CN107665966A - A kind of lithium-sulfur cell - Google Patents
A kind of lithium-sulfur cell Download PDFInfo
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- CN107665966A CN107665966A CN201610595001.4A CN201610595001A CN107665966A CN 107665966 A CN107665966 A CN 107665966A CN 201610595001 A CN201610595001 A CN 201610595001A CN 107665966 A CN107665966 A CN 107665966A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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Abstract
The invention discloses a kind of lithium-sulfur cell using multilayer composite membrane.Multilayer composite membrane is the side surface coated polymer layer A and another side surface coating inorganic layers of solid material and polymeric layer B in basilar partition, and solid inorganic material layer is between basilar partition and polymeric layer B.Solid inorganic material layer can increase the mechanical strength of barrier film, when using the ceramic material acted on lithium ion conduction, can effectively improve the ionic conductivity of barrier film, reduce the polarity effect in charge and discharge process.The electrolyte that lithium-sulfur cell uses contains additive, so improve the interface state of positive pole, negative pole, barrier film, so that charging and discharging currents density is more uniform on cathode of lithium surface, and it can effectively reduce the activity of cathode of lithium in the electrolytic solution, the formation possibility of Li dendrite is greatly reduced, improves the stability of cathode of lithium when in use.
Description
Technical field
The invention belongs to lithium-sulfur cell field, more particularly to a kind of multilayer composite membrane for lithium-sulfur cell.
Background technology
Today's society, while economic fast development makes people's acquisition abundant material life, energy crisis and environment are dirty
Dye problem also increasingly annoyings the existence of the mankind.Under this severe situation, new green energy resource and regenerative resource are developed, and
Corresponding energy conversion and memory technology are scientific worker institute urgent problems to be solved instantly.Asked under the pressure of what is currently faced
Topic, new-energy automobile and other electronic equipments arise at the historic moment, however, the lithium ion battery energy for circulating in the market more is close
Spend relatively low and requirement of the Novel electric equipment to high-energy-density can not be met.New power supply system is developed to meet electrical appliance pair
High-energy-density, the requirement of high safety performance are imperative.
Traditional lithium-sulfur cell is using lithium metal as negative pole, and using elemental sulfur as positive pole, the theoretical specific capacity of lithium is 3860mAh/
G, the theoretical specific capacity of sulphur is 1675mAh/g, and the theoretical energy density of battery is up to 2600Wh/Kg, be currently known remove lithium
Energy density highest lithium secondary battery system beyond empty battery.In addition, positive electrode sulphur abundance, cheap, and poison
Property is relatively low.
No doubt lithium-sulfur cell has the incomparable high-energy-density advantage of the lithium ion battery to be circulated on Vehicles Collected from Market, but
Its commercialization also faces more difficulty.At present, the limitation commercialized problem of lithium-sulfur cell is mainly manifested in the following aspects：
(1) the caused intermediate product Li in charge and discharge process2Sn(4≤n≤8), are soluble in electrolyte, and increase is electrolysed the same of fluid viscosity
When, lithium anode is diffused to through barrier film under concentration difference effect, and reacted with lithium and generate the Li of short chain2Sn(4≦n≦8)
And Li2S2And Li2S, corrode lithium metal；And " shuttle effect " is formed, reduce the coulombic efficiency of battery.(2) product Li2S2、
Li2S is deposited on electrode surface insoluble in electrolyte, and the two is insulator, cause active material loss and electrode with
The change of electrolyte interface state so that the cycle performance of battery is deteriorated.(3) in charge and discharge process, due to cathode of lithium surface
Current density is uneven, and forms Li dendrite, causes " dead reason ", reduces the cycle life of battery.
In order to solve the above problems, mainly set about from the following aspects：(1) optimize anode structure, suppress Li2Sn(4≦n
≤ 8) dissolution from sulphur positive pole；(2) cathode of lithium is pre-processed, suppresses Li2Sn(4≤n≤8) and the reaction of cathode of lithium；(3)
Optimize electrolyte composition, add electrolysis additive, cathode of lithium surface is formed stable SEI films；(4) composite diaphragm is developed,
Enhancing is every film strength, stop Li2SnThe diffusion of (4≤n≤8), and the pick up of increase barrier film.
In terms of positive pole preparation, PVP is loaded into hollow carbon nanocoils and obtains PVP-C composites by Cui Yi etc., then with
Elemental sulfur is compound, and lithium sulfur battery anode material is made, and under discharge-rate 0.5C, after 100 circulations, specific discharge capacity is about
810mAh/g(Zheng G,Zhang Q,Cha J J,et al.Amphiphilic surface modification of
hollow carbon nanofibers for improved cycle life of lithium-sulfur batteries
[J].Nano letters,2013,13(3):1265-1270).Used in Chinese patent CN103151524A and sulphur is assembled into gold
In the hole for belonging to organic backbone (MOF), sulphur composite is prepared, it is then that it is compound with carbon, so improve following for lithium-sulfur cell
Ring performance, but load capacity of the S in MOF is smaller, obtained battery energy density is smaller.
