CN107994184A - A kind of membrane for improving lithium-sulphur cell positive electrode sulfur content, preparation method and applications - Google Patents
A kind of membrane for improving lithium-sulphur cell positive electrode sulfur content, preparation method and applications Download PDFInfo
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- CN107994184A CN107994184A CN201711053046.XA CN201711053046A CN107994184A CN 107994184 A CN107994184 A CN 107994184A CN 201711053046 A CN201711053046 A CN 201711053046A CN 107994184 A CN107994184 A CN 107994184A
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- 239000012528 membrane Substances 0.000 title claims abstract description 119
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 28
- 239000011593 sulfur Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 polypropylene Polymers 0.000 claims abstract description 14
- 229920001021 polysulfide Polymers 0.000 claims abstract description 12
- 239000005077 polysulfide Substances 0.000 claims abstract description 12
- 150000008117 polysulfides Polymers 0.000 claims abstract description 12
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 210000004027 cell Anatomy 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000010586 diagram Methods 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000003321 amplification Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 150000004862 dioxolanes Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of membrane for improving lithium-sulphur cell positive electrode sulfur content, preparation method and applications.Membrane substrate is commercial polypropylene diaphragm, carbon black or other carbon material layers are coated thereon, to coat carbon-coating as cathode, lithium piece is anode, assembles button cell, and button cell circulates 3~5 times under 1~0.3V voltage windows, solid electrolyte membrane SEI is formed on the carbon-coating of coating, SEI films form one layer of compacted zone together with coating carbon-coating on membrane, prevent polysulfide from shuttling to anode, suppress shuttle effect.The membrane of above-mentioned raising lithium-sulphur cell positive electrode sulfur content is applied to assembling lithium-sulfur cell.Membrane provided by the invention can effectively improve the sulfur content in lithium-sulphur cell positive electrode, improve to 90%.
Description
Technical field
The invention belongs to energy storage material field, is related to a kind of preparation method of lithium-sulfur cell membrane and its in lithium-sulfur cell
In application.
Background technology
With social constantly development and progress, the energy density for the lithium ion battery being used widely is
Deficiency has met the needs of much applying, therefore the lithium-sulfur cell with higher energy density has received widespread attention and grinds
Study carefully.But lithium-sulfur cell has the application that many defects restrict it, such as：Low-sulfur utilization rate caused by low electrical conductivity；It is middle
Weak cyclical stability caused by " shuttle effect " that product polysulfide is soluble in electrolyte and then produces.Researcher puts into
Many energy solves the problems, such as these, but has a shortcoming not receive extensive concern but --- content of the sulphur in cathode.
Content of the sulphur in cathode directly affects the Area Power Density of sulphur cathode.Then in most of research work,
Sulphur content in cathode is generally very low, is 30%~70%.It is difficult mainly traditional the reason for raising consolidate to cause sulfur content
Sulphur strategy.In traditional solid sulphur strategy, researcher is using physically or chemically effect absorption polysulfide, in order to adsorb more sulphur
Compound, it is necessary to which enough solid sulfur materials provide sufficiently large specific surface area, so cause sulfur content not high.To understand
Certainly this problem, some researchers are directed to preparing the solid sulfur materials with superhigh specific surface area, and by this method, sulphur exists
Content in cathode is raised to 90%.But in these work, preparation process is generally sufficiently complex with technique, does not utilize
Actual application.
The content of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of new raising lithium-sulphur cell positive electrode sulfur content membrane and
Its preparation method.
The technical scheme is that：
A kind of membrane for improving lithium-sulphur cell positive electrode sulfur content, membrane substrate are commercial polypropylene diaphragm, thereon carbon coating
Black or other carbon material layers, to coat carbon-coating as cathode, lithium piece is anode, assembles button cell, is carbon materials because there is commercial membrane
Expect substrate, be not required to use membrane again.Button cell circulates 3~5 times under 1~0.3V voltage windows, is formed on the carbon-coating of coating
Solid electrolyte membrane SEI.Battery is dismantled in glove box, takes out membrane, you can the membrane of SEI modifications is obtained, wherein with SEI
Film forms one layer of compacted zone together with the carbon-coating of coating on membrane, prevents polysulfide from shuttling to anode, so as to suppress to shuttle
Effect.The membrane is named as SEI membranes.The membrane can effectively improve the sulfur content in lithium-sulphur cell positive electrode, improve extremely
90%.
Other carbon materials include graphite, carbon nanotubes, graphene etc..
