CN103531840A - Double-electrolyte system lithium sulphur battery and preparing method thereof - Google Patents
Double-electrolyte system lithium sulphur battery and preparing method thereof Download PDFInfo
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Abstract
The invention relates to a double-electrolyte system lithium sulphur battery and a preparing method thereof. The double-electrolyte system lithium sulphur battery comprises a positive electrode and a negative electrode, wherein solid electrolyte is arranged between the positive electrode and the negative electrode, and the gap between the solid electrolyte and the positive electrode and the gap between the solid electrolyte and the negative electrode are filled with electrolyte solution or polymer electrolyte. The positive electrode and the negative electrode are separated by the solid electrolyte, the gap between the solid electrolyte and the positive electrode and the gap between the solid electrolyte and the negative electrode are filled with the electrolyte solution or the polymer electrolyte, polysulfide is prevented from shuttling between the positive electrode and the negative electrode, the full contact between electrode active materials and electrolyte is guaranteed, and accordingly active materials in electrodes can be well utilized. The lithium sulphur battery of a new structure can fundamentally solve the shuttling effect and can achieve high electrochemical performance.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell and preparation method thereof, specifically, relate to lithium-sulfur cell of a kind of two-electrolyte system and preparation method thereof, belong to lithium-sulfur cell technical field.
Background technology
Along with economic fast development, energy crisis and environmental pollution become two large focal spots of global concern.According to present depletion rate, estimate, petroleum resources face exhaustion.The communications and transportation of consumption of petroleum maximum, the tail gas major polluting atmosphere environment discharging, causes serious haze weather in China in recent years, causes respiratory disease widely.In numerous energy-saving and emission-reduction measures, the automobile that taps a new source of energy is an extremely important job, has had at present many moneys hybrid vehicle large-scale application.In order to improve flying power and the security performance of electric motor car, exploitation high-performance energy-storage battery is the key of electric automobile extensive use.Lithium rechargeable battery because open circuit voltage is high, the advantage such as energy density is large, have extended cycle life, memory-less effect, on portable mobile apparatus, be used widely, in hybrid vehicle and pure electric automobile, be developed rapidly simultaneously.Yet the widely used lithium secondary battery energy density of institute is limited at present, make electric automobile need very large space to hold the battery that maintains its operation, this makes electric motor car lightness could meet continuation of the journey requirement.Lithium-sulfur cell adopts sulphur and lithium metal respectively as positive pole and negative pole, and the two mutually mates and makes lithium-sulfur cell have high theoretical energy density and theoretical specific capacity, is that the lithium secondary battery using at present obtains more than 5 times.With lithium-sulfur cell, substitute traditional lithium secondary battery energy of continuing a journey in the situation that battery quality is constant and improve 5 times; And in identical flying power situation, the lithium-sulfur cell that volume and quality are little can be saved more spaces.Therefore, development lithium-sulfur cell is subject to extensive concern as used for electric vehicle energy-storage battery of future generation.
Although lithium-sulfur cell has the advantages such as cost is low, energy density is high, raw material sources are abundant, comes with some shortcomings too, still needs Improvement.Lithium-sulfur cell is divided into two stages in discharge process, and the first stage is that lithium metal is converted into Li<sup TranNum="67">+</sup>, by electrolyte, move to the Li that anodal surface and reaction of Salmon-Saxl generate solubility<sub TranNum="68">2</sub>s<sub TranNum="69">8</sub>, then continue to be converted into Li<sub TranNum="70">2</sub>s<sub TranNum="71">n</sub>(4≤n<8); The solubility Li that second stage generates<sub TranNum="72">2</sub>s<sub TranNum="73">n</sub>continue to be converted into insoluble Li<sub TranNum="74">2</sub>s<sub TranNum="75">2</sub>or Li<sub TranNum="76">2</sub>s is deposited on anodal surface.Because sulphur is originally as electronics and ion insulator, in electrochemical reaction process, be difficult to be utilized completely, simultaneously final discharging product poorly conductive, is deposited on electrode surface and can causes serious polarization; In addition, be dissolved into the many lithium sulfides in electrolyte in discharge process, shuttle and lithium anode is caused to corrosion in charge and discharge process between both positive and negative polarity, the many lithium sulfides of part are difficult to be utilized completely after being dissolved into electrolyte, have caused the loss of active material.
