CN106848156A - Lithium-sulfur cell diaphragm material and its application - Google Patents
Lithium-sulfur cell diaphragm material and its application Download PDFInfo
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- CN106848156A CN106848156A CN201710130852.6A CN201710130852A CN106848156A CN 106848156 A CN106848156 A CN 106848156A CN 201710130852 A CN201710130852 A CN 201710130852A CN 106848156 A CN106848156 A CN 106848156A
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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
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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
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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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- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- 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
Abstract
The present invention relates to lithium-sulfur cell diaphragm material and its application, the diaphragm material is dried to obtain after being coated on polypropylene surface by catalyst, conductive agent, binding agent slurry, is micron-sized；Catalyst is metal oxide, metal nitride, metal sulfide or metal simple-substance；Conductive agent is acetylene black, Ketjen black or CNT；Binding agent is Kynoar, polyvinylidene fluoride, Pluronic F-127 or polyacrylic acid.Described conductive agent is nanoscale with catalyst.The barrier film can hinder many sulphions to be spread to negative pole, make many sulphions in its surface aggregation, and catalyst can activate many sulphions, improve the actual specific capacity and cyclical stability of lithium-sulfur cell system.The lithium-sulfur cell prepared using the lithium-sulfur cell diaphragm material, with performance is high, long lifespan, it is safe the characteristics of.
Description
Technical field
The present invention relates to a kind of function barrier film and its application in lithium-sulfur cell, belong to field of electrochemical batteries.
Background technology
With continuing to develop for Science ＆ Society, people are continuously increased to the demand of new energy, such as electric automobile, intelligence electricity
The emerging markets such as net propose requirement higher, particularly electric automobile field to new energy resources system and require that electrokinetic cell energy is close
Degree reaches 500 Wh kg-1More than.But, nowadays commercialized lithium ion battery energy density is subject to traditional positive electrode
(LiCoO2、LiMn2O4、LiFePO4Deng) and carbon negative pole material itself theoretical capacity limitation, be only capable of reaching 150-200 Wh kg-1。350-400 Wh kg-1Close to the limit of lithium ion battery energy density, it is difficult to further improve.For electrokinetic cell
Speech, except meeting its power performance, economic adaptability is also an important consideration, according to United States advanced battery alliance (the US
Advanced Battery Consortium) to analyze, battery bag price will drop to $ 150 (kW h)-1Ability commercial applications,
And the price of lithium ion battery bag is in $ 400-600 (kW h) at present-1.Therefore, exploitation high-energy-density of new generation and low is explored
The battery system of cost turns into current people's study hotspot.
The theoretical capacity of lithium-sulfur cell is up to 1675 mAh g-1, the Wh kg of energy density 2600-1, than traditional lithium ion
Battery an order of magnitude high.Additionally, elemental sulfur rich reserves, cheap and environment-friendly in nature.So lithium sulphur
Battery theoretical energy density and low cost high, as one of most potential high specific energy chemical cell system of new generation.
But, elemental sulfur and its discharging product are non-conductive, and the middle many lithium sulfides of discharging product are soluble in organic electrolyte and lithium metal
All influence lithium-sulfur cells such as Li dendrite safety problem chemical property and practical application.
Lithium-sulfur cell is mainly made up of positive electrode, electrolyte, barrier film and negative material.Barrier film is used as lithium-sulfur cell
One of important component, its performance quality has important influence to battery overall performance, during charge and discharge cycles, uses
It is short-circuited in preventing both positive and negative polarity from contacting, and allows the lithium ion to carry out free migration.
Must possess certain porous, bendability, shrinkage, wetability and ionic conductivity as diaphragm material, at present
Conventional lithium-sulfur cell barrier film is mostly traditional olefines barrier film, is primarily referred to as polypropylene (PP) microporous barrier, polyethylene (PE)
Microporous barrier and the multilayer composite membrane of Celgard companies production (PP/PE two-layers are compound or tri- layers of PP/PE/PP is combined), polyene
Hydrocarbon barrier film production cost is relatively low, aperture size is controllable, with preferable chemistry and electrochemical stability and good machinery
Intensity, but its thickness, intensity, porosity be difficult to take into account, and its high temperature resistant and resistance to high rate during charging-discharging are poor, are applied to power
There is huge potential safety hazard in lithium-sulfur cell.Meanwhile, lithium-sulfur cell is due to the complexity and electrolyte of discharge and recharge reaction process
Diversity, traditional polyalkene diaphragm can not well suppress the diffusion of lithium-sulfur cell intermediate product polysulfide, therefore, open
Hair higher quality diaphragm material also turns into and improves one of lithium-sulfur cell overall performance important directions.
