CN106876783B - A kind of all solid state lithium-sulfur cell - Google Patents
A kind of all solid state lithium-sulfur cell Download PDFInfo
- Publication number
- CN106876783B CN106876783B CN201510909038.5A CN201510909038A CN106876783B CN 106876783 B CN106876783 B CN 106876783B CN 201510909038 A CN201510909038 A CN 201510909038A CN 106876783 B CN106876783 B CN 106876783B
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulfonic acid
- lithiumation
- acid polymer
- sulphur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
-
- 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
-
- 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
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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 invention discloses a kind of all solid state lithium-sulfur cell, the sulfonic acid polymer solid electrolyte diaphragm including sulphur anode, lithium or lithium alloy cathode and lithiumation；Solid electrolyte diaphragm is located between sulphur anode and lithium or lithium alloy cathode；Sulphur anode includes the sulfonic acid polymer of sulfur-bearing active material, conductive agent and lithiumation；Sulphur anode, the sulfonic acid polymer solid electrolyte of lithiumation, lithium or lithium alloy cathode successively overlap and are assembled into battery.The conductivity at room temperature of the sulfonic acid polymer solid electrolyte of lithiumation is > 10‑5S/cm, it is not necessary that lithium salts is complexed, preparation method is simple, also, the conductivity at room temperature of the sulfonic acid polymer solid electrolyte of lithiumation is better than general inorganic-organic hybrid solid electrolyte.Sulphur anode pole piece is prepared using polymer emulsion, efficient " sulphur/carbon/solid electrolyte " interface is constructed in electrode interior, improves the activity of sulfur electrode, obtain the battery of function admirable；And existing pole coating technique and equipment can be used, be conducive to large-scale production.
Description
Technical field
The present invention relates to a kind of using sulfonic acid polymer solid electrolyte of lithiumation and preparation method thereof, all solid lithium sulphur electricity
Pond.
Background technique
Lithium-sulfur cell is because the advantages that energy density is high, low in cost, is as next-generation new secondary cell system.But at present
The lithium-sulfur cell of research report mostly uses greatly the lower organic electrolyte of boiling point, still has some technical problems urgently to be resolved.
1. the electric discharge intermediate product polysulfide of sulphur anode is dissolved in electrolyte, shuttle effect is on the one hand caused, reduces coulombic efficiency；It is another
Aspect polysulfide passes through diaphragm and is diffused into cathode, corrodes lithium metal.2. using in the battery of organic electrolyte, due to lithium ion
Nonuniform deposition, lithium anode dendrite easily generated, on the one hand generating dead lithium influences the cycle performance of battery；Another aspect branch
Crystalline substance pierces through diaphragm and causes battery short circuit.3. organic electrolyte boiling point is lower, in abuse conditions, such as overcharge, over-discharge, external force needle thorn
Battery, it will cause battery that the perils such as burning and explosion occur.
In view of the above-mentioned problems, solution route first is that with can the solid electrolytes of conducting lithium ions substitute organic electrolysis
Liquid, i.e. design prepare all solid state lithium-sulfur cell.Currently reported all solid state lithium-sulfur cell solid electrolyte mainly includes
Inorganic solid electrolyte and two kinds of polymer dielectric.Inorganic solid electrolyte is divided into solid oxide electrolyte and sulfide again
Solid electrolyte.The ionic conductivity of the oxide inorganic solid electrolyte of research report is lower at present, sulfide solid electrolysis
Although matter ionic conductivity is higher (up to 12mS/cm), to air-sensitive, material preparation and battery assembly are difficult.Also,
Inorganic solid electrolyte brittleness is larger, not easily molded, larger with the interface impedance of positive and negative anodes；It is prepared using inorganic solid electrolyte
All-solid-state battery be not easy to be made into various shape, be unable to satisfy modern society to the various requirement of battery.Polymer dielectric point
For dry state and two kinds of gel polymer electrolyte.Solvent-free polymer electrolytes conductivity at room temperature lower (10-9), S/cm not yet
There is a possibility that practical application.Gel polymer electrolyte is usually to be made of polymer complex lithium salts, room-temperature ion electricity
Conductance reaches 10-3S/cm has a possibility that practical application.The gel polymer electrolyte of research report is most of by height at present
Molecular complex lithium salts, infiltration solvent are constituted, and still there are problems that the dissolution of active material and the generation of metal Li dendrite.
CN200910043325.7 discloses a kind of use and is grafted organic dihalide main chain as matrix using PEO, prepares after lithium salts is complexed
Copolymer solid electrolyte all solid state lithium-sulfur cell, the ether oxygen group on PEO chain can be complexed with lithium ion, pass through polymerization
Swinging back and forth for owner's chain reaches the function of transmission lithium ion；CN201110445406.7 discloses a kind of using organic and inorganic
The all solid state lithium-sulfur cell of composite polymer electrolyte, composite electrolyte include PEO, Li4Ti5O12And lithium salts, at 90 degree, Gu
The ionic conductivity of body electrolyte is 10-3S/cm, sulphur anode first discharge specific capacity are~1500mAh/g；JP2011060649-
A discloses a kind of using chalcogenide glass or all solid state lithium-sulfur cell of glass ceramics solid electrolyte, sulfide solid electrolysis
The surface exhibits that matter is fused to electrode material go out higher ionic conductance, and do not react with electrode active material, prevent interface
The increase of resistance；WO2013024537-A1 discloses a kind of lithium ion conductor Li3+3/4xBxP1-3/4xS4(0.155≤x≤1.3),
Contain β-Li3PS4, and a part of P atom is replaced by B atom, reduces the internal resistance of cell, improves output characteristics.