The principle of sulfur content is in membrane raising lithium-sulphur cell positive electrode：(1) compacted zone cause polysulfide cannot pass through every
Film reaches anode, so as to suppress shuttle effect；(2) lithium ion can penetrate SEI, so compacted zone does not interfere with lithium ion
Conduction；Since solid sulphur is in itself not against absorption, so enough solid sulfur materials are not required to provide enough ratio surfaces
Product, as long as conductive material provides the place of reaction of Salmon-Saxl.
The preparation method of the membrane of above-mentioned raising lithium-sulphur cell positive electrode sulfur content, comprises the following steps：
The first step, prepares the membrane of carbon material coating
By coating material and binding agent PVD according to mass ratio 7:3~8:2 to be dissolved in suitable 1-methyl-2-pyrrolidinone NMP molten
Obtained slurry is uniformly mixed in agent；Slurry is coated on commercial polypropylene diaphragm, 50~60 DEG C of 12~24h of vacuum drying, are used
Tablet machine drift is pressed into the sequin of diameter 16mm, obtains the membrane of carbon material coating.The membrane, which is named as, applies carbon membrane.
The coating material includes carbon black or other carbon materials, wherein, other carbon materials include graphite, carbon
Nanotube, graphene etc..
Second step, prepares the membrane for possessing dense film, i.e. SEI films
The membrane that the carbon material that the first step is prepared coats and lithium piece composition button cell, coating carbon-coating is as just
Pole, lithium piece are anode, are carbon material substrate due to there is commercial membrane, are not required to use membrane again.Electrolyte, which is selected, contains 1M hexafluoro phosphorus
Sour lithium (LiPF6) ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solvent.To assembled battery in 0.3~1.5V
Voltage range in discharge and recharge 1~5 time, solid electrolyte membrane SEI is formed on the carbon-coating of coating.Electricity is dismantled in glove box
Pond, takes out membrane, you can obtains the membrane membrane of SEI modifications, wherein SEI is formed together with carbon material to be come for polysulfide
The dense film said, so as to prepare SEI membranes.The volume ratio of ethylene carbonate and diethyl carbonate in the electrolyte is
1:1。
The membrane of above-mentioned raising lithium-sulphur cell positive electrode sulfur content is applied to assembling lithium-sulfur cell.Specially：Using content as
90% carbon nanotubes/sulphur CNT/S composite electrodes are cathode, and lithium piece forms button cell for anode.Membrane is preparation
SEI membranes, SEI film surfaces are towards cathode of lithium.Electrolyte is selected containing the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M
Lithium nitrate (LiNO3) 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) mixed solvent.
The 1,3- dioxolanes and the volume ratio of glycol dimethyl ether are 1:1.
Beneficial effects of the present invention are：(1) compacted zone causes polysulfide to cannot pass through membrane and reach anode, so as to press down
Shuttle effect processed；(2) lithium ion can penetrate SEI, so compacted zone does not interfere with the conduction of lithium ion；Due to solid sulphur in itself
Not against absorption, so being not required enough solid sulfur materials to provide enough specific surface areas, as long as conductive material provides
The place of reaction of Salmon-Saxl.
Brief description of the drawings
Fig. 1 (a) is the state of the charge and discharge process that SEI films are formed and impedance diagram and corresponding following impedance diagram；Fig. 1 b- scheme
1g is the impedance diagram of each state bottom electrode, wherein, Fig. 1 (b) is the impedance diagram of non-circulating electrode；Fig. 1 (c) is to be discharged to first
The impedance diagram of electrode during 0.3V；Fig. 1 (d) is the impedance diagram of the electrode after 0.3~1V is circulated 1 time；Fig. 1 (e) is in 0.3~1V
The impedance diagram of electrode after circulating 2 times；Fig. 1 (f) is the impedance diagram of the electrode after 0.3~1V is circulated 3 times；Fig. 1 (g) be 0.3~
The impedance diagram of electrode after 1V is circulated 4 times.
Fig. 2 a- Fig. 2 c are the scanning electron microscope (SEM) photograph for applying carbon membrane：Fig. 2 (a) is the SEM of 200 000 times of amplification；Fig. 2 (b) is
Amplify 100 000 times of SEM；Fig. 2 (c) is the SEM of 50 000 times of amplification.Fig. 2 d- Fig. 2 f are SEI membrane scanning electron microscope (SEM) photographs：Figure
2 (d) is the SEM of 200 000 times of amplification；Fig. 2 (e) is the SEM of 100 000 times of amplification；Fig. 2 (f) is 50 000 times of amplification
SEM。
Fig. 3 is the x-ray photoelectron spectroscopy XPS analysis of SEI films.Fig. 3 (a) is the C1s swarming figures for applying carbon membrane；Fig. 3
(b) it is the C1s swarming figures of SEI membranes.