The content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of lithium-sulfur cell diaphragm material, using this
Lithium-sulfur cell prepared by lithium-sulfur cell diaphragm material, with performance is high, long lifespan, it is safe the characteristics of.
In order to realize foregoing invention purpose, the application employs following technical scheme：
Lithium-sulfur cell diaphragm material, is dried to obtain after being coated on polypropylene surface by catalyst, conductive agent, binding agent slurry,
The thickness of film is micron-sized, and specifically, film thickness is 5-10 microns.
Described catalyst is metal oxide, metal nitride, metal sulfide or metal simple-substance；Specifically
It is titanium dioxide, manganese dioxide, cobalt oxide, titanium nitride, titanium disulfide or platinum.
Described conductive agent is acetylene black, Ketjen black or CNT.
Conductive agent is 9 with the mass ratio of binding agent with the mixture of catalyst：1；Catalyst and conductive agent mass ratio are 7：
2。
It is preferred that conductive agent is nanoscale with catalyst.
Described binding agent is Kynoar（PVDF）, polyvinylidene fluoride, in Pluronic F-127 or polyacrylic acid extremely
Few one kind.
Barrier film of the invention can hinder many sulphions to be spread to negative pole in terms of physics, chemistry two, many sulphions is existed
Its surface aggregation, and membrane surface load catalyst can further activation utilization low electric conductivity many sulphions, so as to carry
The actual specific capacity and cyclical stability of lithium-sulfur cell system high.Additionally, function barrier film has alleviates Li dendrite puncture ability,
Further improve the security of lithium-sulfur cell.
The lithium-sulfur cell assembled using function barrier film of the invention, solve conventional lithium-sulfur cell difference cyclical stability,
The problems such as interface problem, lithium metal potential safety hazard of positive pole and barrier film.Additionally, the cost of raw material of the novel lithium sulphur battery system
Cheap, production technology is easy, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 assembles routine lithium-sulfur cell schematic diagram by comparative example 1.
Fig. 2 is the lithium-sulfur cell schematic diagram that embodiment 1-11 assembles barrier film of the present invention.
Fig. 3 is the SEM photograph of the barrier film that embodiment 1 and 2 is obtained.
Fig. 4 is comparative example 1（PP in figure）With the cyclicity of the lithium-sulfur cell that embodiment 1,2 assembles new function barrier film
Energy（0.5 C）（The corresponding PP+C65 of embodiment 1, the corresponding PP+C65+TiO of embodiment 2）.
Fig. 5 is microporous polypropylene membrane Celgard 2400 in comparative example 1（Fig. 5 a-c）With function barrier film gold in embodiment 2
Category lithium punctures the contrast of ability.
Fig. 6 is by comparative example 1 and the cycle performance of the lithium-sulfur cell of the assembling new function barrier film of embodiment 1,7（0.5
C）.
Specific embodiment
Specific embodiment of the invention is described further below in conjunction with drawings and Examples, but does not limit this
The scope of invention.
Comparative example 1
With bright sulfur as positive active material, with conductive agent acetylene black, binding agent Kynoar（PVDF）In mass ratio 6:3:1 mixes
Close, with METHYLPYRROLIDONE（NMP）It is solvent, is coated in current collector aluminum foil after stirring, then at 60 DEG C
12 h are dried in vacuum drying chamber, as positive electrode.Metal lithium sheet is used as negative pole, microporous polypropylene membrane Celgard 2400
It is barrier film, using 1 mol L-1LiTFSI and 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether,
Volume ratio 1:1）For electrolyte assembles conventional lithium-sulfur cell, as shown in Figure 1.
