing, so as to improve the performances such as the cyclical stability of electrode (Wang JL, et al.Adv.Mater.2002；14(13-14):
963-5.；Wang Jiulin, Yang Jun, solution is sparkling and crystal-clear, waits publication numbers：CN 1384556).Although it is designed by cathode material structure, high score
The son modes such as compound can improve element sulphur utilization rate, and part inhibits the generation and diffusion of polysulfide, but its specific cycle performance
It still greatly differs from each other away from functionization with energy density.
In the recent period, other researchers are conceived to the components such as cathode and diaphragm in lithium-sulfur rechargeable battery, it is desirable to " be moved by inhibiting
Move effect " improve the stability of battery system, such as：Zhang etc. by adding lithium nitrate additive negative in the electrolytic solution
Pole surface forms inertia protective layer (Zhang SS.Electro.Acta.2012；70:344-8.), Huang etc. is by diaphragm
Upper coating Nafion prepares ion selective separator (Huang JQ, et al.Energy Environ.Sci.2014；7(1):
347-53.).These trials inhibit the diffusion of polysulfide to a certain extent, but its capacity characteristic is still not fully up to expectations.If energy
Using the design of lithium-sulfur cell system component itself, a kind of asymmetry for the recyclable active material of lithium-sulfur rechargeable battery is developed
Diaphragm is then expected to greatly improve the capacity and cyclical stability of battery, and then promotes the development of lithium-sulfur rechargeable battery.
Invention content
The object of the present invention is to provide a kind of asymmetric diaphragm and the application in lithium-sulfur rechargeable battery, specific technical solutions
It is as follows：
A kind of asymmetry diaphragm, the asymmetry diaphragm are made of macromolecule matrix layer with conductive carbon layer, and conduction is utilized
The adhesive of the electric conductivity of carbon-coating, high-specific surface area speciality and macromolecule matrix layer；The conductive carbon layer is bonded in polymer-based
On body layer；The conductive carbon layer main body is carbon material, by binding agent adhesion or carbon material from adhesion.
Preferably, the carbon material is carbon black, micro-pore carbon material, meso-porous carbon material, macropore carbon material, multi-stage porous carbon materials
One or more in material, carbonaceous mesophase spherules, fullerene, carbon nano-fiber, carbon nanotube, graphene, carbon aerogels,
And above-mentioned oxygen, nitrogen, boron, sulphur, phosphorus or transition metal atoms doped forms.
Preferably, the binding agent is Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrole
One kind in alkanone, polyacrylic acid, butadiene-styrene rubber, sodium carboxymethylcellulose, chitosan, poly-dopamine, sodium alginate, cyclodextrin
Or more than one.
Preferably, the macromolecule matrix layer is polypropylene diaphragm, polypropylene-polyethylene-polypropylene diaphragm, polyimides
Diaphragm, Kynoar, polysulfones diaphragm, poly- perfluoro sulfonic acid membrane, polybenzimidazole membrane or porous cellulose film.
Preferably, the thickness of the asymmetric diaphragm is 1-1000 μm, and the thickness of conductive carbon layer is 0.0001-1000 μm.
Preferably, the binding agent is 0-60% in the mass fraction of conductive carbon layer.
Application of the asymmetry diaphragm as described above in lithium-sulfur rechargeable battery：The conductive carbon layer connects with composite sulfur anode
It touches；Macromolecule matrix level is contacted to cathode with lithium metal.
The asymmetry diaphragm is for the utilization of polysulfide of the promotion to being generated in lithium-sulfur rechargeable battery charge and discharge process
Rate simultaneously inhibits its diffusion.
Beneficial effects of the present invention are：
The present invention leads to that active material effective rate of utilization is low, cyclical stability is poor for polysulfide migration in lithium-sulfur cell
The defects of, propose a kind of asymmetric diaphragm for the recyclable active material of lithium-sulfur rechargeable battery.