Fig. 4 is the first charge-discharge curve map using the button cell of commercial membrane；Cathode is using sulfur content 90%
CNT/S anode composites, lithium piece are anode.
Fig. 5 is the first charge-discharge curve map using the button cell for applying carbon membrane；Cathode is using sulfur content 90%
CNT/S anode composites, lithium piece are anode.
Fig. 6 is the first charge-discharge curve map using the button cell of SEI membranes.Cathode is using sulfur content 90%
CNT/S anode composites, lithium piece are anode.
Embodiment
SEI membranes of the present invention and lithium-sulfur cell preparation method are further illustrated below by way of specific implementation case.
The characterization and electro-chemical test of obtained SEI membranes are as follows：
(1) sem test and X-ray diffractometer test.Electro-chemical test：It is using instrument model：LAND batteries
Test system, Wuhan, test parameter：0.3~1V of charging/discharging voltage section, 1.5V~3V, charge and discharge electro-temperature：25℃；
Case study on implementation 1：
The first step, prepares the membrane of carbon material coating
By coating material and binding agent PVD according to mass ratio 8:2 are dissolved in suitable 1-methyl-2-pyrrolidinone (NMP) solvent
In be uniformly mixed obtained slurry；Slurry is coated on commercial polypropylene diaphragm, 60 DEG C of vacuum drying 12h, with tablet press machine punching press
Into the sequin of diameter 16mm, the membrane of carbon material coating is obtained.The membrane, which is named as, applies carbon membrane.
The coating material includes carbon black or other carbon materials, wherein, other carbon materials include graphite, carbon
Nanotube, graphene etc..
Second step, prepares the membrane for possessing dense film, i.e. SEI films.
The membrane that the carbon material that the first step is prepared coats and lithium piece composition button cell, coating carbon-coating is as just
Pole, lithium piece are anode, are carbon material substrate due to there is commercial membrane, are not required to use membrane again.Electrolyte, which is selected, contains 1M hexafluoro phosphorus
Sour lithium (LiPF6) ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solvent (v:v,1:1).Exist to assembled battery
Discharge and recharge 4 times in the voltage range of 0.3~1.5V, form solid electrolyte membrane SEI on the carbon-coating of coating.In glove box
Battery is dismantled, takes out membrane, you can obtains the membrane membrane of SEI modifications, wherein SEI is formed together with carbon material for more sulphur
Dense film for compound, so as to prepare SEI membranes.
3rd step, assembles lithium-sulfur cell.
For the CNT/S composite electrodes for being 90% using content as cathode, lithium piece forms button cell for anode.Membrane is
The SEI membranes of preparation, SEI film surfaces are towards cathode of lithium.Electrolyte select containing the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and
Lithium nitrate (the LiNO of 0.2M3) 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) (1:1, v/v) mixed solvent.
The SEI membranes prepared to the implementation case are tested, as a result as follows：
(1) characterization of electrode
As shown in Figure 1, before the loop, ac impedance spectroscopy (EIS) shows a semicircle, only exists electrolyte/carbon material
Interface, with the circulation under 0.3~1V voltage windows, gradually there are double semicircular rings to EIS figures in display in figure, and in 4 circulations
After show complete double semicircular rings, it is shown that the generation at another interface, it was demonstrated that the formation of stable SEI films.
Fig. 2 is the SEM figures for applying carbon membrane and SEI membranes, it can be seen from the figure that on carbon membrane is applied, is deposited between carbon black
In many gaps so that polysulfide is without hindrance to be passed through from membrane.And on SEI membranes, most gaps are by SEI
Film is filled, and is suppressed polysulfide and is passed through membrane.
Fig. 3 is that the x-ray photoelectron spectroscopy (XPS) of SEI films is analyzed, and on carbon membrane is applied, does not find that SEI's is main
Component, and on SEI membranes, the key component of SEI is all found, e.g., lithium carbonate (Li2CO3), lithium fluoride (LiF) etc..XPS
The presence of SEI films is confirmed from component.