It is positive electrode that the lithium-sulfur cell uses bright sulfur, and electronic conductance is low in itself for sulphur, and actual specific capacity is low；With electric discharge
Process, sulphur is transformed into many lithium sulfides of high price that are soluble in electrolyte so that capacity attenuation, and cyclical stability is poor.Current density 0.5
During C, after the circle of circulation 500, specific discharge capacity only has 176 mAh g-1, PP in such as Fig. 4.Additionally, in charge and discharge process, conventional poly- third
Alkene barrier film causes the potential safety hazard of Fire explosion, such as Fig. 5 a-c easily by Li dendrite through internal short-circuit is caused.
Embodiment 1
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, Ketjen black and binding agent Kynoar（PVDF）In mass ratio 9:1 mixing, with N-
N-methyl-2-2-pyrrolidone N（NMP）It is solvent, is coated on after stirring on microporous polypropylene membrane Celgard 2400, Ran Hou
12 h are dried in 60 DEG C of drying box, as function barrier film.The homogeneous load microporous polypropylene membrane of nano level Ketjen black
On Celgard 2400, such as Fig. 3 a.The thickness of function barrier film is 7.5 um, such as Fig. 3 b.Using 1 mol L-1LiTFSI and 0.2
mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）It is electrolyte assembling function barrier film
Lithium-sulfur cell, such as Fig. 2.
The function barrier film for coating Ketjen black is capable of many lithium sulfides of physics obstruction lithium-sulfur cell electric discharge generation to negative pole diffusion,
The generation of " shuttle effect " is reduced, the problem of capacity attenuation is extenuated.In 0.5 C of current density, first discharge specific capacity is 550
mAh g-1, after the circle of circulation 500, specific discharge capacity is 332 mAh g-1, PP+C65 in such as Fig. 4.
Embodiment 2
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, Nano titanium dioxide, Ketjen black and binding agent Kynoar（PVDF）By quality
Than 7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane is coated on after stirring
On Celgard 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Nano level titanium dioxide is answered
On the homogeneous load microporous polypropylene membrane Celgard 2400 of condensation material, such as Fig. 3 c.The thickness of function barrier film is 7.5 um, is such as schemed
3d.Titanium, oxygen, carbon are uniformly dispersed on microporous polypropylene membrane Celgard 2400, such as Fig. 3 e-h.Using 1 mol L-1
LiTFSI and 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）It is electrolyte group
Fill the lithium-sulfur cell of function barrier film, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium dioxide can be inhaled nano-level titania functional barrier film by chemistry
It is attached further to adsorb many sulphions, it is gathered in function membrane surface, titanium dioxide has certain to many sulphions in addition
PP+C65+TiO in catalytic action so that the activation process time of lithium-sulfur cell is shortened, such as Fig. 4.This chemisorbed and catalysis
Synergy greatly improves the actual specific capacity and cyclical stability of lithium-sulfur cell.In 0.5 C of current density, put first
Electric specific capacity is 1206 mAh g-1, after the circle of circulation 500, specific discharge capacity is 501 mAh g-1, PP+C65+TiO in such as Fig. 4.
In addition, this function barrier film is punctured with certain protective capability to Li dendrite so that the security performance of lithium-sulfur cell changes significantly
It is kind, such as Fig. 5 d-f.
Embodiment 3
With mesoporous carbon/sulphur as positive active material, with conductive agent acetylene black, binding agent Kynoar（PVDF）In mass ratio 6:
3:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, is coated in current collector aluminum foil after stirring, then 60
DEG C vacuum drying chamber in dry 12 h, as positive electrode.
Metal lithium sheet is used as negative pole, Nano titanium dioxide, Ketjen black and binding agent Kynoar（PVDF）By quality
Than 7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane is coated on after stirring
On Celgard 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1 LiTFSI
With 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）For electrolyte assembles function
The lithium-sulfur cell of barrier film, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium dioxide can be inhaled nano-level titania functional barrier film by chemistry
It is attached further to adsorb many sulphions, it is gathered in function membrane surface, titanium dioxide has certain to many sulphions in addition
Catalytic action so that the activation process time of lithium-sulfur cell is shortened.This chemisorbed is greatly improved with catalyzing cooperation effect
The actual specific capacity and cyclical stability of lithium-sulfur cell.In addition, this function barrier film is punctured with certain guarantor to Li dendrite
Shield ability so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 4
With titanium dioxide/sulphur as positive active material, with conductive agent acetylene black, binding agent Kynoar（PVDF）In mass ratio
6:3:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, is coated in current collector aluminum foil after stirring, Ran Hou
12 h are dried in 60 DEG C of vacuum drying chamber, as positive electrode.
Metal lithium sheet is used as negative pole, Nano titanium dioxide, Ketjen black and binding agent Kynoar（PVDF）By quality
Than 7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane is coated on after stirring
On Celgard 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1 LiTFSI
With 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）For electrolyte assembles function
The lithium-sulfur cell of barrier film, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium dioxide can be inhaled nano-level titania functional barrier film by chemistry
It is attached further to adsorb many sulphions, it is gathered in function membrane surface, titanium dioxide has certain to many sulphions in addition
Catalytic action so that the activation process time of lithium-sulfur cell is shortened.This chemisorbed is greatly improved with catalyzing cooperation effect
The actual specific capacity and cyclical stability of lithium-sulfur cell.In addition, this function barrier film is punctured with certain guarantor to Li dendrite
Shield ability so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 5
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, nanometer electrode manganese dioxide, Ketjen black and binding agent Kynoar（PVDF）By quality
Than 7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane is coated on after stirring
On Celgard 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1 LiTFSI
With 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）For electrolyte assembles function
The lithium-sulfur cell of barrier film, such as Fig. 2.Nanometer electrode manganese dioxide function barrier film in addition to the effect described in embodiment 1, manganese dioxide energy
Many sulphions are further enough adsorbed by chemisorbed, it is gathered in function membrane surface, and the carbon of membrane surface can be passed
Transmission of electricity so that function barrier film potentially acts as secondary collector, greatly improves actual specific capacity and the circulation of lithium-sulfur cell
Stability.In addition, this function barrier film is punctured with certain protective capability to Li dendrite so that the security performance of lithium-sulfur cell
Substantially improve.
Embodiment 6
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, nanometer grade cobalt oxide, Ketjen black and binding agent Kynoar（PVDF）In mass ratio
7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane Celgard is coated on after stirring
On 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1LiTFSI and 0.2
mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）It is electrolyte assembling function barrier film
Lithium-sulfur cell, such as Fig. 2.
In addition to the effect described in embodiment 1, cobalt oxide can be entered nanometer grade cobalt oxide function barrier film by chemisorbed
One step adsorbs many sulphions, it is gathered in function membrane surface, and the carbon of membrane surface can transmit electronics so that function every
Film potentially acts as secondary collector, greatly improves the actual specific capacity and cyclical stability of lithium-sulfur cell.In addition, this work(
Energy barrier film is punctured with certain protective capability to Li dendrite so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 7
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, nanoscale titanium nitride, Ketjen black and binding agent Kynoar（PVDF）In mass ratio
7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane Celgard is coated on after stirring
On 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1LiTFSI and 0.2
mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）It is electrolyte assembling function barrier film
Lithium-sulfur cell, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium nitride can be entered nanoscale titanium nitride function barrier film by chemisorbed
One step adsorbs many sulphions, it is gathered in function membrane surface, and the carbon of membrane surface can transmit electronics so that function every
Film potentially acts as secondary collector, greatly improves the actual specific capacity and cyclical stability of lithium-sulfur cell.In current density
During 0.5 C, after the circle of circulation 1000, specific discharge capacity is 390 mAh g-1, PP+C65+TiN in such as Fig. 6.In addition, this function
Barrier film is punctured with certain protective capability to Li dendrite so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 8
With Graphene/sulphur as positive active material, with conductive agent acetylene black, binding agent Kynoar（PVDF）In mass ratio 6:
3:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, is coated in current collector aluminum foil after stirring, then 60
DEG C vacuum drying chamber in dry 12 h, as positive electrode.