In terms of cathode of lithium protection, the technology such as Polyplus companies of U.S. using plasma assistant depositing, evaporation difference
Ion conducting layer (is typically contained into Al2O3、P2O5、SiO2Deng the glass-ceramic electrolyte of composition) and it is preferable with lithium compatibility
Transition zone (such as Li-Sn, Li-Cu, Li3N) deposition is prepared in metallic lithium surface, so as to form multilayer complex films knot on lithium surface
Structure, to prevent lithium directly and electrolyte contacts.This method will also add multiple transition zones in preparation process, each each to ensure
Compatibility between layer, but the internal resistance of battery is the increase in, and preparation technology is complicated.K.Chung etc. is sunk using RF magnetron sputterings
The amorphous of 0.95 μ m-thick, smooth, fine and close LiPON films are accumulated.Linear voltammetric scan is carried out in 0.0-5.5V, finds LiPON films
The oxidation and decomposition of electrolyte under high pressure can be suppressed, be good passivation layer.The film causes electrode surface homogeneous current distribution,
Improve cyclical stability (Chung, the K of battery；Kim,WS；Choi,YK.Lithium phosphorous oxynitride
as a passive layer for anodes in lithium secondary batteries[J].JOURNAL OF
ELECTROANALYTICAL CHEMISTRY,2004,566(2):263-267).Park etc. is existed using ultraviolet light-initiated PEGDME
Li negative terminal surfaces polymerize, and suppress S to form protective layern 2-(4≤n≤8) directly react with lithium metal, then in lithium-sulfur cell
Use LiClO4-PVDF-HFP base GPE, plasticizer TEGDME.Experiment shows, GPE and cathode of lithium surface polymer protective layer
Cycle performance (Lee Y M, Choi N-S, Park J H, the et al.Electrochemical of lithium-sulfur cell can be effectively improved
performance of lithium/sulfur batteries with protected Li anodes[J].Journal
of Power Sources,2003,119-121:964-972)。
In terms of electrolyte composition is optimized, Aurbach etc. using the methods of EIS, FT-IR, XPS to being electrolysed in DME+DOL
Add LiNO3 in liquid to be analyzed so as to improve the mechanism of lithium-sulfur cell performance, it is believed that LiNO3Main function be protection gold
Belong to cathode of lithium.LiNO3Can be with DOL in electrolyte and Li2Sn(4≤n≤8) react, and it is blunt to form one layer of SEI on cathode of lithium surface
Change protective layer, to reduce (Aurbach D, Pollak E, Elazari R, the et al.On the of the shuttle phenomenon in lithium-sulfur cell
Surface Chemical Aspects of Very High Energy Density,Rechargeable Li-Sulfur
Batteries[J].Journal of the Electrochemical Society,2009,156(8):694-702)。
The researchs such as Liang find to add P in the electrolytic solution2S5The cycle performance of lithium-sulfur cell can be significantly improved.In 1mol/L LiTFSI/
5%P is with the addition of in TEGDME2S5Lithium-sulfur cell under 0.1C multiplying powers 20 times circulation after specific discharge capacity capacity be stable at
900mAh/g, until 40 circulation specific discharge capacities also have no obvious decay, and coulombic efficiency is then always held at more than 90%,
Cycle performance is relatively not added with P2S5Lithium-sulfur cell (Lin Z, Liu Z, Fu W, et al.Phosphorous is substantially improved
Pentasulfide as a Novel Additive for High-Performance Lithium-Sulfur
Batteries[J].Advanced Functional Materials,2013,23(8):1064-1069)。
In terms of diagram modification, modified graphene is made slurry and is coated in barrier film by Chinese patent CN104393349A
On, obtain modified diaphragm, to suppress lithium-sulfur cell in charge and discharge process polysulfide " shuttle effect ".Arumugan
Manthirn etc. prepares modified diaphragm in common PP barrier films side coating microporous carbon-polyethylene glycol, with the lithium sulphur of the modified diaphragm
For battery in 0.5C multiplying power dischargings, after 200 circulations, specific discharge capacity is still 795mAh/g.But the preparation method is complicated,
Material expensive, still there are more active material loss (Chung S H, Manthiram A.A Polyethylene in discharge and recharge
Glycol-Supported Microporous Carbon Coating as a Polysulfide Trap for
Utilizing Pure Sulfur Cathodes in Lithium-Sulfur Batteries[J].Advanced
Materials,2014,26(43):7352-7357).The method of the using plasmas such as Ju Lan grafting is grafted in PP membrane surfaces
Lithium sulfonate radical (SO3Li) group and methyl methacrylate (MMA) group, this method effectively suppress lithium metal repeatedly molten
The formation of dendrite in solution/deposition cycle, but the preparation method requirement condition is higher, it is difficult to produce (Ju Lan, Li Zhi in enormous quantities