(2) electrochemical property test
Fig. 4-Fig. 6 is charge-discharge test figure, and for the CNT/S combination electrodes for being 90% using sulfur content as cathode, lithium piece is negative
Pole, various difference membranes assemble button cell, the charge-discharge test under 0.2C for membrane.As shown in Fig. 4, using commercial membrane
Battery can not charge normal, it is shown that greatly shuttle effect.Although Fig. 5 displays apply carbon membrane due to the presence of carbon black
It can help to adsorb polysulfide, but since S contents are still very high, so polysulfide cannot be adsorbed, so using painting completely
The button cell of carbon membrane can not be still charged normal to 3V.And such as Fig. 6 so, the SEI membranes prepared using present case
Button cell can normal discharge and recharge, it is shown that SEI membranes can effectively suppress shuttle effect, ensure the normal charge and discharge of battery.
SEI membranes prepared by present case show extraordinary captured sulfur result in lithium-sulfur cell test, absolutely prove
The reasonability of this patent design.
Case study on implementation 2：
The first step, prepares the membrane of carbon material coating
By coating material and binding agent PVD according to mass ratio 7:3 are dissolved in suitable 1-methyl-2-pyrrolidinone (NMP) solvent
In be uniformly mixed obtained slurry；Slurry is coated on commercial polypropylene diaphragm, 50 DEG C of vacuum drying 24h, with tablet press machine punching press
Into the sequin of diameter 16mm, the membrane of carbon material coating is obtained.The membrane, which is named as, applies carbon membrane.
The coating material includes carbon black or other carbon materials, wherein, other carbon materials include graphite, carbon
Nanotube, graphene etc..
Second step, prepares the membrane for possessing dense film, i.e. SEI films.
The membrane that the carbon material that the first step is prepared coats and lithium piece composition button cell, coating carbon-coating is as just
Pole, lithium piece are anode, are carbon material substrate due to there is commercial membrane, are not required to use membrane again.Electrolyte, which is selected, contains 1M hexafluoro phosphorus
Sour lithium (LiPF6) ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solvent (v:v,1:1).Exist to assembled battery
Discharge and recharge 2 times in the voltage range of 0.3~1.5V, form solid electrolyte membrane SEI on the carbon-coating of coating.In glove box
Battery is dismantled, takes out membrane, you can obtains the membrane membrane of SEI modifications, wherein SEI is formed together with carbon material for more sulphur
Dense film for compound, so as to prepare SEI membranes.
3rd step, assembles lithium-sulfur cell.
For the CNT/S composite electrodes for being 90% using content as cathode, lithium piece forms button cell for anode.Membrane is
The SEI membranes of preparation, SEI film surfaces are towards cathode of lithium.Electrolyte select containing the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and
Lithium nitrate (the LiNO of 0.2M3) 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) (1:1, v/v) mixed solvent.
Case study on implementation 3：
The first step, prepares the membrane of carbon material coating
By coating material and binding agent PVD according to mass ratio 8:2 are dissolved in suitable 1-methyl-2-pyrrolidinone (NMP) solvent
In be uniformly mixed obtained slurry；Slurry is coated on commercial polypropylene diaphragm, 55 DEG C of vacuum drying 16h, with tablet press machine punching press
Into the sequin of diameter 16mm, the membrane of carbon material coating is obtained.The membrane, which is named as, applies carbon membrane.
The coating material includes carbon black or other carbon materials, wherein, other carbon materials include graphite, carbon
Nanotube, graphene etc..
Second step, prepares the membrane for possessing dense film, i.e. SEI films.
The membrane that the carbon material that the first step is prepared coats and lithium piece composition button cell, coating carbon-coating is as just
Pole, lithium piece are anode, are carbon material substrate due to there is commercial membrane, are not required to use membrane again.Electrolyte, which is selected, contains 1M hexafluoro phosphorus
Sour lithium (LiPF6) ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solvent (v:v,1:1).Exist to assembled battery
Discharge and recharge 5 times in the voltage range of 0.3~1.5V, form solid electrolyte membrane SEI on the carbon-coating of coating.In glove box
Battery is dismantled, takes out membrane, you can obtains the membrane membrane of SEI modifications, wherein SEI is formed together with carbon material for more sulphur
Dense film for compound, so as to prepare SEI membranes.
3rd step, assembles lithium-sulfur cell.
For the CNT/S composite electrodes for being 90% using content as cathode, lithium piece forms button cell for anode.Membrane is
The SEI membranes of preparation, SEI film surfaces are towards cathode of lithium.Electrolyte select containing the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and
Lithium nitrate (the LiNO of 0.2M3) 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) (1:1, v/v) mixed solvent.
Claims (5)
1. a kind of membrane for improving lithium-sulphur cell positive electrode sulfur content, it is characterised in that the membrane substrate is commercial polypropylene
Membrane, coats carbon black or other carbon material layers thereon, and to coat carbon-coating as cathode, lithium piece is anode, assembles button cell；Button
Battery circulates 3~5 times under 1~0.3V voltage windows, and solid electrolyte membrane, solid electrolyte membrane are formed on the carbon-coating of coating
One layer of compacted zone is formed on membrane with the carbon-coating of coating, prevents polysulfide from shuttling to anode, is being improved lithium-sulfur cell just
The membrane of pole sulfur content.
A kind of 2. membrane for improving lithium-sulphur cell positive electrode sulfur content according to claim 1, it is characterised in that described its
Its carbon material includes graphite, carbon nanotubes, graphene.
3. the preparation method of the membrane described in claim 1 or 2, it is characterised in that following steps：
The first step, prepares the membrane of carbon material coating
By coating material and binding agent according to mass ratio 7:3~8:2 are dissolved in 1-methyl-2-pyrrolidinone uniformly mixed obtained slurry；
Slurry is coated on commercial polypropylene diaphragm, 50~60 DEG C of 12~24h of vacuum drying, are pressed into disk with tablet machine drift, obtain
The membrane of carbon material coating；
Second step, prepares the membrane for possessing dense film, i.e. SEI films
The membrane that the carbon material that the first step is prepared coats and lithium piece composition button cell, coating carbon-coating is as cathode, lithium
Piece is anode；Electrolyte in button cell selects the mixing of the ethylene carbonate containing 1M lithium hexafluoro phosphates and diethyl carbonate
Solvent；Discharge and recharge 1~5 time in the voltage range of 0.3~1.5V of the button cell of assembling, solid-state is formed on the carbon-coating of coating
Dielectric film SEI.
4. preparation method according to claim 3, it is characterised in that ethylene carbonate and carbonic acid diethyl in the electrolyte
The volume ratio of ester is 1:1.
5. the membrane application assembling lithium-sulfur cell of the raising lithium-sulphur cell positive electrode sulfur content described in claim 1 or 2, its feature exist
In the carbon nanotubes that the lithium-sulfur cell is 90% using content/sulphur composite electrode is cathode；Using lithium piece as anode；Electricity
It is 1 to solve matter and select volume ratio:1 1,3-dioxolane and the mixed solvent of glycol dimethyl ether, contain in 1,3-dioxolane
The lithium nitrate of the double trifluoromethanesulfonimide lithiums of 1M and 0.2M；Membrane to improve lithium-sulphur cell positive electrode sulfur content is used as lithium sulphur electricity
The membrane in pond, the one of compacted zone is facing to cathode of lithium on membrane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114223078A (en) * | 2020-06-17 | 2022-03-22 | 株式会社Lg新能源 | Capsule for lithium-sulfur secondary battery and lithium-sulfur secondary battery comprising same |
| CN115275525A (en) * | 2022-08-23 | 2022-11-01 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttling effect, preparation process thereof and lithium-sulfur battery using diaphragm |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106450102A (en) * | 2016-09-06 | 2017-02-22 | 四川大学 | Modified graphite separator for lithium-sulfur battery, preparation method of modified graphite separator and lithium-sulfur battery |
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| CN106450102A (en) * | 2016-09-06 | 2017-02-22 | 四川大学 | Modified graphite separator for lithium-sulfur battery, preparation method of modified graphite separator and lithium-sulfur battery |
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| S.S. ZHANG等: "EIS study on the formation of solid electrolyte interface in Li-ion battery", 《ELECTROCHIMICA ACTA》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114223078A (en) * | 2020-06-17 | 2022-03-22 | 株式会社Lg新能源 | Capsule for lithium-sulfur secondary battery and lithium-sulfur secondary battery comprising same |
| CN114223078B (en) * | 2020-06-17 | 2024-03-15 | 株式会社Lg新能源 | Capsule for lithium-sulfur secondary battery and lithium-sulfur secondary battery comprising same |
| CN115275525A (en) * | 2022-08-23 | 2022-11-01 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttling effect, preparation process thereof and lithium-sulfur battery using diaphragm |
| CN115275525B (en) * | 2022-08-23 | 2023-08-22 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttle effect, preparation process thereof and lithium sulfur battery using diaphragm |
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