(1) micropore/meso/macroporous structure using carbon material formation and its larger specific surface area, realize for more
The physical barriers of sulfide and absorption, will diffuse out anode and the polysulfide returned that shuttles from negative side is uniformly dispersed and fixed
In asymmetric diaphragm, the concentration gradient of polysulfide, positive and negative so as to reduce polysulfide between gentle side of the positive electrode and negative side
The migration effect of interpolar improves the cyclical stability of lithium-sulfur cell.
(2) using the electric conductivity of carbon material, by introducing conducting matrix grain, active material utilization is improved, is eliminated lazy
Property layer, so as to greatly promote the positive electrode capacity of lithium-sulfur cell, reduces the internal resistance of battery.
(3) for the present invention for the applied widely of carbon material, preparation method is simple, huge to lithium-sulfur cell performance boost,
And using cooperation high power capacity positive electrode, the lithium-sulfur cell of high-energy density can be obtained.
Specific embodiment
The present invention is further described with reference to specific embodiment, but the present invention is not limited solely to following implementation
Example.
Embodiment 1
By the double-walled carbon nano-tube that the method for swimming is grown with polytetrafluoroethylene (PTFE) according to mass ratio 1:1 is sufficiently mixed drying
Afterwards, the conductive carbon layer that thickness is about 100 μm is made.By rolling by the conductive carbon layer and 25 μm of polypropylene diaphragm compound, shape
Into the asymmetric diaphragm of recyclable active material, thickness is 125 μm.Simultaneously using sulphur/multi-wall carbon nano-tube composite material as anode,
Metal lithium sheet is cathode, and the ethylene glycol dimethyl ether solution of lithium perchlorate is as electrolyte, the polypropylene matrix layer of asymmetric diaphragm
In face of metal lithium sheet.Under the charge-discharge velocity of 2C, 982mAh/ is reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm
G, preceding 200 circle cycle individual pen attenuation rate about 0.03%, far below the lithium-sulfur cell (about 0.29%) using common diaphragm.
Embodiment 2
Will be using magnesia as template, meso-porous carbon material that chemical vapour deposition technique is grown is distributed to mass fraction and is
In 1% aqueous povidone solution, the asymmetric diaphragm for polypropylene diaphragm surface, forming that thickness is 26 μm is filtered.
Wherein conductive carbon layer contains the meso-porous carbon material of mass fraction 90% and 10% polyvinylpyrrolidone, and thickness is 1 μm, and poly- third
Alkene diaphragm is 25 μm.By the polypropylene one side of the asymmetry diaphragm to lithium anode, using sulphur/absorbent charcoal composite material as just
Pole, 1, the 3- dioxolanes of methyl triethyl group LiBF4,1,2- dimethoxyethane solutions are assembled into lithium as electrolyte
Sulphur battery.Under the discharge rate of 0.01C, 1589mAh/g is reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm, it is preceding
200 circle cycle individual pen attenuation rates are about 0.04%, far below the lithium-sulfur cell (about 0.5%) using common diaphragm.
Embodiment 3
The nitrating carbon nano-fiber that electrospinning polyacrylonitrile fibre is carbonized is with polyvinyl alcohol with 8:2 mass ratio mixing
After scratch onto 50 μm of polypropylene-polyethylene-polypropylene diaphragms, form asymmetric diaphragm.Conductive carbon layer thickness is 200 μm, no
Symmetrical membrane thicknesses are 250 μm.Sulphur/carbon black composite material anode is supported in the conductive carbon layer of the asymmetry diaphragm, with gold
Belong to polypropylene-polyethylene-polypropylene side that lithium faces the diaphragm for cathode, use trifluoromethyl sulfonic acid lithium, lithium nitrate, more sulphur
Change 1, the 3- dioxolanes of lithium, 1,2- dimethoxyethane solutions as electrolyte, making lithium-sulfur cell.In 0.2C charge and discharge speed
Under rate, 1053mAh/g is reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm, preceding 200 circle cycle individual pen number case is
0.06%, far below common lithium-sulfur cell (about 0.45%).