Metal lithium sheet is used as negative pole, nanoscale titanium nitride, Ketjen black and binding agent Kynoar（PVDF）In mass ratio
7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane Celgard is coated on after stirring
On 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1LiTFSI and 0.2
mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）It is electrolyte assembling function barrier film
Lithium-sulfur cell, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium nitride can be entered nanoscale titanium nitride function barrier film by chemisorbed
One step adsorbs many sulphions, it is gathered in function membrane surface, and the carbon of membrane surface can transmit electronics so that function every
Film potentially acts as secondary collector, greatly improves the actual specific capacity and cyclical stability of lithium-sulfur cell.In addition, this work(
Energy barrier film is punctured with certain protective capability to Li dendrite so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 9
With cobaltosic oxide/sulphur as positive active material, with conductive agent acetylene black, binding agent Kynoar（PVDF）By quality
Than 6:3:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, is coated in current collector aluminum foil after stirring, then
12 h are dried in 60 DEG C of vacuum drying chamber, as positive electrode.
Metal lithium sheet is used as negative pole, nanoscale titanium nitride, Ketjen black and binding agent Kynoar（PVDF）In mass ratio
7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane Celgard is coated on after stirring
On 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1LiTFSI and 0.2
mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）It is electrolyte assembling function barrier film
Lithium-sulfur cell, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium nitride can be entered nanoscale titanium nitride function barrier film by chemisorbed
One step adsorbs many sulphions, it is gathered in function membrane surface, and the carbon of membrane surface can transmit electronics so that function every
Film potentially acts as secondary collector, greatly improves the actual specific capacity and cyclical stability of lithium-sulfur cell.In addition, this work(
Energy barrier film is punctured with certain protective capability to Li dendrite so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 10
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, nanoscale titanium disulfide, Ketjen black and binding agent Kynoar（PVDF）By quality
Than 7:2:1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane is coated on after stirring
On Celgard 2400,12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1 LiTFSI
With 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）For electrolyte assembles function
The lithium-sulfur cell of barrier film, such as Fig. 2.
In addition to the effect described in embodiment 1, titanium disulfide can be inhaled nanoscale titanium disulfide function barrier film by chemistry
It is attached further to adsorb many sulphions, it is gathered in function membrane surface, and the carbon of membrane surface can transmit electronics so that work(
Energy barrier film potentially acts as secondary collector, greatly improves the actual specific capacity and cyclical stability of lithium-sulfur cell.In addition, this
Plant function barrier film and certain protective capability is punctured with to Li dendrite so that the security performance of lithium-sulfur cell is substantially improved.
Embodiment 11
The preparation method of coating sulphur positive electrode is with comparative example 1 on a current collector.
Metal lithium sheet is used as negative pole, nanoscale platinum, Ketjen black and binding agent Kynoar（PVDF）In mass ratio 7:2:
1 mixing, with METHYLPYRROLIDONE（NMP）It is solvent, microporous polypropylene membrane Celgard 2400 is coated on after stirring
On, 12 h are then dried in 60 DEG C of drying box, as function barrier film.Using 1 mol L-1LiTFSI and 0.2 mol L-1 LiNO3/DOL+DME（Dioxolanes and glycol dimethyl ether, volume ratio 1:1）The lithium sulphur of function barrier film is assembled for electrolyte
Battery, such as Fig. 2.
In addition to the effect described in embodiment 1, platinum can further be adsorbed nanoscale platinum function barrier film by chemisorbed
Many sulphions, make it be gathered in function membrane surface, and platinum has certain catalytic action to many sulphions in addition so that lithium sulphur electricity
The activation process time in pond is shortened.This chemisorbed greatly improves the actual specific volume of lithium-sulfur cell with catalyzing cooperation effect
Amount and cyclical stability.In addition, this function barrier film is punctured with certain protective capability to Li dendrite so that lithium-sulfur cell
Security performance is substantially improved.
The conductive agent of above-described embodiment 1-11 also can be replaced acetylene black or CNT, binding agent Kynoar
（PVDF）Also polyvinylidene fluoride, Pluronic F-127 or polyacrylic acid are can be replaced, current collector aluminum foil also can be replaced carbon coated
Aluminium foil.
The above embodiments are intended to illustrate the present invention, rather than limitation, therefore with it is of the invention
Any change in claims suitable implication and scope, is all considered as being included within the scope of the claims.
Claims (5)
1. lithium-sulfur cell diaphragm material, be coated on by catalyst, conductive agent, binding agent slurry it is dry after polypropylene surface
Arrive, the thickness of film is micron-sized；
Catalyst is metal oxide, metal nitride, metal sulfide or metal simple-substance；
Conductive agent is acetylene black, Ketjen black or CNT；
Binding agent is Kynoar, polyvinylidene fluoride, Pluronic F-127 or polyacrylic acid.