In order to address these problems, normally sulphur and electric conducting material are carried out to the compound conductivity that improves electrode, electric conducting material can also adsorb electric discharge intermediate product to a certain extent simultaneously, suppresses the stripping diffusion of many lithium sulfides.Between sulfur electrode and barrier film, add one deck conductive carbon film also can effectively adsorb in the middle of discharging product (Nature Communications, 2012,3:1166).In the anodal process of preparation, add third phase also can effectively improve battery efficiency (CN201210526096).In addition, can also in electrolyte, add in a small amount of additive reaction process and prevent the corrosion behavior of many lithium sulfides to lithium metal at lithium metal surface formation passivating film, suppress to shuttle back and forth effect (patent No. US20040081894).
Adopt said method can suppress to a certain extent the effect of shuttling back and forth, improve cycle performance of battery, but be still difficult to fundamentally solve the problem existing in lithium-sulfur cell.The Polyplus company of the U.S. utilize vacuum sputtering or plasma-reinforced chemical vapour deposition method in lithium coating surface a layer thickness the glassy state lithium ion conductor film at 50～200nm, this film can provide a physics barrier, avoids cathode of lithium to contact with liquid electrolyte and the direct of dissolvable sulfide.But this preparation method's technological requirement is harsh, and cost is higher, be not easy to large-scale production application.There is at present article report directly to adopt all solid state electrolyte to substitute organic electrolyte, utilize it to lead lithium ion and can not lead the character of polysulfide ion, suppress the effect of shuttling back and forth of many lithium sulfides completely.But adopt chalcogenide glass pottery as electrolyte, in positive pole, must add a large amount of electrolytes to improve the conductance of sulphur positive pole, this will cause in electrode active sulfur content lower, this preparation technology need to adopt higher pressure to make close contact between each component simultaneously, technique is relatively loaded down with trivial details, and battery can only flow down work in small electric, be difficult to meet the demand of used for electric vehicle energy-storage battery.
Summary of the invention
The object of the invention is to propose a kind of lithium-sulfur cell of two-electrolyte system, to solve the problems referred to above that exist in existing lithium-sulfur cell.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of two-electrolyte system lithium-sulfur cell, the positive pole and the negative pole that comprise battery, it is characterized in that: between the positive pole of described battery and negative pole, be provided with solid electrolyte, and between described solid electrolyte and positive pole and between solid electrolyte and negative pole, be all filled with electrolyte or polymer dielectric.
As a kind of preferred version, in described electrolyte, be provided with membrane for polymer.
As further preferred version, described membrane for polymer comprises porous polyethylene barrier film, porous polypropylene barrier film, polyethylene/polypropylene composite membrane, cellulose barrier film, fibreglass diaphragm, nonwoven fabrics barrier film and with any one in the membrane for polymer of ceramic coating.
A method of preparing lithium-sulfur cell of the present invention, it comprises the steps:
A) preparation is as electrode slice or the conducting film of anode; Prepare electrolyte or polymer dielectric; Prepare solid electrolyte;
B) assembled battery.
As a kind of preferred version, described electrode slice is selected any one in bright sulfur positive electrode, sulphur/carbon composite, sulphur/conducting polymer composite material, sulphur/oxide composite, lithium sulfide, phosphoric sulfide lithium, polysulfide, sulfide; Described conducting film is selected any one in conduction carbon paper, conductive carbon fibre cloth, conductive polymer membrane, conductive carbon nanotube film, conductive graphene film, conductive porous metal film, foam metal, conductive porous oxidation film.
As further preferred version, the preparation method of described electrode slice comprises the steps: the mixture of sulphur and electric conducting material to carry out after vacuum heat, be mixed into slurry with conductive black, binding agent again, after being coated with, through drying, cutting with roll-in, obtain electrode slice, or electric conducting material and conductive black, binding agent are mixed into slurry, after being coated with, through drying, cutting with roll-in, obtain electrode slice; The preparation method of described conducting film comprises the steps: electric conducting material and conductive black, binding agent to be mixed into slurry, after being coated with, through drying, cutting with roll-in, obtains unsupported conducting film.
As a kind of preferred version, described solid electrolyte is electrolyte sheet or dielectric film, and the preparation method of described electrolyte sheet first prepares conductive ceramic powder, then through compressing tablet, isostatic compaction, sintering, obtains electrolyte sheet; The preparation method of described dielectric film first prepares conductive ceramic powder, then through curtain coating and sintering, obtains dielectric film.
As further preferred version, the preparation method of described conductive ceramic powder selects solid phase method, sol-gal process, coprecipitation, combustion method or hot pressing sintering method.
As a kind of preferred version, described solid electrolyte is selected the Li of NASICON structure
(1+x)ti
(2+x)al
xp
3o
12and Li
(1+x)ge
(2-x)al
xp
3o
12, perovskite structure La
(2/3-x)li
3xtiO
3, LISICON type lithium ceramic electrolyte, glassy state lithium solid electrolyte, garnet structure Li
7la
3zr
2o
12or the above-mentioned system of different element dopings.
As a kind of preferred version, described electrolyte is that lithium salts is added in solvent and is prepared from; Described lithium salts is selected lithium perchlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium, two (fluoro sulfonyloxy methyl) imine lithium, three (trimethyl fluoride sulfonyl) lithium methides, di-oxalate lithium borate, lithium nitrate, many lithium sulfide (Li<sub TranNum="111">2</sub>s<sub TranNum="112">n</sub>, 2<n≤8) at least one; Described solvent is selected glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, Polyethylene glycol dimethyl ether, N, at least one in dinethylformamide, oxolane, DOX, thioether, ionic liquid, carbonates solvent.
As a kind of preferred version, described polymer dielectric is selected polyoxyethylene base electrolyte (PEO), polyacrylonitrile base electrolyte (PAN), polymethyl methacrylate base electrolyte (PMMA), Kynoar base electrolyte (PVDF), Kynoar-hexafluoropropylene base electrolyte (PVDF-HFP), poly ion liquid electrolyte, polystyrene-based at least one in electrolytical, or the copolymer of above-mentioned at least two kinds of monomers.
As a kind of preferred version, described method for preparing polymer electrolytes is selected any one in the tape casting, casting method, dip-coating method, spin-coating method, method of electrostatic spinning, phase inversion, non-aqueous sol-gel method, ultraviolet ray initiation radical polymerization, thermopolymer method, wherein, described the tape casting comprises the steps:
I) mixture of polymer or polymer and lithium salts, filler and plasticizer is dissolved in solvent, is prepared into uniform solution;
Ii) solution is coated on to the material surface of surfacing, by naturally volatilizing and/or vacuum drying method removal solvent, obtains polymer dielectric.
As further preferred version, described filler is selected SiO
2, Al
2o
3, ZrO
2, MgO, ZnO
2, TiO
2, LiTaO
3, glass, γ-LiAlO
2, BaTiO
3, clay, imvite, zeolite, LiN
3, LiAg
4i
5, Li
0.5la
0.5tiO
3, Li
(1+x)ti
(2-x)al
xp
3o
12, Li
(1+x)ge
(2-x)al
xp
3o
12, LISICON type lithium ceramic electrolyte, oxide type lead at least one in lithium glass, glassy state sulfide, the electrolytical powder of garnet structure, butyl titanate, aluminium isopropoxide, tetraethoxysilane, zirconium iso-propoxide.
As a kind of preferred version, the assemble method of described battery comprises the steps: for solid/liquid two-electrolyte system lithium-sulfur cell, first solid electrolyte to be enclosed on the mould of both ends open, then between battery cathode and solid electrolyte, add one deck to adsorb the barrier film of electrolyte, can guarantee that like this negative pole and solid electrolyte are fully wetting, battery cathode side is sealed, then between positive pole and solid electrolyte, add electrolyte or adsorbed the barrier film of electrolyte, finally side of the positive electrode is sealed; For solid/polymer two-electrolyte system lithium-sulfur cell, in the both sides of solid electrolyte and electrode contact, respectively add one layer of polymeric electrolyte, finally whole battery is sealed.
As further preferred version, described battery cathode is selected carbon negative pole material, oxide material, Li
4ti
5o
12, alloy material of cathode, phosphide, lithium, above-mentioned material embedding lithium product in any one.
Research shows: compare with existing lithium-sulfur cell, the lithium-sulfur cell of the two-electrolyte system of preparing according to the present invention has high stability, the corrosion behavior of intermediate product to lithium metal that can suppress to discharge, can guarantee that active material in positive pole can not be dissolved in a large number simultaneously in electrolyte, to cause capacitance loss.
Accompanying drawing explanation
Fig. 1 is solid/liquid two-electrolyte system lithium-sulfur cell structural representation of the present invention;
Fig. 2 is solid/polymer two-electrolyte system lithium-sulfur cell structural representation of the present invention;
Fig. 3 does not contain the lithium-sulfur cell first charge-discharge curve of solid electrolyte in the present invention;
Fig. 4 is solid/liquid two-electrolyte system lithium-sulfur cell first charge-discharge curve of the present invention;
Fig. 5 is the electron scanning micrograph of solid/polymer two-electrolyte system lithium-sulfur cell of the present invention;
Fig. 6 is solid/polymer two-electrolyte system lithium-sulfur cell first charge-discharge curve of the present invention.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Solid/liquid two-electrolyte system lithium-sulfur cell structure of the present invention as shown in Figure 1, between the positive pole 1 of battery and negative pole 2, be provided with solid electrolyte 3, between solid electrolyte 3 and anodal 1 and be all filled with electrolyte 4 between solid electrolyte 3 and negative pole 2, in electrolyte 4, be also provided with barrier film 5.
Solid/polymer two-electrolyte system lithium-sulfur cell structure of the present invention as shown in Figure 2, between the positive pole 1 of battery and negative pole 2, be provided with solid electrolyte 3, between solid electrolyte 3 and anodal 1 and be all filled with polymer dielectric 6 between solid electrolyte 3 and negative pole 2.
One, conductive carbon black is mixed by ball milling with sublimed sulfur, after solvent evaporates, at 155 ℃, carry out vacuum heat and obtain sulphur/carbon complex, after it is mixed in solvent with conductive agent and binding agent, on aluminium foil, be coated with post-drying and prepare anode;
Two, by Li
2cO
3, α-Al
2o
3, GeO
2, NH
4h
2pO
4the ratio that is Li:Al:Ge:P=1.5:0.5:1.5:3 according to atomic ratio is carried out ball milling, is dried, is sieved, and the powder obtaining roasting 6h at 800 ℃ is obtained to LAGP powder, and 900 ℃ of sintering 12h after LAGP powder compressing tablet are obtained to LAGP potsherd;
Three, potsherd is sealed in the mould of design, two (trifluoromethane sulfonic acid) imine lithium 1 with glass fibre membrane absorption 1mol/L, after 3-dioxolanes/glycol dinitrate ether electrolyte (LiTFSI DME/DOL), be attached to potsherd on one side, then on glass fibre membrane, press lithium sheet, negative side is sealed; At side of the positive electrode, add equally the glass fibre membrane that one deck has adsorbed identical electrolyte, then on glass fibre membrane, press the positive plate of preparation, finally side of the positive electrode is sealed and obtain solid/liquid two-electrolyte system lithium-sulfur cell.As shown in Figure 4, this battery first discharge capacity surpasses 800mAhg to the battery first charge-discharge curve of this structure
-1, Area Ratio capacity reaches 1.18mAhcm
-2, and because ceramic electrolyte has stopped the effect of shuttling back and forth of many lithium sulfides in course of reaction, can there is not the unconfined phenomenon that overcharges in battery charging process.
Comparative example 1
Conductive carbon black is mixed by wet ball grinding with sublimed sulfur, after solvent evaporates, at 155 ℃, carry out vacuum heat and obtain sulphur carbon complex, after it is mixed in solvent with conductive agent and binding agent, on aluminium foil, be coated with post-drying and prepare anode.Anode and lithium metal, barrier film and electrolyte are sealed in CR2025 button cell and carry out charge-discharge test, and electrolyte adopts the LiTFSI DME/DOL of 1mol/L.First charge-discharge curve as shown in Figure 3.Owing to not having solid electrolyte to stop the effect of shuttling back and forth of the many lithium sulfides of reaction intermediate, battery charging process unrestrictedly goes on, and is difficult to reach the restriction charging voltage of setting.
One, be distributed in water Graphene is ultrasonic, add sodium thiosulfate to stir, by dripping hydrochloric acid, make sodium thiosulfate hydrolysis at Graphene Surface Creation nano-sulfur, finally by suction filtration, obtain self-supporting Graphene/sulphur cell positive electrode;
Two, by Li
2cO
3, α-Al
2o
3, GeO
2, NH
4h
2pO
4the ratio that is Li:Al:Ge:P=1.5:0.5:1.5:3 according to atomic ratio is carried out ball milling, is dried, is sieved, and the powder obtaining roasting 6h at 800 ℃ is obtained to LAGP powder, and 900 ℃ of sintering 12h after powder compressing tablet are obtained to LAGP potsherd;
Three, LAGP potsherd is sealed in the mould of design, after LiTFSIDME/DOL organic electrolyte with glass fibre membrane absorption 1mol/L, be attached to LAGP potsherd on one side, then on glass fibre membrane, press lithium sheet, negative side is sealed, at side of the positive electrode, add equally one deck and adsorbed 0.3M LiTFSI+0.2M Li
2s
6the polypropylene diaphragm of DME electrolyte then presses the positive pole of preparation on polypropylene diaphragm, finally side of the positive electrode is sealed and obtains solid/liquid two-electrolyte system lithium-sulfur cell.
One, carbon nano-tube is processed and made its surface form functional group with red fuming nitric acid (RFNA), then ultrasonic being distributed in the aqueous solution, finally obtains carbon nano-tube film anode by suction filtration;
Two, by Li
2cO
3, α-Al
2o
3, TiO
2, NH
4h
2pO
4the ratio that is Li:Al:Ti:P=1.4:0.4:1.6:3 according to atomic ratio is carried out ball milling, is dried, is sieved, by the powder that obtains first at 350 ℃ roasting 2h, after at 800 ℃ roasting 0.5h, obtain LATP powder, 900 ℃ of sintering 6h after powder compressing tablet are obtained to LATP potsherd;
Three, potsherd is sealed in the mould of design, after LiTFSI DME/DOL organic electrolyte with glass fibre membrane absorption 1mol/L, be attached to potsherd on one side, then on glass fibre membrane, press lithium sheet, negative side is sealed, at side of the positive electrode, add equally one deck and adsorbed 2M Li
2s
6the glass fibre membrane of DOL-DME electrolyte then presses the carbon nano-tube film of preparation as positive pole on glass fibre membrane, finally side of the positive electrode is sealed and obtains solid/liquid two-electrolyte system lithium-sulfur cell.
One, after sulphur is mixed according to mass ratio 1:1 with electric polypyrrole, 155 ℃ of heat treatment 10h obtain compound, after then mixing in solvent with conductive agent and binding agent, are coated on aluminium foil surface, carry out vacuumize and obtain anode after solvent evaporates;
Two, by Li
2cO
3, α-Al
2o
3, TiO
2, NH
4h
2pO
4the ratio that is Li:Al:Ti:P=1.4:0.4:1.6:3 according to atomic ratio is carried out ball milling, is dried, is sieved, by the roasting 2h at 350 ℃ of powder elder generation obtaining, after at 800 ℃ roasting 0.5h, obtain LATP powder, 900 ℃ of sintering 6h after LATP powder compressing tablet are obtained to LATP potsherd;
Three, by the two fluoroform sulfimide ionic liquid (LiTFSI-P of N-methyl-N butyl pyrrolidine of commercially available PVDF-HFP and 0.5mol/L
14tFSI) according to the mass ratio of 3:7, be dissolved in acetone, be coated on LATP potsherd surface after mixing, after solvent evaporates, vacuumize obtains one side with the composite electrolyte of polymer dielectric, as shown in Figure 5; By forming on ceramic electrolyte surface the interface impedance that one layer of polymeric electrolyte can effectively reduce electrode and ceramic electrolyte, can suppress lithium metal simultaneously and contact side reaction occurs with pottery.
Four, positive pole is immersed in to 0.5M LiTFSI-P
14in TFSI electrolyte, make positive pole wetting well, then with not with a side contacts of polymer dielectric, with lithium sheet in polymer dielectric one side pressure, finally cell package is got up to test, as shown in Figure 6, discharge capacity reaches 1526mAh to first charge-discharge curve first
g -1.
One, sulphur is dissolved into CS
2in be prepared into homogeneous solution, then get active carbon fiber fabrics and be immersed in solution sulphur can be penetrated in the micropore of activated carbon fiber cloth as conducting base, then take out that to make solvent evaporates obtain sulphur carbon battery anodal;
Two, by Li
2cO
3, α-Al
2o
3, GeO
2, NH
4h
2pO
4the ratio that is Li:Al:Ge:P=1.5:0.5:1.5:3 according to atomic ratio is carried out ball milling, is dried, is sieved, and the powder obtaining roasting 6h at 800 ℃ is obtained to LAGP powder; By after LAGP powder compressing tablet at 900 ℃ sintering 12h obtain potsherd;
Three, the two fluoroform sulfimide poly ion liquid liquid of polydiene propyl-dimethyl amine is dissolved in the solution of acetone and water, is poured on glass plate, after solvent evaporates, take off white film.After this apertured polymeric film being immersed in to the LiTFSI DME/DOL organic electrolyte of 1mol/L, be attached to potsherd both sides, then contact with polymer dielectric respectively with metal lithium sheet sulphur is anodal, be finally encapsulated in specific mould and test.
One, sulphur and conductive agent and binding agent ball milling in suitable solvent are mixed into uniform slurry, then apply and aluminium foil surface, after solvent evaporates, carry out vacuum drying and be finally prepared into anode;
Two, by LiNO
3, La
2o
3, ZrO
2the ratio that is Li:La:Zr=7:3:2 according to atomic ratio is carried out ball milling, is dried, is sieved, and the powder obtaining roasting 6h at 800 ℃ is obtained to powder, and 900 ℃ and 1100 ℃ of sintering 12h after powder compressing tablet are obtained to potsherd;
Three, in glove box by poly(ethylene oxide) (PEO), LiTFSI, gas phase SiO
2and plasticizer Polyethylene glycol dimethyl ether (PEGDME) is added in acetonitrile, vigorous stirring is prepared the mixed glue solution of even thickness, then the glue of preparation is poured in polytetrafluoroethyldisk disk, after solvent evaporates, after vacuumize, the polymer dielectric obtaining is cut into required form;
Four, according to the structure of negative pole/polymer dielectric/ceramic electrolyte/polymer dielectric/positive pole, be stacked into one, then by this sealing structure in particular mold.Before test, by be incubated 3h at 60 ℃, make to contact better with each component after PEO electrolyte melting.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (15)
1. a two-electrolyte system lithium-sulfur cell, the positive pole and the negative pole that comprise battery, it is characterized in that: between the positive pole of described battery and negative pole, be provided with solid electrolyte, and between described solid electrolyte and positive pole and between solid electrolyte and negative pole, be all filled with electrolyte or polymer dielectric.
2. two-electrolyte system lithium-sulfur cell as claimed in claim 1, is characterized in that: in described electrolyte, be provided with membrane for polymer.
3. two-electrolyte system lithium-sulfur cell as claimed in claim 2, is characterized in that: described membrane for polymer is selected porous polyethylene barrier film, porous polypropylene barrier film, polyethylene/polypropylene composite membrane, cellulose barrier film, fibreglass diaphragm, nonwoven fabrics barrier film, had at least one in the membrane for polymer of ceramic coating.
4. a preparation method for two-electrolyte system lithium-sulfur cell as claimed in claim 1, is characterized in that, comprises the steps:
A) preparation is as electrode slice or the conducting film of anode; Prepare electrolyte or polymer dielectric; Prepare solid electrolyte;
B) assembled battery.
5. preparation method as claimed in claim 4, is characterized in that: described electrode slice is selected any one in bright sulfur positive electrode, sulphur/carbon composite, sulphur/conducting polymer composite material, sulphur/oxide composite, lithium sulfide, phosphoric sulfide lithium, polysulfide, sulfide; Described conducting film is selected any one in conduction carbon paper, conductive carbon fibre cloth, conductive polymer membrane, conductive carbon nanotube film, conductive graphene film, conductive porous metal film, foam metal, conductive porous oxidation film.
6. preparation method as claimed in claim 5, it is characterized in that, the preparation method of described electrode slice comprises the steps: the mixture of sulphur and electric conducting material to carry out after vacuum heat, be mixed into slurry with conductive black, binding agent again, after being coated with, through drying, cutting with roll-in, obtain electrode slice, or electric conducting material and conductive black, binding agent are mixed into slurry, after being coated with, through drying, cutting with roll-in, obtain electrode slice; The preparation method of described conducting film comprises the steps: electric conducting material and conductive black, binding agent to be mixed into slurry, after being coated with, through drying, cutting with roll-in, obtains unsupported conducting film.