Embodiment 4
By the methylpyrrolidone solution of conductive black and 2% Kynoar with 7:3 mass ratioes mix, after being uniformly dispersed
Spin coating loads to 10 μ m-thick polypropylene diaphragm surfaces, forms the asymmetric diaphragm that conductive layer thickness is about 1 μm, membrane thicknesses 11
μm.The asymmetry diaphragm is applied in lithium-sulfur cell, conductive carbon layer faces anode, using sulphur/graphene composite material as anode,
Lithium metal is cathode, and 1, the 3- dioxolanes, 1,2- dimethoxyethane solutions of two (trimethyl fluoride sulfonyl) imine lithiums are used as electricity
Solve liquid.Under the discharge rate of 0.5C, 1011mAh/g, preceding 400 circle are reached using the lithium-sulfur cell initial capacity of asymmetric diaphragm
It is about 0.07% to recycle individual pen attenuation rate, far below the lithium-sulfur cell (about 0.5%) using common diaphragm.
Embodiment 5
By phosphorus doping carbonaceous mesophase spherules and carbon nano pipe array according to mass ratio 1:3 are combined conductive carbon layer, thickness
About 800 μm, using carbon nano pipe array from blocking characteristics, shape on 200 μm of polybenzimidazoles matrixes is adhered to by rolling
Into asymmetric diaphragm, thickness is 1000 μm.By the asymmetry diaphragm in lithium-sulfur cell, conductive carbon layer to face anode, with sulphur/
Mesoporous carbon complex is anode, and lithium metal is cathode, tetraethyl LiBF4,1, the 3- dioxolanes of lithium nitrate, 1,2- bis-
Ethyl Methyl Ether solution makes lithium-sulfur cell as electrolyte.Under 5C current densities, using the lithium sulphur electricity of the asymmetry diaphragm
Pond initial capacity reaches 734mAh/g, and preceding 200 circle cycle individual pen rate of decay is 0.03%, far below the lithium using common diaphragm
Sulphur battery (about 0.33%).
Embodiment 6
By the boron-doping carbon nanotube and graphene oxide of chemical vapor deposition growth and poly-dopamine according to mass ratio 1:1:1
Ratio composite coating in 10 μm of polyimide diaphragms, the conductive carbon layer thickness of formation is 5 μm, obtains the conduction that thickness is 15 μm
Carbon-coating/polyimides asymmetry diaphragm.By the asymmetry diaphragm in lithium-sulfur cell, conductive carbon layer to face anode, with sulphur/Jie
Hole carbon composite is anode, and lithium metal is cathode, trifluoromethyl sulfonic acid lithium, lithium nitrate, more lithium sulfides 1,3- dioxolanes,
1,2- dimethoxyethane solution is electrolyte, prepares lithium-sulfur cell.Under 1C current densities, using the lithium of the asymmetry diaphragm
Sulphur battery initial capacity reaches 1082mAh/g, and preceding 150 circle cycle individual pen rate of decay is 0.04%, far below using commonly every
The lithium-sulfur cell (about 0.3%) of film.
Embodiment 7
By porous nitrogen, sulphur codope graphene and sodium alginate soln according to mass ratio be 1:1 is spin-coated on 1 μm of polyvinylidene fluoride
On alkene diaphragm, the conductive carbon layer of 10nm thickness is obtained, forms the asymmetric diaphragm that thickness is 1.01 μm.The asymmetry diaphragm is used for
Lithium-sulfur cell, conductive carbon layer face anode, and using sulphur/micropore carbon complex as anode, lithium metal is cathode, with two (trifluoromethyls
Sulphonyl) imine lithium, lithium nitrate four (glycol dimethyl ether) solution as electrolyte, make lithium-sulfur cell.It is close in 0.05C electric currents
Under degree, 1432mAh/g, preceding 200 circle cycle individual pen rate of decay are reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm
It is 0.04%, far below the lithium-sulfur cell (about 0.25%) using common diaphragm.