There are following one or more defects: organic and inorganic in the lithium-sulfur cell or lithium sulphur flow battery having been reported
Composite solid electrolyte conductivity at room temperature is low；Sulfide solid electrolyte chance water electrode is unstable, easily decomposes, and preparation is difficult；
It is larger with the interfacial contact impedance of positive and negative anodes；Inorganic solid electrolyte matter is crisp frangible, not easily molded；Preparation step is cumbersome, uncomfortable
Close large-scale production.
In view of the above-mentioned problems, the present invention is designed using the sulfonic acid polymer solid electrolyte of lithiumation and is prepared for a kind of complete solid
State lithium-sulfur cell.The sulfonic acid polymer film conductivity at room temperature of lithiumation can be greater than 10-5S/cm can satisfy lithium-sulfur cell
It is required that.Lithiumation sulfonic acid polymer solid electrolyte used has the function of lithium ion conduction, it is not necessary that lithium salts is complexed.It is just extremely active
The sulfonic acid polymer solid electrolyte mixed grinding of substance sulphur or sulfur-containing compound, conductive additive and lithiumation is uniformly coated in afterwards
Made of on collector.Wherein, conductive additive plays the role of conducting electronics, and the sulfonic acid polymer of lithiumation plays conducting lithium ions
Effect.Cathode is lithium metal, lithium alloy.For the strong reducing property for avoiding lithium metal, improve the cycle performance of battery, in cathode and
Separation layer can be increased between copolymer solid electrolyte diaphragm.Lead between positive, lithiumation sulfonic acid polymer solid electrolyte
The mode for crossing hot pressing adheres to integrally, and anode, the sulfonic acid polymer solid electrolyte of lithiumation, cathode pass through mechanical compaction mode group
Dress up battery.The all solid state lithium-sulfur cell that the present invention designs can be applied to scale energy storage, electric car, battery-operated motor cycle, electronic
The fields such as bicycle, portable electronic device, electric tool, uninterruptible power supply, wearable device.
It is had not been reported using all solid state lithium-sulfur cell of the sulfonic acid polymer solid electrolyte of lithiumation.
Summary of the invention
It is an object of the invention to design a kind of all solid lithium sulphur electricity of sulfonic acid polymer solid electrolyte using lithiumation
Pond, realize a kind of high-energy density, high security, the long-life, low cost all solid lithium sulfur rechargeable battery.
The present invention is characterized in that: the sulfonic acid polymer film conductivity at room temperature of lithiumation can be greater than 10-5S/cm, can be with
Meet the requirement of lithium-sulfur cell.Lithiumation sulfonic acid polymer solid electrolyte used has the function of lithium ion conduction, without complexing
Lithium salts.The just extremely sulfonic acid polymer solid electrolyte mixing of active material sulphur or sulfur-containing compound, conductive additive and lithiumation
After grinding uniformly made of coating on a current collector.Wherein, conductive additive plays the role of conducting electronics, and the sulfonic acid of lithiumation is poly-
It closes object and plays conducting lithium ions.Cathode is lithium metal, lithium alloy.For the strong reducing property for avoiding lithium metal, battery is improved
Cycle performance can increase separation layer between cathode and copolymer solid electrolyte diaphragm.The sulfonic acid polymer of anode, lithiumation
It is adhered to by way of hot pressing between solid electrolyte integrally, anode, the sulfonic acid polymer solid electrolyte of lithiumation, cathode are logical
It crosses mechanical compaction mode and is assembled into battery.The all solid state lithium-sulfur cell that the present invention designs can be applied to scale energy storage, electric car,
The fields such as battery-operated motor cycle, electric bicycle, portable electronic device, electric tool, uninterruptible power supply, wearable device.
The specific preparation process of the sulfonic acid polymer solid electrolyte diaphragm of the lithiumation are as follows: be electrolysed sulfonic acid polymer
Plasma membrane is put into the LiOH solution that concentration is 0.1~2mol/L, is impregnated at 20~100 DEG C 0.5~96 hour, then molten with LiOH
The solvent of liquid washs 3~10 times, removes the LiOH of film surface, then dries 1~6 hour in 65~120 DEG C of air blast, after again 40
~100 DEG C are dried in vacuo 0.5~48 hour, obtain the sulfonic acid polymer film of lithiumation；
The sulfonic acid polymer solid electrolyte film can be perfluorinated sulfonic acid-polytetrafluoroethylene film, polytrifluorostyrene
One of sulfonate film, poly- difluoro styrene sulfonic acid film, poly(aryl ether ketone) sulfonate film, polyimides sulfonate film, sulfonated polysulfone membrane or
Two kinds or more；
The solvent of the LiOH solution can be water, methanol, ethyl alcohol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, dimethyl
One of carbonic ester, diethyl carbonate or two kinds or more.