7. preparation method as claimed in claim 4, is characterized in that: described solid electrolyte is electrolyte sheet or dielectric film; The preparation method of described electrolyte sheet first prepares conductive ceramic powder, then through compressing tablet, isostatic compaction, sintering, obtains electrolyte sheet; The preparation method of described dielectric film first prepares conductive ceramic powder, then through curtain coating and sintering, obtains dielectric film.
8. preparation method as claimed in claim 7, is characterized in that: the preparation method of described conductive ceramic powder selects any one in solid phase method, sol-gal process, coprecipitation, combustion method, hot pressing sintering method.
9. the preparation method as described in claim 4 or 7, is characterized in that: described solid electrolyte is selected the Li of NASICON structure
(1+x)ti
(2+x)al
xp
3o
12and Li
(1+x)ge
(2-x)al
xp
3o
12, perovskite structure La
(2/3-x)li
3xtiO
3, LISICON type lithium ceramic electrolyte, glassy state lithium solid electrolyte, garnet structure Li
7la
3zr
2o
12in any one.
10. preparation method as claimed in claim 4, is characterized in that: described electrolyte is that lithium salts is added in solvent and is prepared from; Described lithium salts is selected at least one in lithium perchlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium, two (fluoro sulfonyloxy methyl) imine lithium, three (trimethyl fluoride sulfonyl) lithium methides, di-oxalate lithium borate, lithium nitrate, many lithium sulfides; Described solvent is selected glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, Polyethylene glycol dimethyl ether, N, at least one in dinethylformamide, oxolane, DOX, thioether, ionic liquid, carbonates solvent.
11. preparation methods as claimed in claim 4, it is characterized in that: described polymer dielectric is selected at least one in polyoxyethylene base electrolyte, polyacrylonitrile base electrolyte, polymethyl methacrylate base electrolyte, Kynoar base electrolyte, Kynoar-hexafluoropropylene base electrolyte, poly ion liquid electrolyte, polystyrene base electrolyte, or the copolymer of above-mentioned at least two kinds of monomers.
12. preparation methods as described in claim 4 or 11, it is characterized in that, described method for preparing polymer electrolytes is selected any one in the tape casting, casting method, dip-coating method, spin-coating method, method of electrostatic spinning, phase inversion, non-aqueous sol-gel method, ultraviolet ray initiation radical polymerization, thermopolymer method, wherein, described the tape casting comprises the steps:
I) mixture of polymer or polymer and lithium salts, filler and plasticizer is dissolved in solvent, is prepared into uniform solution;
Ii) solution is coated on to the material surface of surfacing, by naturally volatilizing and/or vacuum drying method removal solvent, obtains polymer dielectric.
13. preparation methods as claimed in claim 12, is characterized in that: described filler is selected SiO
2, Al
2o
3, ZrO
2, MgO, ZnO
2, TiO
2, LiTaO
3, glass, γ-LiAlO
2, BaTiO
3, clay, imvite, zeolite, LiN
3, LiAg
4i
5, Li
0.5la
0.5tiO
3, Li
(1+x)ti
(2-x)al
xp
3o
12, Li
(1+x)ge
(2-x)al
xp
3o
12, LISICON type lithium ceramic electrolyte, oxide type lead at least one in lithium glass, glassy state sulfide, the electrolytical powder of garnet structure, butyl titanate, aluminium isopropoxide, tetraethoxysilane, zirconium iso-propoxide.
14. preparation methods as claimed in claim 4, it is characterized in that, the assemble method of described battery comprises the steps: for solid/liquid two-electrolyte system lithium-sulfur cell, first solid electrolyte is enclosed on the mould of both ends open, then between battery cathode and solid electrolyte, add one deck to adsorb the barrier film of liquid electrolyte, battery cathode side is sealed, then between positive pole and solid electrolyte, add electrolyte or adsorbed the barrier film of electrolyte, finally side of the positive electrode is sealed; For solid/polymer two-electrolyte system lithium-sulfur cell, be respectively to add one layer of polymeric electrolyte in the both sides of solid electrolyte and electrode contact, finally whole battery is sealed.
15. preparation methods as claimed in claim 14, is characterized in that: described battery cathode adopts carbon negative pole material, oxide material, Li
4ti
5o
12, alloy material of cathode, phosphide, lithium, above-mentioned material embedding lithium product in any one.
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