Embodiment 8
Carbon nanotube that template pyrolysismethod is prepared mixes cobalt multi-stage porous carbon material and polyethylene glycol material according to matter
Measure ratio 6:3:1 ratio, the surface of 5 μm of polysulfones diaphragms is supported on by knife coating, and repressed rear conductive carbon layer thickness is about
500nm, asymmetric membrane thicknesses are 5.5 μm.The asymmetry diaphragm is used as lithium-sulfur cell diaphragm, conductive carbon layer is in polysulfones diaphragm
Between anode, while using sulphur/acrylonitrile composite material as anode, metal lithium sheet is as cathode, the carbonic acid of lithium hexafluoro phosphate
Dimethyl ester, diethyl carbonate solution make lithium-sulfur cell as electrolyte.It is not right using this under the charge-discharge velocity of 0.8C
The lithium-sulfur cell initial capacity of diaphragm is claimed to reach 946mAh/g, preceding 200 circle cycle individual pen attenuation rate about 0.01%, far below use
The lithium-sulfur cell (about 0.19%) of common diaphragm.
Embodiment 9
By fullerene, sulfur doping carbon aerogels and polyacrylic acid according to mass ratio 1:2:3 mixing dispersions in aqueous solution, are led to
The polyvinylidene fluoride surface at 5 μm after filtering is crossed, thickness is made as 10 μm of conductive carbon layers, the thickness of obtained asymmetry diaphragm
It is 15 μm.Simultaneously using sulphur/ordered mesopore carbon as anode, lithium metal is cathode, and the Kynoar of asymmetric diaphragm is born in face of lithium
Pole, the ethylene glycol dimethyl ether solution of methyl triethyl group LiBF4 make lithium-sulfur cell as electrolyte.In 10C charge and discharge
Under rate, 632mAh/g is reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm, preceding 100 circle cycle individual pen number case is
0.02%, far below the lithium-sulfur cell (about 0.3%) using common diaphragm.
Embodiment 10
The microporous carbon and chitosan obtained after sucrose is carbonized is according to mass ratio 3:1 solid phase mixing, rolling is in porous fibre
Plain film surface forms asymmetric diaphragm, 200 μm of conductive carbon layer thickness, asymmetric 500 μm of membrane thicknesses.By the asymmetry diaphragm
For lithium-sulfur cell, conductive carbon layer faces anode, is negative using lithium metal using sulphur/carbon nano-tube/poly dopamine as anode
Pole, 1, the 3- dioxolanes of more lithium sulfides, 1,2- dimethoxyethane solutions make lithium-sulfur cell as electrolyte.It is filled in 1C
Under discharge rate, 1231mAh/g, preceding 300 circle cycle individual pen number are reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm
Case is 0.02%, far below the lithium-sulfur cell (about 0.35%) using common diaphragm.
Embodiment 11
Using conductive black, the macropore carbon of opal structural is inverted as carbon-coating, butadiene-styrene rubber, sodium carboxymethylcellulose conduct
Binding agent, according to mass ratio 2:6:1:Aqueous slurry is made in 1 mixing dispersion, coated in 25 μm of polypropylene screen surface, after drying
Gained conductive carbon layer thickness is 105 μm, and the obtained thickness of asymmetric diaphragm is 130 μm.The asymmetry diaphragm is used for lithium sulphur
Battery, conductive carbon layer faces anode, using sulphur/carbon nanotube/graphene oxide as anode, using lithium metal as cathode, trifluoro
The ethylene glycol dimethyl ether solution of pyrovinic acid lithium makes lithium-sulfur cell as electrolyte.Under 0.02C charge-discharge velocities, use
The lithium-sulfur cell initial capacity of the asymmetry diaphragm reaches 1408mAh/g, and preceding 400 circle cycle individual pen number case is 0.08%, far
Less than the lithium-sulfur cell (about 0.5%) using common diaphragm.