The active material of the sulphur anode can be elemental sulfur or sulfide；
The elemental sulfur can be one of rhombic sulfur, monoclinic sulphur, rhombic sulfur, elastic sulfur, polymerised sulphur or two kinds with
On；
The sulfide can be the sulphur selenium compound of inorganic metal sulfide or inorganic metal or the sulphur of inorganic metal
Tellurium compound or sulphur selenium solid solution SxSe1-x(0 < x < 1) or sulphur tellurium solid solution SxTe1-x(0 < x < 1) or organic sulfur compound or vulcanization are poly-
Close the mixture of one of object or two kinds or more；
Wherein the cation of the inorganic metal sulfide can be Fe2+、Fe3+、Ni2+、Ni3+、Ti4+、Cu+、Cu2+、
Co2+、W4+、Mo4+、Zn2+、Cd2+、Li+One of or two kinds or more；
Wherein the sulphur selenium compound of the inorganic metal can be M (SxSe1-x)2(one in M=Ge, Mo, Co, Sn, Ta
Kind or two kinds or more) (0 < x < 1), MY (SxSe1-x)2(M=Cu, Ag, Li, Tl；One of Y=Ga, Al, Sb, In, Zn or two
Kind or more) (0 < x < 1), Cu2Zn(SxSe1-x)4(0<x<1)、Cu2FeSn(SxSe1-x)4(0<x<1)、CuInP2(SxSe1-x)6(0<x
<1)、Cu2(ZnyFe1-y)Sn(SxSe1-x)4One of (0 < x < 1,0 < y < 1) or two kinds or more；
Wherein the sulphur tellurium compound of the inorganic metal can be Pb1-y(SxTe1-x)y(0 < x < 1,0 < y < 1), CuIn
(SxTe1-x)(0<x<1)、Ag9FeTe2S4Or Ag16FeBiTe3S8Or Ag6TeS2Or Ag8SnTe2S4One of or two kinds or more；
Wherein the organic sulfur compound can be mercaptan, thiophenol, thioether, dimercapto sulfide, polysulfide, vulcanize and gather
Close one of object or two kinds or more；
Wherein the sulfide polymer can be sulfurized polyacrylonitrile, vulcanization polypyrrole, vulcanization polythiophene, poly- pair of vulcanization
Benzene, vulcanization polyphenylacetylene, vulcanization polyaniline, vulcanization one of polyphenylene sulfide or two kinds or more.
The conductive agent can be acetylene black, BALCK PEARLS 2000, section's qin carbon black, Super-P, carbon nanotube,
One of carbon nano-fiber, active carbon, graphene or two kinds or more；
The preparation method of the sulphur anode is by the sulfonic acid polymer lotion of lithiumation and sulphur or sulfide, conductive agent and molten
It is mixed in the way of stirring or ball milling after agent mixing, is made slurry, the solid content of slurry is 5%~50%, then using silk
Slurry is coated in one or both sides surface or the painting of plus plate current-collecting body by the mode of wire mark brush or spraying or coating or transfer coated
Overlay on a side surface of the sulfonic acid polymer solid electrolyte diaphragm of lithiumation；
The sulfonic acid polymer lotion of the lithiumation is the sulfonic acid polymer solid electrolyte film of lithiumation in 20~100 DEG C of items
It is dissolved under part made of solvent, the mass concentration of the sulfonic acid polymer of lithiumation is 1%~50%；
Solvent used in sulfonic acid polymer lotion and slurry described in wherein is N-Methyl pyrrolidone, N, N- dimethyl
Formamide, dimethyl acetamide, dimethyl sulfoxide, diphenyl ether, sub-phosphono triamine, one in the phosphono triamine of Hexaethyl Asia
Kind or two kinds or more；
The plus plate current-collecting body is aluminium foil or copper foil or carbon-coated aluminum foils or nickel foam or foam copper.
The mass ratio of sulphur or sulfide and conductive agent in the sulphur anode is 1:9~19:1；
The mass ratio of sulphur or sulfide and the sulfonic acid polymer of lithiumation in the sulphur anode is 1:9~9:1.
Wherein the lithium alloy can be lithium and Mg, Ca, Al, Si, Ge, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn,
The alloy of one of Cd, Hg or two kinds or more metal, the mass content of lithium is 10%-95% in alloy.
Wherein unprotect layer or it can be equipped with protective layer between the lithium or lithium alloy cathode and solid electrolyte diaphragm,
Protective layer can be by LiPON, lithium silicon phosphorous oxynitride, lithium phosphate, lithium vanadium silicon oxygen, lithium carbonate, lithium nitride, lithium borohydride, metatitanic acid
One of lithium, amorphous carbon or two kinds of composition described above.
Interlayer between cathode of lithium and solid electrolyte diaphragm the preparation method comprises the following steps: with lithium band or lithium alloy band or lithiumation
Sulfonic acid polymer solid electrolyte diaphragm is substrate, utilizes magnetron sputtering deposition or pulse laser deposition or vacuum thermal evaporation technology
Or electrostatic spray deposition or blade coating or one of sol-gal process or two kinds or more are in one side surface of substrate deposition protective layer system
It is standby to form.
The sulfonic acid polymer solid electrolyte diaphragm of sulphur anode and lithiumation coated in one side surface of plus plate current-collecting body passes through
Hot pressing mode adherency is integral；The hot-pressing processing temperature of sulphur anode and the sulfonic acid polymer solid electrolyte of lithiumation is 80-240
DEG C, pressure 0.5-5MPa.
The mode of assembled battery is mechanical compaction；Outer packing is aluminum plastic film flexible package or one of aluminum hull or steel shell；Outside
Shape is button-type or cylinder or rectangular.
All solid state lithium-sulfur cell can be applied to scale energy storage, electric car, battery-operated motor cycle, electric bicycle, portable
The fields such as electronic equipment, electric tool, uninterruptible power supply, wearable device.
Excellent place of the invention is:
1, compared with the lithium-sulfur cell using organic electrolyte, using the sulfonic acid polymer electrolyte all solid lithium of lithiumation
Sulphur battery does not have shuttle effect caused by the dissolution of polysulfide, avoids the corrosion of lithium anode, improves battery
Coulombic efficiency and cycle life；And there is no electrolyte inflammable and reveal brought security risk, improve the safety of battery.
Liquid need not be encapsulated, can be manufactured using roll-to-roll mode large area, improve production efficiency.