Brave membrane surfaces are modified method and improve metal lithium electrode cycle performance [J] functional materials, 2012,12 (43):1640-1642).In
State patent 104916802A discloses a kind of composite diaphragm for lithium ion battery, and the composite diaphragm is the one of micropore basal membrane
Face applies polymeric layer, another side coated with ceramic layer.Polymer coating improves the wellability and ionic conductivity of barrier film, ceramic layer
It is favorably improved the heat endurance of barrier film.The composite diaphragm of the structure is applied certain advantage in lithium ion battery, still
Apply in lithium-sulfur cell, easily reacted due to extremely strong active of lithium metal with ceramic layer, therefore need further to optimize.In
State patent CN101326658A discloses a kind of organic/inorganic composite diaphragm with morphocline, will contain inoganic solids and glue
The porous active layer for tying agent polymer is coated on perforated substrate, and porous active layer has concentration gradient, to strengthen barrier film
Antistripping and scratch.But the barrier film is difficult to ensure that in preparation process and obtains the good porous active layer of morphocline, and
And application is in the lithium secondary battery, the porous active layer easily causes interfacial instability when being directly in contact with lithium metal.
The content of the invention
To solve the problems, such as that the cycle life that lithium-sulfur cell faces is shorter, the present invention is changed for lithium-sulfur cell barrier film
Property, it is therefore intended that effectively suppress shuttle of the polysulfide between positive and negative electrode, improve the contact between cathode of lithium and electrolyte
Stability, the corrosion of lithium metal is reduced, meanwhile, improve every film strength, ensure that battery has higher security performance.
The present invention provides a kind of lithium-sulfur cell, and for its barrier film used for multilayer composite membrane, multilayer composite membrane is in base
A side surface coated polymer layer A and another side surface coating inorganic layers of solid material and polymeric layer B for bottom barrier film, and it is inorganic
Layers of solid material is between basilar partition and polymeric layer B.And in use, positive pole is placed on the polymer of multilayer composite membrane
Layer A sides, negative pole are placed on polymeric layer B sides.
Described multilayer composite membrane using commercially available polyethylene diagrams, polypropylene diaphragm, polyethylene/polypropylene it is compound every
One kind in film, polypropylene, polyethylene/polypropylene composite materials barrier film, polyimide diaphragm, nonwoven cloth diaphragm is as its substrate.
Polymeric material used in described polymeric layer A can be PVDF, PTFE, PVP, PEO, LA132, SBR/CMC,
One kind in PAA, gelatin, cyclodextrin, sodium alginate；
Polymeric material used in described polymeric layer B can be polyacrylic acid, polymethylacrylic acid, polymethyl
It is sour methyl esters, polyvinyl acetate, polybutyl methacrylate, polyethyl acrylate, polyethylene glycol oxide, chlorosulfonated polyethylene, complete
Fluorosulphonate polymer, polyvinyl alcohol, polyacrylonitrile, polyvinylpyrrolidone, polyacrylamide, butadiene-styrene rubber, carboxymethyl are fine
Tie up element, sodium carboxymethylcellulose, hydroxyethyl cellulose, methyl hydroxyethylcellulose, carboxyethyl cellulose, Kynoar, gather
One kind in vinylidene fluoride-hexafluoropropylene copolymer, sodium alginate.
Described solid inorganic material layer includes ultra-fine inorganic solid material and polymeric material；And solid inorganic material
Mass percent is 15%-75%.
Described ultra-fine inorganic solid material can have lithium ion conduction characteristic, and it is special can also not have lithium ion conduction
Property.Ultra-fine inorganic solid material with lithium ion conduction characteristic, can be Li3xLa2/3-xTiO3(0.04 ＜ x ＜ 0.17),
Li14ZnGe4O16、Li1+xA2-xBx(PO4)3(one kind in A=Ti, Ge；One kind in B=Al, Ga, Sc, In, Y；0≤x≤
0.7)、Li5+xLa3-xAxM2O12(one kind in A=Ba, Sr；One kind in M=Zr, Ta, Nb, Sb, Bi；0≤x≤2)、xLi2S-
(1-x)P2S5(0 ＜ x ＜ 1), xLi2S-(1-x)SiS2(0 ＜ x ＜ 1), Li10GeP2S12、Li4GeS、Li3Zn0.5GeS4、
Li3.25Ge0.25P0.75S4、Li3.4Si0.4P0.6S4、Li4.8Si0.2Al0.8S4、Li6PS5X (X=Cl, Br, I), lithium nitride, lithium phosphate,
One or more in lithium metasilicate, lithium aluminate, lithium borohydride；Ultra-fine inorganic solid material without lithium ion conduction characteristic,
Can be aluminum oxide, zirconium oxide, titanium oxide, silica, cerium oxide, magnesia, yittrium oxide, tin oxide, lanthana, alumina silicate,
One or more in magnesium silicate, manganous silicate, barium titanate, lead titanates, zirconia titanate, titanium nitride, boron nitride, boron carbide.
Described ultra-fine inorganic solid material particle size range is 0.5nm-5 μm.
Polymeric material in described solid inorganic material layer, which has, to be bonded and filming function, can be polyacrylic acid,
Polymethylacrylic acid, polymethyl methacrylate, polyvinyl acetate, polybutyl methacrylate, polyethyl acrylate, polyoxy
Change ethene, chlorosulfonated polyethylene, perfluorinated sulfonate polymer, polyvinyl alcohol, polyacrylonitrile, polyvinylpyrrolidone, polypropylene
Acid amides, butadiene-styrene rubber, carboxymethyl cellulose, sodium carboxymethylcellulose, hydroxyethyl cellulose, methyl hydroxyethylcellulose, carboxylic second
One kind in base cellulose, Kynoar, Kynoar-hexafluoropropylene copolymer, sodium alginate.
Described polymeric layer A thickness is 0.2 μm -10 μm；Polymeric layer B thickness is 0.2 μm -10 μm；It is inorganic solid
The thickness of body material layer is 0.5 μm -10 μm.
Elemental sulfur in described sulphur positive pole：Conductive carbon：The mass ratio of binding agent is 50-80:10-40:10.
Conductive carbon is the one or more in AB, AC, BP2000, CMK3, Super P in described sulphur positive pole.
The binding agent that described sulphur positive pole uses is identical with the polymeric material used in polymeric layer A, through heat pressing process
Processing can be bonded well with sulphur positive pole, be advantageous to battery structure stabilization and suppressed polysulfide dissolving, improve stable circulation
Property；Polymeric material used in polymeric layer B is identical with the polymeric material for playing cementation used in inorganic material layer.
Contain additive in described lithium-sulfur cell electrolyte, promote shape between solid inorganic material layer, electrolyte, negative pole
Into solid electrolyte interface film, the cyclical stability of negative pole is improved；
Electrolyte lithium salt is LiPF in described lithium-sulfur cell electrolyte6、LiAsF6、LiClO4、LiAlCl4、LiBF6、
LiCF3SO3With LiN (CF3SO2)2In one or more；Solvent is volume ratio 1:1-1:9 DOL, DME mixed solvent；Electrolysis
Solution additive can be ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, diformazan Asia
Sulfone, methyl acrylate, gamma-butyrolacton, 1,3- propane sultones, 1,4- butane sultones, ethylmethane sulfonate, methyl sulphur
Acid butyl ester, vinylene carbonate, toluene, benzene, quinone imines, naphthalane, copolymer, the polyoxy second of dimethylsilane and expoxy propane
Alkene, polyoxyethylated dimethyl ether, PFOS lithium, LiBOB, LiNO3、SnI2、AlI3、P2S5, in bipyridyliumses compound
One or more.
The content of described additive is 0.01moL/L-0.6moL/L.
The excellent part of the present invention is：
With multilayer composite membrane when in use, polymer coating A aids in hot pressing lithium-sulfur cell close to sulphur positive pole side
Technique, make the contact between positive plate and barrier film more abundant, this can substantially reduce the internal resistance of battery, and polymer coating A is big
The big imbibition ability for improving barrier film, make electrolyte infiltration in the coating, in discharge and recharge, with the increase of cycle-index, barrier film
Polymer coating have the function that to be sustained electrolyte, can so improve the cycle performance of battery.
The polymer coating of barrier film has adsorption capacity, can effectively adsorb dissolving polysulfide in the electrolytic solution, suppress more
Sulfide migrates to cathode of lithium, avoids reaction therebetween, reduces polysulfide " shuttling and imitating in charge and discharge process
Should ".
With multilayer composite membrane when in use, solid inorganic material layer is close to cathode of lithium side, the coating energy for lithium-sulfur cell
Increase the mechanical strength of barrier film, when using the ceramic material acted on lithium ion conduction, the ion of barrier film can be effectively improved
Electrical conductivity, reduce the polarity effect in charge and discharge process.In addition, the side of solid inorganic material coating and cathode contact is coated with
Polymeric layer B also has the imbibition ability to electrolyte, can ensure have enough electrolyte to add in electrochemistry cyclic process
Agent and cathode of lithium is added to act on forming solid electrolyte film.In addition, the presence of the polymeric layer it also avoid solid inorganic material layer
With directly contacting for cathode of lithium, the interface stability of the two ensure that.
When multilayer composite membrane is used for lithium-sulfur cell, both sides coating fits together with both positive and negative polarity respectively, and infiltrates in electricity
Solve in liquid, the polymer and solid inorganic material on such barrier film coating interact and formd with the additive in electrolyte
Solid electrolyte interface film, so improve the interface state of positive pole, negative pole, barrier film so that charging and discharging currents density is born in lithium
Pole surface is more uniform, and can effectively reduce the activity of cathode of lithium in the electrolytic solution, and the formation for greatly reducing Li dendrite can
Energy property, improves the stability of cathode of lithium when in use.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.These embodiments are intended merely to have the present invention
The explanation of body, rather than limit the scope of the present invention.
Embodiment 1
5g PVDF are weighed, 95g NMP prepare PVDF solution according to mass fraction 5%, then the oxidation by particle diameter for 50nm
Titanium ceramic particle and PVDF solution mixing systems are into slurry, and the mass fraction of ceramic particle is 65% in slurry.By what is be well mixed
Inorganic ceramic slurry coating in commercial polyethylene barrier film one side, then by barrier film in convection oven with 60 DEG C of drying 8h, until
After solvent is evaporated completely, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring inorganic, ceramic layer is 5 μm.
8g PVDF is weighed, is dissolved in NMP, it is 8% solution to prepare PVDF contents, with czochralski method by resulting slurries
Both sides coated in above-mentioned individual layer composite diaphragm, barrier film is then dried into 8h in convection oven with 60 DEG C, until solvent volatilizees
After complete, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring polymer coating is respectively 8 μm.This results in two-sided modification
Multilayer composite membrane.
Embodiment 2
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVDF with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 1, electrolyte
(CF3SO2)2,DOL:DME=1:2(V:V),0.3M LiNO3, CR2016 type button cells are assembled, and test the cyclicity of battery
Energy.When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1239mAh/g, by 80
Capability retention still reaches 87% after secondary circulation.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery is put first
Electric specific capacity is 1165mAh/g, and capability retention still reaches 81% after 80 circulations.
Embodiment 3
5g PVDF are weighed, 95g NMP prepare PVDF solution according to mass fraction 5%, then by ultra-fine boron nitride ceramics
Grain is with PVDF solution mixing systems into slurry, and the mass fraction of ceramic particle is 65% in slurry.By well mixed inorganic ceramic
Slurry coating in commercial polyethylene barrier film one side, then by barrier film in convection oven with 60 DEG C of drying 8h, until solvent volatilizees
After complete, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring inorganic, ceramic layer is 5 μm.
10g PVDF is weighed, is dissolved in NMP, it is 10% solution to prepare PVDF contents, with czochralski method by resulting slurry
Liquid is coated in the both sides of above-mentioned individual layer composite diaphragm, and barrier film then is dried into 8h with 60 DEG C in convection oven, until solvent is waved
After distributing, then with vacuum drying oven with 60 DEG C of drying 12h.This results in the multilayer composite membrane of two-sided modification, polymer is measured
The thickness of coating is respectively 8 μm.
Embodiment 4
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVDF with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 3, electrolyte
(CF3SO2)2,DOL:DME=1:2(V:V),0.3M LiNO3, CR2016 type button cells are assembled, and test the cyclicity of battery
Energy.When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1343mAh/g, by 80
Capability retention still reaches 84% after secondary circulation.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery is put first
Electric specific capacity is 1206mAh/g, and capability retention still reaches 80% after 80 circulations.
Embodiment 5
5g PEO are weighed, are dissolved in the water and normal propyl alcohol (4 of certain mass:1) in mixed liquor, it is 5% to prepare mass fraction
PEO solution, then by ultra-fine Li10GeP2S12Ceramic particle and PEO solution mixing systems are into slurry, the matter of ceramic particle in slurry
It is 75% to measure fraction.By well mixed inorganic ceramic slurry coating in commercial polypropylene barrier film one side, then by barrier film in drum
With 60 DEG C of drying 8h in wind baking oven, until after solvent is evaporated completely, then with vacuum drying oven inorganic ceramic is measured with 60 DEG C of drying 12h
The thickness of layer is 6 μm.
10g PEO is weighed, is dissolved in water and normal propyl alcohol (4:1) in mixed liquor, it is 20% solution to prepare PEO contents, by institute
Obtained slurries are coated in the both sides of above-mentioned individual layer composite diaphragm, and barrier film then is dried into 8h with 60 DEG C in convection oven, treated
After being evaporated completely to solvent, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring double-sided polymerization thing coating is respectively 10 μm.This
Sample has obtained the multilayer composite membrane of two-sided modification.
Embodiment 6
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PEO with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 5, electrolyte
(CF3SO2)2,DOL:DME=1:2(V:V), 0.3M ES, CR2016 type button cells are assembled, and tests the cycle performance of battery.
When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1310mAh/g, is followed by 80 times
Capability retention still reaches 87% after ring.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery discharges ratio first
Capacity is 1186mAh/g, and capability retention still reaches 81% after 80 circulations.
Embodiment 7
5g PVP are weighed, the PVP aqueous solution are prepared according to mass fraction 5%, then by ultrafine titanium oxide ceramic particle and PVP
Solution mixing system is into slurry, and the mass fraction of ceramic particle is 70% in slurry.By well mixed inorganic ceramic slurry coating
In commercial polyethylene barrier film one side, barrier film is then dried into 8h in convection oven with 60 DEG C, until after solvent is evaporated completely, then use
For vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring inorganic, ceramic layer is 6 μm.
10g PVP is weighed, dissolving in deionized water, prepares the aqueous solution that PVP contents are 10%, by resulting slurry
Liquid is coated in the both sides of above-mentioned individual layer composite diaphragm, and barrier film then is dried into 8h with 60 DEG C in convection oven, until solvent is waved
After distributing, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring double-sided polymerization thing coating is respectively 10 μm.This results in
The multilayer composite membrane of two-sided modification.
Embodiment 8
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVP with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 7, electrolyte
(CF3SO2)2,DOL:DME=1:2(V:V), 0.3M gamma-butyrolactons, CR2016 type button cells are assembled, and tests following for battery
Ring performance.When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1260mAh/g, warp
Capability retention still reaches 83.5% after crossing 80 circulations.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery
First discharge specific capacity is 1142mAh/g, and capability retention still reaches 78% after 80 circulations.
Embodiment 9
5g PMMA are weighed, 95g NMP prepare PMMA solution according to mass fraction 5%, will then prepared with high temperature solid-state method
Ultra-fine Li14ZnGe4O16Ceramic particle and PMMA solution mixing systems are into slurry, and the mass fraction of ceramic particle is in slurry
80%.By well mixed inorganic ceramic slurry coating in commercial polyethylene barrier film one side, then by barrier film in convection oven
With 60 DEG C of drying 8h, until after solvent is evaporated completely, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness of inorganic, ceramic layer is measured
For 8 μm.
10g PMMA is weighed, is dissolved in NMP, it is 10% solution to prepare PMMA contents, and resulting slurries are coated in
The inorganic solid layer side of above-mentioned individual layer composite diaphragm, barrier film is then dried into 8h in convection oven with 60 DEG C, until solvent
After being evaporated completely, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring polymer coating is respectively 10 μm.
10g PVDF is weighed, is dissolved in NMP, it is 10% solution to prepare PVDF contents, is then answered coated in above-mentioned individual layer
Barrier film opposite side is closed, barrier film is then dried into 8h in convection oven with 60 DEG C, until after solvent is evaporated completely, then use vacuum drying oven
With 60 DEG C of drying 12h, the thickness for measuring polymer coating is respectively 10 μm.This results in the multilayer composite membrane of two-sided modification.
Embodiment 10
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVDF with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 9, electrolyte
(CF3SO2)2,DOL:DME=1:5(V:V),0.3M LiNO3, CR2016 type button cells are assembled, and test the cyclicity of battery
Energy.When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1392mAh/g, by 80
Capability retention still reaches 86.4% after secondary circulation.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery is first
Specific discharge capacity is 1303mAh/g, and capability retention still reaches 81.6% after 80 circulations.
Embodiment 11
5g PVDF are weighed, 95g NMP prepare PVDF solution according to mass fraction 5%, then by ultra-fine lithium phosphate ceramics
Grain is with PVDF solution mixing systems into slurry, and the mass fraction of ceramic particle is 80% in slurry.By well mixed inorganic ceramic
Slurry coating in commercial polyethylene barrier film one side, then by barrier film in convection oven with 60 DEG C of drying 8h, until solvent volatilizees
After complete, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring inorganic, ceramic layer is 10 μm.
10g PVDF is weighed, is dissolved in NMP, it is 10% solution to prepare PVDF contents, with czochralski method by resulting slurry
Liquid is coated in the both sides of above-mentioned individual layer composite diaphragm, and barrier film then is dried into 8h with 60 DEG C in convection oven, until solvent is waved
After distributing, then with vacuum drying oven with 60 DEG C of drying 12h, the thickness for measuring polymer coating is respectively 10 μm.This results in two-sided
Modified multilayer composite membrane.
Embodiment 12
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVDF with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 11, electrolyte
(CF3SO2)2,DOL:DME=1:2(V:V), 0.3M dimethyl sulfoxides, CR2016 type button cells are assembled, and tests the circulation of battery
Performance.When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1275mAh/g, is passed through
Capability retention still reaches 86.4% after 80 circulations.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery is first
Secondary specific discharge capacity is 1154mAh/g, and capability retention still reaches 78.5% after 80 circulations.
Embodiment 13
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVDF with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN using metallic lithium foil as negative pole, using the barrier film obtained in embodiment 11, electrolyte
(CF3SO2)2,DOL:DME=1:2(V:V),0.3M LiNO3, CR2016 type button cells are assembled, and test the cyclicity of battery
Energy.When 25 DEG C of battery testing temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1305mAh/g, by 80
Capability retention still reaches 88.3% after secondary circulation.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery is first
Specific discharge capacity is 1276mAh/g, and capability retention still reaches 83.5% after 80 circulations.
Embodiment 14
By sulphur carbon complex (it is 70% to carry sulfur content), acetylene black, PVDF with 7:2:1 prepares slurry coating in carbon-coated aluminum foils
Prepare positive pole, use 0.85M LiN (CF using metallic lithium foil as negative pole, using commercially available polypropylene diaphragm, electrolyte3SO2)2,
DOL:DME=1:2(V:V),0.3M LiNO3, CR2016 type button cells are assembled, and test the cycle performance of battery.Work as battery
25 DEG C of test temperature, when test multiplying power is 0.05C, battery first discharge specific capacity is 1315mAh/g, is held after 80 circulations
Amount conservation rate still reaches 71.4%.When 25 DEG C of battery testing temperature, when test multiplying power is 0.08C, battery first discharge specific capacity
For 1256mAh/g, capability retention still reaches 64.2% after 80 circulations.
Claims (11)
- A kind of 1. lithium-sulfur cell, it is characterised in that：For its barrier film used for multilayer composite membrane, multilayer composite membrane is in substrate A side surface coated polymer layer A and another side surface coating inorganic layers of solid material and polymeric layer B for barrier film, and it is inorganic solid Body material layer is between basilar partition and polymeric layer B；When the composite diaphragm is used in lithium-sulfur cell, sulphur positive pole is placed on The polymeric layer A sides of multilayer composite membrane, negative pole are placed on polymeric layer B sides.
- 2. lithium-sulfur cell according to claim 1, it is characterised in that：Multilayer composite membrane using commercially available polyethylene every Film, polypropylene diaphragm, polyethylene/polypropylene composite diaphragm, polypropylene, polyethylene/polypropylene composite materials barrier film, polyimides every One kind in film, nonwoven cloth diaphragm is as its substrate.
- 3. lithium-sulfur cell according to claim 1, it is characterised in that：Polymeric material used in polymeric layer A can be One or two or more kinds in PVDF, PTFE, PVP, PEO, LA132, SBR/CMC, PAA, gelatin, cyclodextrin, sodium alginate；Polymeric material used in polymeric layer B can be polyacrylic acid, polymethylacrylic acid, polymethyl methacrylate, poly- Vinylacetate, polybutyl methacrylate, polyethyl acrylate, polyethylene glycol oxide, chlorosulfonated polyethylene, perfluorinated sulfonate gather Compound, polyvinyl alcohol, polyacrylonitrile, polyvinylpyrrolidone, polyacrylamide, butadiene-styrene rubber, carboxymethyl cellulose, carboxymethyl Sodium cellulosate, hydroxyethyl cellulose, methyl hydroxyethylcellulose, carboxyethyl cellulose, Kynoar-hexafluoropropene copolymerization One or two or more kinds in thing, sodium alginate.
- 4. lithium-sulfur cell according to claim 1, it is characterised in that：Described solid inorganic material layer includes ultra-fine inorganic Solid material and polymeric material；And the mass percent of solid inorganic material is 15%-75%.
- 5. lithium-sulfur cell according to claim 4, it is characterised in that：Described ultra-fine inorganic solid material can have lithium Ionic conduction characteristic, or can also not have the one or two or more kinds in lithium ion conduction elastomeric material；Passed with lithium ion The ultra-fine inorganic solid material of characteristic is led, can be Li3xLa2/3-xTiO3(0.04<x<0.17)、Li14ZnGe4O16、Li1+xA2-xBx (PO4)3(one kind in A=Ti, Ge；One kind in B=Al, Ga, Sc, In, Y；0≤x≤0.7)、Li5+xLa3-xAxM2O12(A= One kind in Ba, Sr；One kind in M=Zr, Ta, Nb, Sb, Bi；0≤x≤2)、xLi2S-(1-x)P2S5(0<x<1)、xLi2S- (1-x)SiS2(0<x<1)、Li10GeP2S12、Li4GeS、Li3Zn0.5GeS4、Li3.25Ge0.25P0.75S4、Li3.4Si0.4P0.6S4、 Li4.8Si0.2Al0.8S4、Li6PS5One in X (X=Cl, Br, I), lithium nitride, lithium phosphate, lithium metasilicate, lithium aluminate, lithium borohydride Kind or more than two kinds；Ultra-fine inorganic solid material without lithium ion conduction characteristic, can be aluminum oxide, zirconium oxide, oxidation Titanium, silica, cerium oxide, magnesia, yittrium oxide, tin oxide, lanthana, alumina silicate, magnesium silicate, manganous silicate, barium titanate, metatitanic acid One or two or more kinds in lead, zirconia titanate, titanium nitride, boron nitride, boron carbide.
- 6. the lithium-sulfur cell according to claim 4 or 5, it is characterised in that：Described ultra-fine inorganic solid material particle diameter model Enclose for 0.5nm-5 μm.
- 7. the lithium-sulfur cell according to claim 4 or 5, it is characterised in that：Polymerization in described solid inorganic material layer Thing material has bonding and filming function, can be polyacrylic acid, polymethylacrylic acid, polymethyl methacrylate, poly-vinegar acid Vinyl acetate, polybutyl methacrylate, polyethyl acrylate, polyethylene glycol oxide, chlorosulfonated polyethylene, perfluorinated sulfonate polymerization Thing, polyvinyl alcohol, polyacrylonitrile, polyvinylpyrrolidone, polyacrylamide, butadiene-styrene rubber, carboxymethyl cellulose, carboxymethyl are fine Tie up plain sodium, hydroxyethyl cellulose, methyl hydroxyethylcellulose, carboxyethyl cellulose, Kynoar, Kynoar-hexafluoro One or two or more kinds in propylene copolymer, sodium alginate.
- 8. lithium-sulfur cell according to claim 1, it is characterised in that：Described polymeric layer A thickness is 0.2 μm of -10 μ m；Polymeric layer B thickness is 0.2 μm -10 μm；The thickness of solid inorganic material layer is 0.5 μm -10 μm.
- 9. lithium-sulfur cell according to claim 1, it is characterised in that：Elemental sulfur in sulphur positive pole：Conductive carbon：The matter of binding agent It is 50-80 to measure ratio:10-40:10；Conductive carbon is the one or two or more kinds in AB, AC, BP2000, CMK3, Super P in sulphur positive pole.
- 10. according to the lithium-sulfur cell described in claim 3,7 or 9, it is characterised in that：Binding agent and polymer used in sulphur positive pole Polymeric material used in layer A is identical, handles and can be bonded well with sulphur positive pole through heat pressing process, it is steady to be advantageous to battery structure Fixed and suppression polysulfide dissolving, improves cyclical stability；Institute in polymeric material and inorganic material layer used in polymeric layer B The polymeric material for playing cementation is identical.
- 11. lithium-sulfur cell according to claim 1, it is characterised in that：Contain addition in described lithium-sulfur cell electrolyte Agent, promote to form solid electrolyte interface film between solid inorganic material layer, electrolyte, negative pole, improve the stable circulation of negative pole Property；Electrolyte lithium salt is LiPF in lithium-sulfur cell electrolyte6、LiAsF6、LiClO4、LiAlCl4、LiBF6、LiCF3SO3And LiN (CF3SO2)2In one or more；Solvent is volume ratio 1:1-1:9 DOL, DME mixed solvent；Electrolysis additive can be with It is ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, dimethyl sulfoxide, acrylic acid first Ester, gamma-butyrolacton, 1,3- propane sultones, 1,4- butane sultones, ethylmethane sulfonate, butyl methyl sulfonate, carbonic acid It is vinylene, toluene, benzene, quinone imines, naphthalane, the copolymer of dimethylsilane and expoxy propane, polyoxyethylene, polyoxyethylated Dimethyl ether, PFOS lithium, LiBOB, LiNO3、SnI2、AlI3、P2S5, one kind in bipyridyliumses compound or two kinds with On；The content of additive is 0.01moL/L-0.6moL/L.
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| CN114927828A (en) * | 2022-07-19 | 2022-08-19 | 浙江金羽新能源科技有限公司 | Composite diaphragm with slow release function and preparation method and application thereof |
| WO2024072221A1 (en) | 2022-09-29 | 2024-04-04 | Lionvolt B.V. | Electrolyte with dual function salt additive |
| NL2033186B1 (en) | 2022-09-29 | 2024-04-08 | Lionvolt B V | Electrolyte with dual function salt additive |
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