2. lithium-sulfur cell diaphragm material according to claim 1, it is characterised in that described catalyst is titanium dioxide, two
Manganese oxide, cobalt oxide, titanium nitride, titanium disulfide or platinum.
3. lithium-sulfur cell diaphragm material according to claim 1, it is characterised in that described conductive agent is with catalyst
Nanoscale.
4. lithium-sulfur cell diaphragm material according to claim 1, it is characterised in that described conductive agent is mixed with catalyst
Compound is 9 with the mass ratio of binding agent：1；Catalyst is 7 with the mass ratio of conductive agent：2.
5. the lithium-sulfur cell for being assembled as the lithium-sulfur cell diaphragm material described in claim 1.
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| CN107359302A (en) * | 2017-07-14 | 2017-11-17 | 东莞理工学院 | Nitrogenize carbon composite and preparation method and application |
| CN108630889A (en) * | 2018-04-17 | 2018-10-09 | 西安交通大学 | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer |
| CN109004163A (en) * | 2018-06-30 | 2018-12-14 | 华南理工大学 | It is a kind of with preventing the lithium-sulfur cell diaphragm of polysulfide shuttle effect-compound pack assembly of sulphur anode |
| CN109065808A (en) * | 2018-08-07 | 2018-12-21 | 河北工业大学 | A kind of preparation method of the functional interlayer for lithium-sulfur cell |
| CN109167010A (en) * | 2018-09-12 | 2019-01-08 | 肇庆市华师大光电产业研究院 | A kind of functional diaphragm and preparation method thereof for lithium-sulfur cell |
| CN109576981A (en) * | 2018-11-19 | 2019-04-05 | 肇庆市华师大光电产业研究院 | A kind of MnO2The coaxial composite fiber membrane of/Ni/PVDF, preparation method and application |
| CN109786634A (en) * | 2018-12-11 | 2019-05-21 | 天津工业大学 | A kind of preparation method of lithium-sulfur cell two-layer compound diaphragm |
| CN110165124A (en) * | 2019-05-16 | 2019-08-23 | 华南师范大学 | It is a kind of applied to double coated separators of lithium-selenium disulfide battery and its preparation method and application |
| CN110571500A (en) * | 2019-09-18 | 2019-12-13 | 昆明理工大学 | lithium-sulfur semi-flow battery |
| CN110649208A (en) * | 2018-09-29 | 2020-01-03 | 合肥工业大学 | Lithium-sulfur battery composite diaphragm and preparation method thereof |
| CN110649213A (en) * | 2019-09-05 | 2020-01-03 | 西安科技大学 | Coating diaphragm material for lithium-sulfur secondary battery and application thereof |
| CN110707269A (en) * | 2019-09-23 | 2020-01-17 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for lithium-sulfur battery, application of diaphragm slurry, diaphragm for lithium-sulfur battery and lithium-sulfur battery |
| US10576429B1 (en) | 2019-04-17 | 2020-03-03 | King Saud University | Method of making an asymmetric polyvinylidene difluoride membrane |
| CN111490285A (en) * | 2020-04-23 | 2020-08-04 | 中航锂电技术研究院有限公司 | Lithium-sulfur battery solid electrolyte membrane, preparation method thereof and lithium-sulfur battery |
| CN111540868A (en) * | 2020-01-21 | 2020-08-14 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm |
| CN112201904A (en) * | 2020-10-30 | 2021-01-08 | 天目湖先进储能技术研究院有限公司 | Diaphragm interlayer material of lithium-sulfur battery and preparation method and application thereof |
| CN112272894A (en) * | 2018-10-26 | 2021-01-26 | 株式会社Lg化学 | Functional separator, method for preparing same, and lithium secondary battery comprising same |
| EP3692590A4 (en) * | 2017-10-04 | 2021-06-02 | Navitas Systems LLC | Separator for lithium sulfur batteries |
| CN112952286A (en) * | 2021-02-02 | 2021-06-11 | 同济大学 | Composite diaphragm, preparation method and application |
| CN113131095A (en) * | 2021-04-16 | 2021-07-16 | 清华大学深圳国际研究生院 | Isolation layer, preparation method thereof and lithium-sulfur battery |
| CN113285177A (en) * | 2020-02-03 | 2021-08-20 | 河北金力新能源科技股份有限公司 | Modified lithium-sulfur battery diaphragm slurry and preparation method and application thereof |
| CN113471627A (en) * | 2021-05-21 | 2021-10-01 | 惠州锂威新能源科技有限公司 | Modified diaphragm and preparation method and application thereof |
| CN113629249A (en) * | 2021-06-10 | 2021-11-09 | 中国科学院金属研究所 | Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode |
| CN113725558A (en) * | 2021-07-29 | 2021-11-30 | 长沙矿冶研究院有限责任公司 | Modified diaphragm of lithium-sulfur battery and preparation method thereof |
| JP2022508931A (en) * | 2019-05-03 | 2022-01-19 | エルジー・ケム・リミテッド | A functional separation membrane with a catalyst site introduced, a manufacturing method thereof, and a lithium secondary battery containing the same. |
| CN114464891A (en) * | 2020-11-09 | 2022-05-10 | 中国科学院物理研究所 | Ultralow-density electrolyte and lithium-sulfur battery |
| CN115020916A (en) * | 2022-06-08 | 2022-09-06 | 天津大学 | Lithium-sulfur battery diaphragm and preparation method and application thereof |
| CN115117553A (en) * | 2022-07-28 | 2022-09-27 | 欣旺达电动汽车电池有限公司 | Functionalized diaphragm and preparation method and application thereof |
| CN115555026A (en) * | 2022-11-29 | 2023-01-03 | 江苏正力新能电池技术有限公司 | Electro-catalytic material, preparation method thereof, isolating membrane and lithium-sulfur battery |
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| CN107359302A (en) * | 2017-07-14 | 2017-11-17 | 东莞理工学院 | Nitrogenize carbon composite and preparation method and application |
| EP3692590A4 (en) * | 2017-10-04 | 2021-06-02 | Navitas Systems LLC | Separator for lithium sulfur batteries |
| CN108630889A (en) * | 2018-04-17 | 2018-10-09 | 西安交通大学 | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer |
| CN109004163A (en) * | 2018-06-30 | 2018-12-14 | 华南理工大学 | It is a kind of with preventing the lithium-sulfur cell diaphragm of polysulfide shuttle effect-compound pack assembly of sulphur anode |
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| CN109065808B (en) * | 2018-08-07 | 2021-09-10 | 河北工业大学 | Preparation method of functional interlayer for lithium-sulfur battery |
| CN109167010A (en) * | 2018-09-12 | 2019-01-08 | 肇庆市华师大光电产业研究院 | A kind of functional diaphragm and preparation method thereof for lithium-sulfur cell |
| CN109167010B (en) * | 2018-09-12 | 2021-07-27 | 肇庆市华师大光电产业研究院 | Functional diaphragm for lithium-sulfur battery and preparation method thereof |
| CN110649208A (en) * | 2018-09-29 | 2020-01-03 | 合肥工业大学 | Lithium-sulfur battery composite diaphragm and preparation method thereof |
| CN112272894B (en) * | 2018-10-26 | 2022-12-20 | 株式会社Lg新能源 | Functional separator, method for preparing same, and lithium secondary battery comprising same |
| CN112272894A (en) * | 2018-10-26 | 2021-01-26 | 株式会社Lg化学 | Functional separator, method for preparing same, and lithium secondary battery comprising same |
| CN109576981A (en) * | 2018-11-19 | 2019-04-05 | 肇庆市华师大光电产业研究院 | A kind of MnO2The coaxial composite fiber membrane of/Ni/PVDF, preparation method and application |
| CN109786634A (en) * | 2018-12-11 | 2019-05-21 | 天津工业大学 | A kind of preparation method of lithium-sulfur cell two-layer compound diaphragm |
| US10576429B1 (en) | 2019-04-17 | 2020-03-03 | King Saud University | Method of making an asymmetric polyvinylidene difluoride membrane |
| JP2022508931A (en) * | 2019-05-03 | 2022-01-19 | エルジー・ケム・リミテッド | A functional separation membrane with a catalyst site introduced, a manufacturing method thereof, and a lithium secondary battery containing the same. |