Embodiment 12
By graphene, microporous activated carbon, cyclodextrin according to mass ratio 2:3:1 it is compound after water system gel, immersion coating is made
Conductive carbon layer is formed on the surface of poly- perfluoro sulfonic acid membrane, carbon layers having thicknesses are about 1 μm, and asymmetric membrane thicknesses are 31 μm.Use this
One diaphragm assembles lithium-sulfur cell, makes conductive carbon layer in face of anode, while using sulphur/nitrogen-doped graphene compound as anode, lithium metal
For cathode, lithium perchlorate, lithium hexafluoro phosphate dimethyl sulfoxide solution as electrolyte, make lithium-sulfur cell.In the charge and discharge of 3C
Under rate, 904mAh/g, preceding 2000 circle cycle individual pen attenuation rate are reached using the lithium-sulfur cell initial capacity of the asymmetry diaphragm
About 0.005%, far below the lithium-sulfur cell (about 0.27%) using common diaphragm.
Claims (4)
1. a kind of asymmetry diaphragm, which is characterized in that the asymmetry diaphragm is made of macromolecule matrix layer with conductive carbon layer, profit
With the adhesive of the electric conductivity of conductive carbon layer, high-specific surface area speciality and macromolecule matrix layer；The conductive carbon layer is bonded in
On macromolecule matrix layer；The conductive carbon layer main body is carbon material, passes through binding agent adhesion；The conductive carbon layer includes template heat
Carbon nanotube that solution is prepared and mix cobalt multi-stage porous carbon material, the binding agent is polyethylene glycol, the carbon nanotube and
The ratio of multi-stage porous carbon material and polyethylene glycol is 6:3:1, the macromolecule matrix layer is polysulfones diaphragm.
2. asymmetry diaphragm according to claim 1, which is characterized in that the thickness of the asymmetry diaphragm is 1-1000 μ
M, the thickness of conductive carbon layer is 0.0001-1000 μm.
3. application of the claim 1~2 any one of them asymmetry diaphragm in lithium-sulfur rechargeable battery, which is characterized in that institute
Conductive carbon layer is stated to contact with composite sulfur anode；Macromolecule matrix level is contacted to cathode with lithium metal.
4. application according to claim 3, which is characterized in that the asymmetry diaphragm is for promotion to lithium-sulfur rechargeable battery
The utilization rate of the polysulfide generated in charge and discharge process simultaneously inhibits its diffusion.
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| CN113555646B (en) * | 2021-08-10 | 2022-04-19 | 大连理工大学 | Preparation method of coagulant type lithium-sulfur battery positive electrode side interlayer material |
| CN116995366A (en) * | 2023-05-31 | 2023-11-03 | 深圳材启新材料有限公司 | Battery diaphragm, preparation method thereof and application of battery diaphragm in preparation of battery |
| CN116632455B (en) * | 2023-07-20 | 2023-10-20 | 宁德新能源科技有限公司 | Separator, electrochemical device including the same, and electronic device |
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| DE102011088910A1 (en) * | 2011-12-16 | 2013-06-20 | Robert Bosch Gmbh | Lithium sulfur cell separator with polysulfide barrier |
| WO2014028218A1 (en) * | 2012-08-17 | 2014-02-20 | Board Of Regents, The University Of Texas System | Porous carbon interlayer for lithium-sulfur battery |
| CN104300128A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Integrated membrane electrode structure for lithium sulfur battery and preparation method thereof |
| CN103474603B (en) * | 2013-09-11 | 2016-11-02 | 清华大学 | Ion selective separator and preparation and application method thereof for lithium-sulfur rechargeable battery |
| CN104362394A (en) * | 2014-10-23 | 2015-02-18 | 清华大学 | Lithium-sulfur rechargeable battery |
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