2, compared with all solid state lithium-sulfur cell using inorganic solid electrolyte, sulfonic acid polymer electrolyte specific gravity is lighter
(~2g/cm3), easily obtain all solid state lithium-sulfur cell compared with high-energy-density.Sulphur anode pole piece is prepared using polymer emulsion, it can be with
Efficient " sulphur (active material)/carbon (electrode)/solid electrolyte " interface is constructed in electrode interior, improves the activity of sulfur electrode,
Obtain the battery of function admirable；And existing pole coating technique and equipment can be used, be conducive to large-scale production.This
Outside, sulfonic acid polymer electrolyte easily form a film, viscoplasticity it is good, good with the compatibility of positive and negative anodes, interfacial contact impedance is small, and battery easily fills
Match；Elasticity modulus is high, and easy processing meets a variety of occasions and use the requirement to battery appearance at various shape.
3, compared with inorganic-organic hybrid solid electrolyte, sulfonic acid polymer solid electrolyte of lithiumation itself can be passed
Lithium ion is led, complexing lithium salts is not needed, preparation method is simple.It overcomes and meets the unstable lithium salts of oxygen using certain chance water, such as
LiTFSi etc., the shortcomings that needing harsh electrode to prepare environment.Also, the sulfonic acid polymer solid electrolyte room-temperature ion of lithiumation
Conductivity is > 10-5S/cm, better than inorganic-organic hybrid solid electrolyte in room temperature generally below 10-5The ion-conductance of S/cm
Conductance.
Detailed description of the invention
Fig. 1 is the structural schematic diagram using all solid state lithium-sulfur cell of the sulfonic acid polymer solid electrolyte of lithiumation.1 is table
The lithium metal of face protection, 2 be the sulfonic acid polymer film of lithiumation, and 3 be all solid lithium sulphur cell positive electrode.
Fig. 2 be using lithiumation sulfonic acid polymer solid electrolyte all solid state lithium-sulfur cell charging and discharging curve, it is described
All solid state lithium-sulfur cell is the positive and negative pole material manufacture of embodiment 1.
Fig. 3 be using lithiumation sulfonic acid polymer solid electrolyte all solid state lithium-sulfur cell stable circulation linearity curve,
The all solid state lithium-sulfur cell is the positive and negative pole material manufacture of embodiment 1.
Specific embodiment
Following embodiment is only to further explain the present invention, and in the case where not violating purport of the invention, the present invention answers unlimited
In the content that following embodiment is specifically expressed.
Embodiment 1
Perfluorinated sulfonic acid-polytetrafluoroethylene film is impregnated 12 hours in 1M LiOH aqueous solution in 80 DEG C, is then washed with solvent
It washs 3~10 times, removes the LiOH of film surface, be then dried in vacuo 48 hours at 60 degree again after 100 degree of air blast are dried 2 hours,
Obtain perfluorinated sulfonic acid-polytetrafluoroethylene film of lithiumation.Using NMP as solvent, the lithiumation that mass fraction is 5% is made at 80 DEG C
Perfluorinated sulfonic acid-polytetrafluoroethylene polymer lotion.By positive active material sulfurized polyacrylonitrile, the perfluor sulphur of acetylene black, lithiumation
Acid-polytetrafluoroethylene polymer 6:2:2 in mass ratio weighing carries out mixed grinding as solvent using NMP and is uniformly coated in aluminium foil afterwards
On, it is dried overnight in 55 DEG C of vacuum drying ovens, obtains sulphur anode.Perfluorinated sulfonic acid-polytetrafluoroethylene film of lithiumation and sulphur anode are existed
120 DEG C, hot pressing 3min under 0.5MPa pressure obtain integrated anode and solid electrolyte film.By a side surface with nitridation
The metal lithium sheet of lithium protective layer, integrated anode and solid electrolyte film are assembled into battery post package in button by Fig. 1 mode
In battery case, with 90 μ A/cm2Current density to battery carry out constant-current discharge, charging/discharging voltage range be 1-3V.With the matter of sulphur
The specific capacity that amount calculates battery is 1200mAh/g, and capacity retention ratio is 62% after 80 this circulation.
Embodiment 2
Polytriflurostyrene sulphonic film is impregnated 12 hours in the DMSO solution of 2M LiOH in 100 DEG C, solvent is then used
Washing 3~10 times, removes the LiOH of film surface, then dries 6 hours in 100 degree air blast, after to be dried in vacuo 48 at 100 degree again small
When, obtain the polytriflurostyrene sulphonic film of lithiumation.Using DMF as solvent, the lithiumation that mass fraction is 10% is made at 60 DEG C
Polytriflurostyrene sulphonic polymer emulsion.By positive active material iron sulfide, Super-P, lithiumation polytrifluorostyrene
Sulfonic acid polymer 5:1:4 in mass ratio weighing carries out mixed grinding as solvent using DMF and is uniformly coated in carbon-coated aluminum foils afterwards, in
It is dried overnight in 55 DEG C of vacuum drying ovens, obtains sulphur anode.By the polytriflurostyrene sulphonic film of lithiumation and sulphur anode 110 DEG C,
Hot pressing 3min under 1MPa pressure obtains integrated anode and solid electrolyte.One side surface is had into lithium borohydride protective layer
Lithium metal, integrated anode and solid electrolyte by Fig. 1 mode be assembled into battery post package in button cell shell, with 90
μA/cm2Current density to battery carry out constant-current discharge, charging/discharging voltage range be 1-3V.With the Mass Calculation electricity of iron sulfide
The specific capacity in pond is 800mAh/g.