| JP7162147B2 (en) | 2019-05-03 | 2022-10-27 | エルジー エナジー ソリューション リミテッド | Functional Separation Membrane Introduced with Catalytic Site, Method for Producing Same, and Lithium Secondary Battery Comprising Same |
| CN110165124B (en) * | 2019-05-16 | 2022-02-22 | 华南师范大学 | Double-coating diaphragm applied to lithium-selenium disulfide battery and preparation method and application thereof |
| CN110165124A (en) * | 2019-05-16 | 2019-08-23 | 华南师范大学 | It is a kind of applied to double coated separators of lithium-selenium disulfide battery and its preparation method and application |
| CN110649213B (en) * | 2019-09-05 | 2022-09-16 | 西安科技大学 | Coating diaphragm material for lithium-sulfur secondary battery and application thereof |
| CN110649213A (en) * | 2019-09-05 | 2020-01-03 | 西安科技大学 | Coating diaphragm material for lithium-sulfur secondary battery and application thereof |
| CN110571500B (en) * | 2019-09-18 | 2023-04-07 | 昆明理工大学 | Lithium-sulfur semi-flow battery |
| CN110571500A (en) * | 2019-09-18 | 2019-12-13 | 昆明理工大学 | lithium-sulfur semi-flow battery |
| CN110707269A (en) * | 2019-09-23 | 2020-01-17 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for lithium-sulfur battery, application of diaphragm slurry, diaphragm for lithium-sulfur battery and lithium-sulfur battery |
| CN111540868A (en) * | 2020-01-21 | 2020-08-14 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm |
| CN113285177A (en) * | 2020-02-03 | 2021-08-20 | 河北金力新能源科技股份有限公司 | Modified lithium-sulfur battery diaphragm slurry and preparation method and application thereof |
| CN111490285A (en) * | 2020-04-23 | 2020-08-04 | 中航锂电技术研究院有限公司 | Lithium-sulfur battery solid electrolyte membrane, preparation method thereof and lithium-sulfur battery |
| CN112201904A (en) * | 2020-10-30 | 2021-01-08 | 天目湖先进储能技术研究院有限公司 | Diaphragm interlayer material of lithium-sulfur battery and preparation method and application thereof |
| CN114464891A (en) * | 2020-11-09 | 2022-05-10 | 中国科学院物理研究所 | Ultralow-density electrolyte and lithium-sulfur battery |
| CN114464891B (en) * | 2020-11-09 | 2023-05-02 | 中国科学院物理研究所 | Ultralow-density electrolyte and lithium sulfur battery |
| CN112952286A (en) * | 2021-02-02 | 2021-06-11 | 同济大学 | Composite diaphragm, preparation method and application |
| CN113131095A (en) * | 2021-04-16 | 2021-07-16 | 清华大学深圳国际研究生院 | Isolation layer, preparation method thereof and lithium-sulfur battery |
| CN113471627A (en) * | 2021-05-21 | 2021-10-01 | 惠州锂威新能源科技有限公司 | Modified diaphragm and preparation method and application thereof |
| CN113629249A (en) * | 2021-06-10 | 2021-11-09 | 中国科学院金属研究所 | Preparation method of MXene-based supported platinum catalyst applied to lithium-sulfur battery anode |
| CN113725558A (en) * | 2021-07-29 | 2021-11-30 | 长沙矿冶研究院有限责任公司 | Modified diaphragm of lithium-sulfur battery and preparation method thereof |
| CN113725558B (en) * | 2021-07-29 | 2022-09-13 | 长沙矿冶研究院有限责任公司 | Lithium-sulfur battery modified diaphragm and preparation method thereof |
| CN115020916A (en) * | 2022-06-08 | 2022-09-06 | 天津大学 | Lithium-sulfur battery diaphragm and preparation method and application thereof |
| CN115117553A (en) * | 2022-07-28 | 2022-09-27 | 欣旺达电动汽车电池有限公司 | Functionalized diaphragm and preparation method and application thereof |
| CN115555026A (en) * | 2022-11-29 | 2023-01-03 | 江苏正力新能电池技术有限公司 | Electro-catalytic material, preparation method thereof, isolating membrane and lithium-sulfur battery |
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