Embodiment 3
Poly- difluoro styrene sulfonic acid film is soaked in the mixed solution of 1M LiOH second alcohol and water (volume ratio 1:1) in 80 DEG C
Bubble 12 hours, then wash 3~10 times with solvent, removes the LiOH of film surface, then in 80 degree of air blast drying 6 hours, after again
It is dried in vacuo 48 hours at 40 degree, obtains the poly- difluoro styrene sulfonic acid film of lithiumation.Using DMAc as solvent, matter is made at 90 DEG C
Measure the poly- difluoro styrene sulfonic acid polymer emulsion for the lithiumation that score is 4%.By positive active material sublimed sulfur selenium solid solution, section
The poly- difluoro styrene sulfonic acid polymers 4:3:3 in mass ratio weighing of qin carbon black, lithiumation, carries out mixed grinding by solvent of DMAc
It is coated on copper foil after uniformly, is dried overnight in 55 DEG C of vacuum drying ovens.Just by the poly- difluoro styrene sulfonic acid film of lithiumation and sulphur
Pole hot pressing 3min under 100 DEG C, 2MPa pressure obtains integrated anode and solid electrolyte.One side surface is had into carbonic acid
The lithium metal of lithium protective layer, integrated anode and solid electrolyte are assembled into battery post package in button cell by Fig. 1 mode
In shell, with 90 μ A/cm2Current density to battery carry out constant-current discharge, charging/discharging voltage range be 1.5-3V.With the solid solution of sulphur selenium
The specific capacity of the Mass Calculation battery of body is 600mAh/g.
Embodiment 4
Poly(aryl ether ketone) sulfonate film is impregnated 12 hours in the acetonitrile solution of 1M LiOH in 78 DEG C, then washs 3 with solvent
~10 times, remove the LiOH of film surface, then dried 2 hours in 80 degree of air blast, after again 50 degree vacuum drying 48 hours, obtain
The poly- difluoro styrene sulfonic acid film of lithiumation.Using diphenyl ether as solvent, the poly- of the lithiumation that mass fraction is 4% is made at 100 DEG C
Aryl ether ketone sulfonic acid polymer lotion.By positive active material sulphur silver telluride, the poly(aryl ether ketone) sulfonic acid polymer of carbon nanotube, lithiumation
Solid electrolyte 4:3:3 in mass ratio weighing carries out mixed grinding as solvent using diphenyl ether and is uniformly coated on foam copper afterwards, in
It is dried overnight in 55 DEG C of vacuum drying ovens, obtains sulphur anode.The poly(aryl ether ketone) sulfonate film of lithiumation and sulphur anode are pressed in 115 DEG C, 1MPa
Hot pressing 3min under power obtains integrated anode and solid electrolyte.By lithium metal, the integrated anode of lithium and solid electrolyte
Battery post package is assembled into button cell shell by Fig. 1 mode, with 90 μ A/cm2Current density to battery carry out constant current put
Electricity, charging/discharging voltage range are 1.5-3V.Specific capacity with the Mass Calculation battery of sulphur silver telluride is 600mAh/g.
Embodiment 5
Polyimides sulfonate film is impregnated 48 hours in the dimethyl carbonate solution of 1M LiOH in 80 DEG C, is then used
Solvent washs 3~10 times, removes the LiOH of film surface, then dries 6 hours in 80 degree air blast, after again in 60 degree of vacuum drying 48
Hour, obtain the polyimides sulfonate film of lithiumation.Using sub-phosphono triamine as solvent, mass fraction, which is made, at 50 DEG C is
The polyimides sulfonic acid polymer lotion of 10% lithiumation.By positive active material Co (SxSe1-x)2, carbon nanotube, lithiumation it is poly-
Acid imide sulfonic acid polymer solid electrolyte 4:3:3 in mass ratio weighing, is mixed by solvent of sub-phosphono triamine
It is coated in nickel foam after grinding uniformly, is dried overnight in 55 DEG C of vacuum drying ovens, obtain sulphur anode.By the polyimides sulphur of lithiumation
Sorrel and sulphur anode hot pressing 3min under 240 DEG C, 1MPa pressure obtain integrated anode and solid electrolyte.Lithium aluminium is closed
Golden, integrated positive and solid electrolyte is assembled into battery post package in button cell shell by Fig. 1 mode, with 90 μ A/cm2
Current density to battery carry out constant-current discharge, charging/discharging voltage range be 1.5-3V.With Co (SxSe1-x)2Mass Calculation electricity
The specific capacity in pond is 450mAh/g.
Embodiment 6
Sulfonated polysulfone membrane is impregnated 12 hours in the carbovinate ester solution of 1M LiOH in 80 DEG C, solvent is then used
Washing 3~10 times, removes the LiOH of film surface, then dries 6 hours in 80 degree air blast, after to be dried in vacuo 48 at 40 degree again small
When, obtain the sulfonated polysulfone membrane film of lithiumation.Using Hexaethyl Asia phosphono triamine as solvent, it is 2% that mass fraction is made at 75 DEG C
Lithiumation sulfonated polysulfone polymers lotion.The sulfonated polysulfone polymers of positive active material thioether, carbon nanotube, lithiumation are consolidated
Body electrolyte 4:3:3 in mass ratio weighing carries out mixed grinding as solvent using Hexaethyl Asia phosphono triamine and is uniformly coated in painting afterwards
It on carbon aluminium foil, is dried overnight in 55 DEG C of vacuum drying ovens, obtains sulphur anode.By the sulfonated polysulfone membrane of lithiumation and sulphur anode 120 DEG C,
Hot pressing 3min under 1MPa pressure obtains integrated anode and solid electrolyte.By Li-Si alloy, integrated anode and solid
Electrolyte is assembled into battery post package in button cell shell by Fig. 1 mode, with 90 μ A/cm2Current density to battery carry out
Constant-current discharge, charging/discharging voltage range are 1.5-3V.Specific capacity with the Mass Calculation battery of thioether is 800mAh/g.
Claims (10)
1. a kind of all solid state lithium-sulfur cell, it is characterised in that: all solid lithium sulphur battery include sulphur anode, lithium or lithium alloy cathode with
And the sulfonic acid polymer solid electrolyte diaphragm of lithiumation；Solid electrolyte diaphragm be located at sulphur anode and lithium or lithium alloy cathode it
Between；Sulphur anode includes the sulfonic acid polymer of sulfur-bearing active material, conductive agent and lithiumation；Sulphur anode, the sulfonic acid polymer of lithiumation are solid
Body electrolyte, lithium or lithium alloy cathode, which successively overlap, is assembled into battery；
The mass ratio of elemental sulfur or sulfide and conductive agent in the sulphur anode is 1:9 ~ 19:1；
The mass ratio of elemental sulfur or sulfide and the sulfonic acid polymer of lithiumation in the sulphur anode is 1:9 ~ 9:1；
The preparation method of the sulphur anode is by the sulfonic acid polymer lotion of lithiumation and elemental sulfur or sulfide, conductive agent and molten
It is mixed in the way of stirring or ball milling after agent mixing, is made slurry, the solid content of slurry is 5% ~ 50%, then using screen printing
Brush or spraying or coating mode by slurry be coated in plus plate current-collecting body one or both sides surface or coated in the sulfonic acid of lithiumation
One side surface of copolymer solid electrolyte diaphragm；
The sulfonic acid polymer lotion of the lithiumation is the sulfonic acid polymer solid electrolyte diaphragm of the lithiumation 20 ~ 100
It is dissolved under the conditions of DEG C made of solvent, the mass concentration of the sulfonic acid polymer of lithiumation is 1% ~ 50%.
2. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: above-mentioned coating is transfer coated.
3. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: the sulfonic acid polymer solid electricity of the lithiumation
Solve the specific preparation process of matter diaphragm are as follows: sulfonic acid polymer solid electrolyte film is put into the LiOH that concentration is 0.1 ~ 2 mol/L
In solution, is impregnated 0.5 ~ 96 hour at 20 ~ 100 DEG C, then washed 3 ~ 10 times with the solvent of LiOH solution, remove film surface
LiOH, then at 65 ~ 120 DEG C air blast dry 1 ~ 6 hour, after be dried in vacuo 0.5 ~ 48 hour at 40 ~ 100 DEG C again, obtain
The sulfonic acid polymer solid electrolyte diaphragm of lithiumation；
The sulfonic acid polymer solid electrolyte film is perfluorinated sulfonic acid-polytetrafluoroethylene film, polytriflurostyrene sulphonic film, gathers
One of difluoro styrene sulfonic acid film, poly(aryl ether ketone) sulfonate film, polyimides sulfonate film, sulfonated polysulfone membrane or two kinds or more；
The solvent of the LiOH solution is water, methanol, ethyl alcohol, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, dimethyl carbonate, two
One of ethyl carbonate ester or two kinds or more.
4. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: the elemental sulfur or sulfide are sulphur anode
Active material；
The elemental sulfur is one of rhombic sulfur, monoclinic sulphur, rhombic sulfur, elastic sulfur, polymerised sulphur or two kinds or more；
The sulfide is the sulphur selenium compound of inorganic metal sulfide or inorganic metal or the sulphur tellurium compound of inorganic metal
Or sulphur selenium solid solution SxSe1-x, 0 < x < 1 or sulphur tellurium solid solution SxTe1-x, one of 0 < x < 1 or organic sulfur compound or two kinds or more
Mixture；
Wherein the cation of the inorganic metal sulfide is Fe2+、Fe3+、Ni2+、Ni3+、Ti4+、Cu+、Cu2+、Co2+、W4+、
Mo4+、Zn2+、Cd2+、Li+One of or two kinds or more；
Wherein the sulphur selenium compound of the inorganic metal is M (SxSe1-x)2, wherein 0 < x < 1, M=Ge, Mo, Co, Sn, Ta
One of or two kinds or more, MY (SxSe1-x)2, wherein 0 < x < 1, M=Cu, Ag, Li, Tl;In Y=Ga, Al, Sb, In, Zn
One or two or more kinds of, Cu2Zn(SxSe1-x)4, 0 < x < 1, Cu2FeSn(SxSe1-x)4, 0 < x < 1, CuInP2(SxSe1-x)6, 0 < x <
1 、Cu2(ZnyFe1-y)Sn(SxSe1-x)4, wherein 0 < x < 1, one of 0 < y < 1 or two kinds or more；
Wherein the sulphur tellurium compound of the inorganic metal is Pb1-y(SxTe1-x)y, wherein 0 < x < 1,0 < y < 1, CuIn
(SxTe1-x), 0 < x < 1, Ag9FeTe2S4Or Ag16FeBiTe3S8Or Ag6TeS2Or Ag8SnTe2S4One of or two kinds or more；
Wherein the organic sulfur compound be mercaptan, thiophenol, thioether, dimercapto sulfide, polysulfide, in sulfide polymer
It is one or two or more kinds of；
Wherein the sulfide polymer is sulfurized polyacrylonitrile, vulcanization polypyrrole, vulcanization polythiophene, vulcanizes and gather to benzene, vulcanization
Polyphenylacetylene, vulcanization polyaniline, vulcanization one of polyphenylene sulfide or two kinds or more.
5. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: the conductive agent is acetylene black, BLACK
One of PEARLS 2000, section's qin carbon black, Super-P, carbon nanotube, carbon nano-fiber, active carbon, graphene or two kinds
More than.
6. all solid state lithium-sulfur cell according to claim 1, it is characterized in that:
Solvent used in sulfonic acid polymer lotion and slurry described in wherein is N-Methyl pyrrolidone, N, N- dimethyl formyl
One of amine, dimethyl acetamide, dimethyl sulfoxide, diphenyl ether, sub-phosphono triamine, Hexaethyl Asia phosphono triamine or
Two kinds or more；
The plus plate current-collecting body is aluminium foil or copper foil or carbon-coated aluminum foils or nickel foam or foam copper.
7. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: wherein the lithium alloy be lithium and Mg, Ca,
The alloy of one of Al, Si, Ge, Sn, Pb, In, Sb, Bi, Fe, Se, Ag, Au, Zn, Cd, Hg or two kinds or more metal, alloy
The mass content of middle lithium is 10%-95%.
8. all solid state lithium-sulfur cell according to claim 1, it is characterized in that: wherein the lithium or lithium alloy cathode with it is upper
State between solid electrolyte diaphragm unprotect layer or be equipped with protective layer, protective layer by LiPON, lithium silicon phosphorous oxynitride, lithium phosphate,
One of lithium vanadium silicon oxygen, lithium carbonate, lithium nitride, lithium borohydride, lithium titanate, amorphous carbon or two kinds of composition described above.
9. all solid state lithium-sulfur cell according to claim 8, it is characterized in that: lithium or lithium alloy cathode and above-mentioned solid electrolytic
Protective layer between matter diaphragm the preparation method comprises the following steps: with lithium piece or lithium alloy piece or the sulfonic acid polymer solid electrolyte of lithiumation every
Film is substrate, deposited using magnetron sputtering deposition or pulse laser deposition or vacuum thermal evaporation technology or electrostatic spray or blade coating or
One of sol-gal process or two kinds or more are prepared in one side surface of substrate deposition protective layer.
10. all solid state lithium-sulfur cell according to claim 7, it is characterized in that: it is coated in plus plate current-collecting body one or both sides
The sulphur anode on surface and the sulfonic acid polymer solid electrolyte diaphragm of lithiumation are adhered to integral by hot pressing mode；Sulphur anode and lithium
The hot-pressing processing temperature of the sulfonic acid polymer solid electrolyte of change is 80-240 DEG C, pressure 0.5-5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510909038.5A CN106876783B (en) | 2015-12-10 | 2015-12-10 | A kind of all solid state lithium-sulfur cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510909038.5A CN106876783B (en) | 2015-12-10 | 2015-12-10 | A kind of all solid state lithium-sulfur cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106876783A CN106876783A (en) | 2017-06-20 |
| CN106876783B true CN106876783B (en) | 2019-07-05 |
Family
ID=59236591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510909038.5A Active CN106876783B (en) | 2015-12-10 | 2015-12-10 | A kind of all solid state lithium-sulfur cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106876783B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107482177B (en) * | 2017-07-03 | 2019-09-13 | 华中科技大学 | A kind of Te/C all-solid-state battery and preparation method thereof |
| CN109509872B (en) * | 2017-09-14 | 2021-01-01 | 中南大学 | All-solid-state lithium sulfur/sodium sulfur battery with halide serving as electrode active substance and catalyst |
| CN109659474A (en) * | 2017-10-12 | 2019-04-19 | 宁德时代新能源科技股份有限公司 | Rigid diaphragm and solid-state lithium metal battery |
| KR20200081405A (en) * | 2017-10-19 | 2020-07-07 | 미츠비시 가스 가가쿠 가부시키가이샤 | Method for manufacturing all-solid-state battery |
| TWI630748B (en) | 2017-12-28 | 2018-07-21 | 財團法人工業技術研究院 | Anode and lithium ion battery employing the same |
| 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 |
| CN109167009A (en) * | 2018-09-12 | 2019-01-08 | 肇庆市华师大光电产业研究院 | A kind of lithium battery diaphragm material and preparation method thereof |
| CN111048744B (en) * | 2018-10-11 | 2021-07-06 | 中国科学技术大学 | Metallic lithium alloy electrode material, preparation method thereof and metallic lithium secondary battery |
| CN109256555B (en) * | 2018-10-16 | 2020-12-22 | 清华大学 | Chalcogenide composite positive electrode material, all-solid-state lithium battery and preparation methods thereof |
| JP6719037B1 (en) * | 2018-11-22 | 2020-07-08 | 出光興産株式会社 | Method for producing solid electrolyte and electrolyte precursor |
| CN109755441B (en) * | 2018-12-19 | 2022-03-11 | 溧阳紫宸新材料科技有限公司 | PP (polypropylene) diaphragm modified by composite solid electrolyte and preparation method thereof |
| CN109818048A (en) * | 2019-03-04 | 2019-05-28 | 江西星盈科技有限公司 | All solid lithium metal battery and its preparation process |
| CN111952669B (en) * | 2019-05-17 | 2021-10-15 | 中南大学 | Lithium-sulfur battery and composite solvent and electrolyte thereof |
| CN110911662A (en) * | 2019-11-06 | 2020-03-24 | 华南理工大学 | Lithium cathode with protective layer and preparation method and application thereof |
| CN112927952A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Flexible lithium titanate cathode of lithium ion hybrid capacitor and preparation method thereof |
| CN114097110A (en) * | 2020-02-27 | 2022-02-25 | 株式会社Lg新能源 | Method of manufacturing lithium metal negative electrode, lithium metal negative electrode manufactured by the method, and lithium sulfur battery including the lithium metal negative electrode |
| CN111799508B (en) * | 2020-08-04 | 2022-04-15 | 电子科技大学 | All-solid-state polymer electrolyte diaphragm, preparation method and all-solid-state lithium ion battery |
| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
| CN112397775B (en) * | 2020-10-27 | 2021-12-03 | 广东东邦科技有限公司 | Li3PS4 solid electrolyte, solid mixed electrolyte, all-solid lithium-sulfur battery and preparation method thereof |
| CN112599754B (en) * | 2021-01-09 | 2022-04-12 | 福州大学 | Polymer modified composite positive electrode for lithium-sulfur battery and preparation method thereof |
| CN113299986A (en) * | 2021-05-24 | 2021-08-24 | 东莞新能安科技有限公司 | Electrolyte membrane, and electrochemical device and electronic device comprising same |
| CN113764723B (en) * | 2021-09-08 | 2024-01-26 | 远景动力技术(江苏)有限公司 | Polymer electrolyte, polymer electrolyte layer and all-solid-state lithium ion battery |
| CN113871710B (en) * | 2021-09-26 | 2023-01-06 | 珠海冠宇电池股份有限公司 | Solid electrolyte and solid battery comprising same |
| CN114242989B (en) * | 2022-02-23 | 2022-05-03 | 中南大学 | Composite electrode material and preparation method and application thereof |
| CN114744194A (en) * | 2022-04-22 | 2022-07-12 | 武汉理工大学 | Composite positive electrode material and preparation method of all-solid-state lithium sulfur battery |
| CN115050943A (en) * | 2022-07-12 | 2022-09-13 | 北京北化工程技术有限公司 | Selenium-doped thiotrithiocyanuric acid material with high compaction density, preparation method thereof and battery positive plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426125A (en) * | 2002-12-26 | 2003-06-25 | 许裕金 | Environment protection polymer high capacity solid accumulator |
| CN1467870A (en) * | 2002-07-08 | 2004-01-14 | 湘潭大学 | High-energy polymer lithium secondary battery and preparation method |
| CN103531840A (en) * | 2013-11-01 | 2014-01-22 | 中国科学院上海硅酸盐研究所 | Double-electrolyte system lithium sulphur battery and preparing method thereof |
| CN104795592A (en) * | 2015-04-24 | 2015-07-22 | 清华大学深圳研究生院 | Polymer lithium-sulfur battery and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9923234B2 (en) * | 2013-04-29 | 2018-03-20 | Seeo, Inc. | Long cycle life lithium sulfur electrochemical cells |
| CN104882606B (en) * | 2015-06-03 | 2017-07-18 | 浙江大学 | Poly- aluminium sulfide lithium organic solution and the poly- aluminium sulfide lithium battery using it as catholyte |
-
2015
- 2015-12-10 CN CN201510909038.5A patent/CN106876783B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467870A (en) * | 2002-07-08 | 2004-01-14 | 湘潭大学 | High-energy polymer lithium secondary battery and preparation method |
| CN1426125A (en) * | 2002-12-26 | 2003-06-25 | 许裕金 | Environment protection polymer high capacity solid accumulator |
| CN103531840A (en) * | 2013-11-01 | 2014-01-22 | 中国科学院上海硅酸盐研究所 | Double-electrolyte system lithium sulphur battery and preparing method thereof |
| CN104795592A (en) * | 2015-04-24 | 2015-07-22 | 清华大学深圳研究生院 | Polymer lithium-sulfur battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《锂硫电池电解质研究进展》;金朝庆等;《化学学报》;20140131;第72卷;第11-20页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106876783A (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106876783B (en) | A kind of all solid state lithium-sulfur cell | |
| CN112397762B (en) | Solid-state battery | |
| CN110838573A (en) | Lithium ion energy storage device lithium supplement slurry and preparation method and application thereof | |
| CN108767263B (en) | Preparation method and application of modified metal lithium negative electrode copper foil current collector | |
| US20190393482A1 (en) | Method of protecting the lithium anode layer in a lithium metal secondary battery | |
| KR20180076709A (en) | All solid state battery and a polymer electrolyte for the same | |
| CN101478039B (en) | Preparation for polypyrole coated lithium iron phosphate | |
| CN102694158A (en) | Silicon-containing lithium cathode, preparation method thereof and lithium sulfur battery with silicon-containing lithium cathode | |
| CN109904514A (en) | Two-layer compound solid electrolyte and its preparation method and application | |
| CN102082259A (en) | Lithium secondary battery electrodes and production method thereof | |
| CN104051695A (en) | Polymer modified diaphragm for lithium sulphur battery, preparation method of polymer modified diaphragm and lithium sulphur battery | |
| CN104157909A (en) | Preparation method of lithium sulfur battery membrane electrode | |
| KR20170050561A (en) | Semi-Interpenetrating Polymer Networks Polymer Electrolyte and All-Solid-State Battery comprising The Same | |
| CN103474723A (en) | Lithium-air battery and preparation method thereof | |
| US20190393542A1 (en) | Method of improving the cycle stability and energy density of a lithium metal secondary battery | |
| CN102097653B (en) | Electrolyte used for Li-S battery, Li-S battery and method for preparing electrolyte membrane contained in same | |
| WO2020050896A1 (en) | Lithium metal secondary battery containing a protected lithium anode | |
| KR20120092918A (en) | Polymer composite electrolyte for rechargeable lithium battery and rechargeable lithium battery including same | |
| JP5632246B2 (en) | Lithium ion secondary battery | |
| CN111082054B (en) | Lithium-sulfur battery positive electrode material, positive electrode, preparation and application thereof | |
| CN108878890B (en) | Lithium ion battery conductive film/metallic lithium/conductive substrate three-layer structure composite electrode and preparation method thereof | |
| Li et al. | Composite solid electrolyte with Li+ conducting 3D porous garnet-type framework for all-solid-state lithium batteries | |
| CN109873111B (en) | High-specific-surface-area lithium metal cathode and preparation and application thereof | |
| CN110611120A (en) | Single-ion conductor polymer all-solid-state electrolyte and lithium secondary battery comprising same | |
| CN109786751A (en) | A kind of negative current collector and preparation method thereof and solid state battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |