CN102956866B - One can fill alkali metal-sulphur flow battery - Google Patents

One can fill alkali metal-sulphur flow battery Download PDF

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CN102956866B
CN102956866B CN201110249169.7A CN201110249169A CN102956866B CN 102956866 B CN102956866 B CN 102956866B CN 201110249169 A CN201110249169 A CN 201110249169A CN 102956866 B CN102956866 B CN 102956866B
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electrolyte
anode
described
positive
alkali metal
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CN201110249169.7A
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CN102956866A (en
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胡勇胜
索鎏敏
李泓
陈立泉
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中国科学院物理研究所
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Abstract

One can fill alkali metal-sulphur flow battery, described battery cathode chamber part, barrier film and anode chamber part, described cathode chamber part comprises positive pole reative cell and the fluid reservoir with cathode chamber pipeline communication, described positive pole reative cell comprises, positive collector electrode and the anode sizing agent circulated between positive pole reative cell and fluid reservoir used as positive pole; Described anode chamber part is negative reaction room, comprises negative pole, negative collector electrode and electrolyte liquid; Described barrier film is single ion conductor film, is arranged between described positive pole reative cell and negative reaction room, and ensures to only have single work ionic conduction between both positive and negative polarity, and without any mass transfer of other inoperative ion; Described anode sizing agent is made up of anode electrolyte and the positive electrode active material be blended in anode electrolyte, and described positive active material is M xs y(M=Li or Na; 0<x≤2; 0<y≤12) in one or more.

Description

One can fill alkali metal-sulphur flow battery

Technical field

The present invention relates to a kind of chemical cell.In particular to a kind of alkali metal-sulphur flow battery.

Background technology

Since lithium ion battery is succeeded in developing, due to its have that fail safe is good, voltage and the advantage such as specific energy is high, the discharge and recharge life-span is long, be thus widely used in the portable electronics such as mobile phone, notebook computer and video camera.Along with electronics miniaturization and portability, and the appearance of the electric automobile of environmental protection and flourish, the lithium ion battery as energy and power resources is had higher requirement.On existing basis, how improve discharge performance under the specific capacity of lithium ion battery and large multiplying power further, become current hotspot problem.In addition, how to improve adopt lithium ion battery dynamical system electronics and power-equipment to the adaptability of temperature, can run well in harsher outdoor environment or work also be current urgent problem.And be the key restriction factors determining the above performance of lithium ion battery as the positive electrode of lithium ion battery important component part.

The anode material for lithium-ion batteries that current commercialization is used mainly concentrates on the embedding oxidate for lithium of transition metal, comprise cobalt, iron, nickel, the oxide of manganese and doped compound thereof, but this compounds is subject to the restriction of self theoretical capacity to bring up at most the energy density of 300Wh/Kg, and be solid due to this kind of material, charge and discharge process intermediate ion is by diffusion control, thus high rate performance promote difficulty and space is little, in addition due to lithium ion, diffusion process is comparatively large by influence of temperature change wherein, makes the lithium ion battery temperature scope of application very limited.Lithium-sulfur cell is due to its high energy density (S 81675mAh/g), theoretical energy density can reach 2800Wh/kg, is considered to the direction of following lithium ion battery development, but due to the larger technical barrier of this system existence, is still in laboratory stage at present.Its subject matter existed is: 1) charge product elemental sulfur S 8with discharging product Li 2s conductivity is similar to insulator, conductivity extreme difference, if need a large amount of electric conducting material of compound to work as active material, or its particle is reduced to Nano grade or molecule rank.In addition, the many sulphions of its discharging product are soluble in electrolyte, go out nonconducting elemental sulfur or polysulfide during charging at conductive agent surface deposition, add the resistance between conductive agent particle and between conductive agent and collector.And along with discharge and recharge number of times increases, the internal resistance of cell constantly rises, and specific energy declines gradually, this is the short main cause of lithium-sulfur cell cycle life.2) reaction of positive electrode elemental sulfur charge and discharge process is multi-step reaction, its intermediate product Li 2s 8, Li 2s 6, Li 2s 4very easily be dissolved in electrolyte, the many sulphions be dissolved in electrolyte also can shuttle between positive and negative electrode, cause that efficiency for charge-discharge is not high, self discharge is larger.How many sulphions are stayed positive pole as far as possible, and the electric transmission making the elemental sulfur deposited during its discharge and recharge not affect positive pole improves the key of lithium-sulfur cell cycle life.

Adopt traditional lithium-sulfur cell technique, specific as follows:

Elemental sulfur powder is mixed with weight ratio 1: 1 with porous carbon, under argon gas condition 155 degree, be incubated 24 hours, resulting materials is as positive active material, it is mixed according to weight ratio 8: 1: 1 with acetylene black and Kynoar, be coated on current collector aluminum foil, the baking in 10 hours of 60 degree of vacuum, obtains anode electrode.

Employing standard button cell CR3032 assembles, and electrolyte adopts 1mol/L LiTFSI to be dissolved as TEGDME, using lithium sheet as negative pole.

At C/10 multiplying power constant current charge-discharge, first all composite material electric discharge 612mAh/g, but overcharge obviously due to strong " effect of shuttling back and forth ", first all efficiency is that after 137%, 50 weeks, specific capacity conservation rate only has 51%.

Summary of the invention

For the problems referred to above that current lithium-sulfur cell exists, the object of the invention is to, propose to adopt elemental sulfur or alkali metal sulphur compound to be positive active material, adopt alkali metal-sulphur flow battery that active material is got up with liquid or slurry form flow circuit.

One can fill alkali metal-sulphur flow battery, described battery cathode chamber part, barrier film and anode chamber part, described cathode chamber part comprises positive pole reative cell and the fluid reservoir with cathode chamber pipeline communication, described positive pole reative cell comprises, positive collector electrode and the anode sizing agent circulated between positive pole reative cell and fluid reservoir used as positive pole; Described anode chamber part is negative reaction room, comprises negative pole, negative collector electrode and electrolyte liquid; Described barrier film is single ion conductor film, is arranged between described positive pole reative cell and negative reaction room, and ensures to only have single work ionic conduction between both positive and negative polarity, and without any mass transfer of other inoperative ion; Described anode sizing agent is made up of anode electrolyte and the positive electrode active material be blended in anode electrolyte, and described positive active material is MxSy (M=Li or Na; 0 < x≤2; 0 < y≤12) in one or more.

Further, positive conductive material is also comprised in described anode sizing agent; Described positive conductive material is material with carbon element: in the carbon of acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, N doping, one or more mixtures are formed.

Further, the addition of described positive conductive material is account for anode electrolyte volume 0 ~ 50%, preferable range: 0% ~ 30%.

Further, described positive pole reative cell also comprises the positive conductive material be arranged in positive collector electrode, and described conductive materials is material with carbon element: in the carbon of acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, N doping, one or more mixtures are formed.

Further, described positive active material concentration range in the electrolytic solution exists: 0.01 ~ 10mol/L, preferable range: 0.1 ~ 3mol/L.

Further, described negative pole is lithium metal or sodium metal or its alloy.

Further, described single ion conductor film only allows the transmission of single work ion, and without other liquid and inoperative ion diffuse; Single ion conductor film is inorganic ceramic membrane, organic polymer films or inorganic/organic composite ceramic membrane.

Further, described inorganic ceramic membrane is single ion conductor inorganic ceramic membrane (xLi 2s+ySiS 2+ zLi 3pO 4(0 < x≤1,0 < y≤1,0 < z≤1), lLi 2s+mGeS 2+ nP 2s 5(0 < l≤1,0 < m≤1,0 < n≤1), hLi 2s+kSiS 2+ jP 2s 5(0 < h≤1,0 < k≤1,0 < j≤1), aLi 2o+bSiO 2+ cTiO 2+ dAl 2o 3+ eP 2o 5(0 < a≤1,0 < b≤1,0 < c≤1,0≤d≤1,0 < e≤1); Described organic polymer films is that isolated sub-conducting organic film is (as perfluorinated ion-exchange membrane (Nafion) film through lithiumation or sodium process; Organic/inorganic compound film is isolated sub-conducting organic/inorganic composite film.(as deposited the adjustable inorganic Al of a layer thickness by technique for atomic layer deposition on organic (Nafion) film 2o 3.

Further, the electrolyte in described positive pole and electrolyte liquid is be selected from following one or more, and lithium salts is: LiPF 6, LiAsF 6, LiSbF 6, LiBF 4, LiClO 4, LiAlCl 4, LiGaCl 4, LiB 10cl 10, LiCF 3sO 3, LiC 4f 9sO 3, LiN (C xf 2x+1sO 2) (C yf 2y+ 1SO 2), wherein, x and y is natural number, LiBFz (CF 3) 4-z, the wherein natural number of z≤4; Sodium salt is: NaPF 6, NaBF 4, NaClO 4, NaAlCl 4, NaCF 3sO 3, NaC 4f 9sO 3, described electrolytical concentration is 0.5 ~ 5.0mol/L.

Further, the solvent in described electrolyte is organic solvent or ionic liquid.

Further, the organic solvent that described organic electrolyte uses is selected from following one or more: propylene carbonate (PC), vinyl carbonate (EC), butylene carbonic ester (BC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid di-n-propyl ester (DPC), diisopropyl carbonate (DIPC), ethyl propyl carbonic acid ester (EPC), ethylene isopropyl ester (EIPC), dimethoxy-ethane (DME), oxolane (THF), 2-methyltetrahydrofuran (MeTHF), diglycol ethylene dimethyl ether (DGM), contracting TRIGLYME (TGM), contracting tetraethyleneglycol dimethyl ether (TEGM), dimethyl sulfoxide (DMSO) (DMSO), sulfolane (TMSO), dimethyl sulfone (MSM), 1, 3-dioxolanes (1, 3-DOL).

Further, described ionic liquid has following kind, and one or more are formed, and are specially: imidazole type ion liquid is as 1-ethyl-3-methylimidazole tetrafluoroborate [EMIM] BF 4, 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM] BF 4, 1-ethyl-3-methylimidazole three cyanogen first salt (two fluoroform sulfimide salt [EMIM] Tf of [EMIM] TCCN, 1-ethyl-3-methylimidazole 2n, three hexyl myristyl phosphorus tetrazolium [P66614] [Tetz], three hexyl myristyl phosphorus imidazole salts [P66614] [Im], 1-ethyl-3-methylimidazole tetrazolium [EMIM] [Tetz], two fluoroform sulfimide salt [BMIM] Tf of 1-butyl-3-methylimidazole 2n, 1-butyl-3-methylimidazole hexafluorophosphate [BMIM] PF 6, two fluoroform sulfimide salt [C8MIM] Tf of 1-butyl-3-methylimidazole fluoroform sulphonate [BMIM] OTF, 1-butyl-3-methylimidazole dicyandiamide salt [BMIM] DCN, 1-octyl group-3-methylimidazole 2n, 1-hexyl-3-methylimidazolium tosylate [C 6mIM] OTS, 1-butyl-3-methylimidazole N, the waste propylhomoserin salt of N-dialkyl group [C 4mIM] BDTC, 1-butyl-3-methylimidazolidinyl trithiocarbonate [C 4mIM] TTC, 1-butyl-3-methylimidazole alkoxyl dithiocarbonate [C4MIM] OTDC; Pyridine type ionic liquid is as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; Piperidines type ionic liquid as N-methyl, the two fluoroform sulfimide salt PP of propylpiperdine 13tFSI, N-methyl, propylpiperdine fluoroform sulphonate PP 13oTF, N-methyl, propylpiperdine hexafluorophosphate PP 13pF 6, N-methyl, propylpiperdine bromination PP 13br; Pyrrolidines type ionic liquid as N-methyl, the two fluoroform sulfimide salt BMPTf of butyl pyrrolidine 2n, ethanaminium, N-methvl, butyl pyrrolidine, chlorination N-methyl, butyl pyrrolidine; Quaternary ammonium type ionic liquid is as TBuA tetrafluoroborate.

Further, described positive and negative electrode collector adopts the net of the metals such as nickel, stainless steel, titanium, aluminium and alloy composition thereof or paper tinsel to make, or with above metal and alloy thereof be base metal foam or porous metals, or carbon class negative material.

Further, carbon class negative material, one or more mixtures such as the carbon of graphite, MCMB (MCMB), hard carbon ball, porous carbon, acetylene black, Graphene, carbon nano-tube, carbon fiber, N doping are formed.

Further, described anode chamber part also comprises the negative pole fluid reservoir be connected by pipeline with anode chamber.

Further, the material that fluid reservoir uses that anode portion adopts can be metal or its alloy as aluminium, aluminium alloy, titanium, titanium alloy, stainless steel, also can be other organic polymer material as polytetrafluoroethylene, PVP, also can use inorganic ceramic composite material.

Present invention utilizes alkali metal sulphide M xs y(M=Li or Na; 0 < x≤2; 0 < y≤12) at different phase different solubility in the electrolytic solution, be dissolved in organic electrolyte, as S by polysulfide 8-M 2s 12-M 2s 8-M 2s 6-M 2s 4-M 2s 2-M 2s is except elemental sulfur, and along with the raising of polysulfide alkali metal content, solubility reduces successively.If the concentration of the polysulfide in electrolyte acquires a certain degree, when polysulfide is when latter stage, alkali metal content raised gradually in electric discharge, there will be alkali metal polysulfide and separate out phenomenon from electrolyte, whole course of reaction can present liquid-solid intersection hybrid reaction.Such as, if the suitable controlled discharge degree of depth, only realizes M by limited capacity on the one hand 2s 8-M 2s 4between conversion, then reactant is always liquid form, can improve mobility to a certain extent, improve dynamic performance.On the other hand, if do not control course of reaction, then solid active agents can be made to flow in a form of slurry, reach the object of circulation.Therefore, this system is a chemical system that can control course of reaction, and we can pass through the controlled discharge degree of depth, realize any two kinds of polysulfides of alkali metal or the Reversible Cycle between elemental sulfur and sulfide by ways such as limited capacity.

Compared with prior art, the present invention has following remarkable advantage:

(1) high-energy-density

As shown in Table 1, sulphur and relevant lithium sulphur compound thereof have the theoretical specific capacity exceeding several times compared with conventional cathode material, even if operating voltage is on the low side, as about 2V, still far away higher than Conventional solid positive electrode after the conversion of output energy density.In addition, owing to adopting liquid fluid system, greatly reduce the proportion of collector in system, therefore, more conventional lithium-ion battery system, the energy density room for promotion of battery system becomes large.

The existing positive electrode of table 1 and alkali metal sulfenyl material contrast

(2) long circulation life

Because cathode chamber and anode chamber achieve separation by single ion conductor film, the transmission of single work ion is only had between two Room, and without other liquid and inoperative ion diffuse, efficiently solve active material and alkali-metal reaction, avoid the shuttle back and forth effect of many sulphions between both positive and negative polarity, ensure that the coulombic efficiency of discharge and recharge is close to a hundred per cent, thus fundamentally thoroughly solving the problem of lithium-sulfur cell cycle performance difference.

(3) wider serviceability temperature scope

Traditional solid active agents is owing to being subject to lithium ion diffusion control, and especially along with the decline of temperature, ionic conductance also reduces rapidly thereupon, thus causes conventional solid electrode material temperature influence comparatively large, low temperature electrochemical poor-performing.This patent is owing to adopting active material and battery system, and conductivity is acted upon by temperature changes not obvious, therefore has good high and low temperature performance.

Accompanying drawing explanation

Fig. 1 is the first embodiment schematic diagram of alkali metal of the present invention-sulphur flow battery;

Fig. 2 is the second embodiment schematic diagram of alkali metal of the present invention-sulphur flow battery;

Fig. 3 is the third embodiment schematic diagram of alkali metal of the present invention-sulphur flow battery;

Fig. 4 is the 4th kind of embodiment schematic diagram of alkali metal of the present invention-sulphur flow battery;

Fig. 5 for the active material in battery of the present invention shown in Fig. 2 be Li 2s 8, conductive materials is when being acetylene black, the first all charging and discharging curve figure of measured typical case;

Fig. 6 for the active material in battery of the present invention shown in Fig. 4 be Li 2s 8, the first all charging and discharging curve figure of measured typical case.

Embodiment

Embodiment 1

As shown in Figure 1, the filled alkali metal in the present embodiment-sulphur flow battery, comprising: cathode chamber part 1, barrier film 2, anode chamber part 3.Wherein, anode portion room 1 mainly comprises fluid reservoir 11, positive pole reative cell 12 and is arranged on and is communicated with piston pump 13 on fluid reservoir 11 and reative cell 12 pipeline and flow valve 14.The just very anode sizing agent of circulation between positive pole reative cell 12 and fluid reservoir 11, anode sizing agent is made up of anode electrolyte and the positive active material be blended in anode electrolyte, and wherein positive active material is M xs y(M=Li or Na; 0 < x≤2; 0 < y≤12) in one or more, during work, need be pumped in positive pole reative cell 12 by piston pump, the size of flow can be controlled by flow valve 14.Positive collector electrode 16 is also provided with conductive materials 15; Conductive materials 15 is concrete dynamic modulus, can conductive materials, by adhesive coated or roll extrusion on collector 16; It act as the response area increased in cathode chamber, improves the conductivity of collector electrode, improves the active material reaction efficiency in anode electrolyte.Barrier film 2 is arranged between positive and negative electrode as positive and negative electrode coupling part; This barrier film 2 is single ion conductor film, and barrier film 2 should ensure to only have single ionic to conduct between both positive and negative polarity, and without other any mass transfer.Anode chamber 3 is closed reaction chamber; The electrolyte liquid 33 comprising negative pole 31, collector 32 and be arranged in anode chamber.

Positive pole reative cell 1:

Anode electrolyte: solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4; Concentration is 1mol/L.

In anode electrolyte, add positive active material be mol ratio be 1: 7 Li 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material concentration is 0.5mol/L 2s 8.

In positive pole reative cell, collector is also provided with positive conductive material acetylene black, its concrete set-up mode is that 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene in positive collector electrode with weight ratio 9: 1.

Positive collector electrode is 100 object stainless (steel) wires.

Barrier film 2:

Barrier film 2 in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3

Anode chamber is closed reaction chamber, and electrolyte liquid is organic solvent PC: DMC=1: 1, and electrolyte is LiBF 4, concentration is 1mol/L.Negative pole adopts metal lithium sheet.

Embodiment 2:

Battery structures in the present embodiment etc. are all substantially the same manner as Example 1, and its difference is that the constituent of the anode sizing agent adopted in the present embodiment is different from embodiment 1, is specially:

Positive pole reative cell 1:

The anode sizing agent just very circulated between cathode chamber and fluid reservoir, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4.Concentration is 1mol/L.

In anode electrolyte, add positive active material be mol ratio be 1: 11 Li 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material concentration is 1mol/L 2s 12.

In positive pole reative cell, collector is also provided with positive conductive material acetylene black, its concrete set-up mode forms in 100 object stainless (steel) wire manufactures for 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene with weight ratio 9: 1.

Barrier film 2:

Barrier film 2 in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3

Anode chamber is closed reaction chamber, and electrolyte liquid is organic solvent PC: DMC=1: 1, and electrolyte is LiBF 4, concentration is 1mol/L.Negative pole adopts metal lithium sheet.

Embodiment 3:

Battery structures in the present embodiment etc. are all substantially the same manner as Example 1, and its difference is that the constituent of the anode sizing agent adopted in the present embodiment is different from embodiment 1, is specially:

Positive pole reative cell 1:

The anode sizing agent just very circulated between cathode chamber and fluid reservoir, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4.Concentration is 1mol/L.The Li that positive active material mol ratio is 1: 9 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.5mol/L 2s 10.

In positive pole reative cell, plus plate current-collecting body is also provided with positive conductive material acetylene black, its concrete set-up mode is that 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene on plus plate current-collecting body with weight ratio 9: 1.

Plus plate current-collecting body is 100 object stainless (steel) wires.

Barrier film 2:

Barrier film 2 in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3

Anode chamber is closed reaction chamber, and electrolyte liquid is organic solvent PC: DMC=1: 1, and electrolyte is LiBF 4, concentration is 1mol/L.Negative pole adopts metal lithium sheet.

Embodiment 4:

Battery structures in the present embodiment etc. are all substantially the same manner as Example 1, and its difference is that the constituent of the anode sizing agent adopted in the present embodiment is different from embodiment 1, is specially:

Positive pole reative cell 1:

The anode sizing agent just very circulated between cathode chamber and fluid reservoir, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4.Concentration is 1mol/L.The Li that positive active material mol ratio is 1: 5 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.3mol/L 2s 6.

In positive pole reative cell, plus plate current-collecting body is also provided with positive conductive material acetylene black, its concrete set-up mode is that 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene on plus plate current-collecting body with weight ratio 9: 1.

Plus plate current-collecting body is 100 object stainless (steel) wires.

Barrier film 2:

Barrier film 2 in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3

Anode chamber is closed reaction chamber, and electrolyte liquid is organic solvent PC: DMC=1: 1, and electrolyte is LiBF 4, concentration is 1mol/L.Negative pole adopts metal lithium sheet.

Embodiment 5:

Battery structures in the present embodiment etc. are all substantially the same manner as Example 1, and its difference is that the constituent of the anode sizing agent adopted in the present embodiment is different from embodiment 1, is specially:

Positive pole reative cell 1:

The anode sizing agent just very circulated between cathode chamber and fluid reservoir, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4.Concentration is 1mol/L.The Li that positive active material mol ratio is 1: 3 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.2mol/L 2s 4.

In positive pole reative cell, plus plate current-collecting body is also provided with positive conductive material acetylene black, its concrete set-up mode is that 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene on plus plate current-collecting body with weight ratio 9: 1.

Plus plate current-collecting body is 100 object stainless (steel) wires.

Barrier film 2:

Barrier film 2 in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3

Anode chamber is closed reaction chamber, and electrolyte liquid is organic solvent PC: DMC=1: 1, and electrolyte is LiBF 4, concentration is 1mol/L.Negative pole adopts metal lithium sheet.

Embodiment 6:

Battery structures in the present embodiment etc. are substantially the same manner as Example 1, and its difference is that the constituent of the anode sizing agent adopted in the present embodiment is different from embodiment 1, is specially:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4.Concentration is 1mol/L.The Li that positive active material mol ratio is 1: 1 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.1mol/L 2s 2.

Embodiment 7 (26)

Battery structure in the present embodiment is substantially the same manner as Example 1, the constituent of the anode sizing agent adopted in the present embodiment, and the material of other battery structures is different from embodiment 1, is specially:

Cathode chamber part 1:

Anode sizing agent: anode electrolyte: solvent is two fluoroform sulfimide salt [EMIM] Tf of ionic liquid 1-ethyl-3-methylimidazole 2n, electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.5mol/L 2s 8.

Plus plate current-collecting body is also provided with positive conductive material: porous carbon, is specially and 100mg porous carbon is mixed rear roll extrusion with binding agent PTFE in nickel foam with weight ratio 9: 1.

Barrier film 2:

Barrier film 2 is the nafion117 film after lithiumation.Concrete lithiumation process is:

A. be 80 degrees Celsius by nafion117 film being immersed in temperature, concentration is 3%H 2o 2hydrogen peroxide solution in, process 1 hour;

B. deionized water rinsing is used 3 times;

C. nafion117 film being immersed in temperature is 80 degree, and concentration is the H of 3% 2o 2in hydrogen peroxide solution, process 1 hour;

D. nafion117 film being immersed in temperature is 80 degree, and concentration is the HNO of 10% 3in the aqueous solution, process 1 hour;

E. deionized water rinsing is used 3 times

F. nafion117 film being immersed in temperature is 80 degrees Celsius, and concentration is in the LiOH lithium hydroxide aqueous solution of 3M (/L), processes 24 hours;

G. use deionized water rinsing 3 times, at 50 degrees Celsius of vacuum dryings, until remove the moisture on nafion117 film completely, can use.

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is TEGDME, and electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole is metal lithium sheet.

Embodiment 8:(29)

A kind of liquid stream chargeable lithium-sulphur battery, adopts scheme 1 detailed process as follows:

Battery structure in the present embodiment is substantially the same manner as Example 1, the constituent of the anode sizing agent adopted in the present embodiment, and the material of other battery structures is different from embodiment 1, is specially:

Cathode chamber part 1:

Anode sizing agent: anode electrolyte: solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4, concentration is 1mol/L.The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.5mol/L 2s 8.

Plus plate current-collecting body is also provided with positive conductive material: the carbon of N doping, is specially: after being mixed with weight ratio 9: 1 with binding agent PTFE by the carbon of 100mg N doping, roll extrusion is at 100 object stainless (steel) wires.

Barrier film 2: be inoganic solids pottery lithium ion conductor film: (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent PC: DMC=1: 1, electrolyte is LiBF 4, concentration is 1mol/L.

Negative pole is metal lithium sheet.

Embodiment 9:

As shown in Figure 2, the liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 1.Difference is between the two to be mixed in anode sizing agent by positive conductive material 15 in the present embodiment to use, and circulates between fluid reservoir and positive pole reative cell with anode sizing agent.

Cathode chamber part 1:

Anode sizing agent is be mixed into positive active material in anode electrolyte and positive conductive material.

Anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.The Na that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Na that active material is concentration 1mol/L 2s 8.

Positive conductive material is account for the acetylene black that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Barrier film in the present embodiment is organic polymer sodium ion conductor film: through the Nafion film of sodium process.

The concrete sodium process of above-mentioned Nafion film is:

A. Nafion film being immersed in temperature is 80 degrees Celsius, and concentration is 3%H 2o 2aqueous hydrogen peroxide solution in, process 1 hour;

B. by Nafion film deionized water rinsing 3 times;

C. Nafion film being immersed in temperature is 80 degrees Celsius, and concentration is 3%H 2o 2aqueous hydrogen peroxide solution in, 1 hour;

D. Nafion film being immersed in temperature is 80 degrees Celsius, does is concentration 0.5M (0.5M/L?) H 2sO 4in the aqueous solution, process 1 hour;

E. by Nafion film deionized water rinsing 3 times;

F. film being immersed in temperature is 80 degrees Celsius, and concentration is in the NaOH sodium hydrate aqueous solution of 5M/L, processes 4 hours;

G. deionized water rinsing 3 times, carries out vacuum drying to Nafion film under 50 degree of conditions, can use after removing the moisture on it.

Anode chamber part 3:

Electrolyte liquid, solution is organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.

Negative pole 31 is sodium metal sheet.

Embodiment 10

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode sizing agent is be mixed into positive active material in anode electrolyte and positive conductive material.

Anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.The Na that positive active material mol ratio is 1: 11 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Na that active material is concentration 1mol/L 2s 12.

Positive conductive material is account for the acetylene black that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Barrier film in the present embodiment is organic polymer sodium ion conductor film: through the Nafion film of sodium process.

Anode chamber part 3:

Electrolyte liquid, solution is organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.

Negative pole 31 is sodium metal sheet.

Embodiment 11

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode sizing agent is be mixed into positive active material in anode electrolyte and positive conductive material.

Anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.Anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.The Na that positive active material mol ratio is 1: 9 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Na that active material is concentration 0.5mol/L 2s 10.

Positive conductive material is account for the acetylene black that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Barrier film in the present embodiment is organic polymer sodium ion conductor film: through the Nafion film of sodium process.

Anode chamber part 3:

Electrolyte liquid, solution is organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.

Negative pole 31 is sodium metal sheet.

Embodiment 12

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode sizing agent: anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.The Na that positive active material mol ratio is 1: 5 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Na that active material is concentration 0.3mol/L 2s 6.

Positive conductive material is account for the acetylene black that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Barrier film in the present embodiment is organic polymer sodium ion conductor film: through the Nafion film of sodium process.

Anode chamber part 3:

Electrolyte liquid, solution is organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.

Negative pole 31 is sodium metal sheet.

Embodiment 13

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode sizing agent: anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.The Na that positive active material mol ratio is 1: 3 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Na that active material is concentration 0.2mol/L 2s 4.

Positive conductive material is account for the acetylene black that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Barrier film in the present embodiment is organic polymer sodium ion conductor film: through the Nafion film of sodium process.

Anode chamber part 3:

Electrolyte liquid, solution is organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.

Negative pole 31 is sodium metal sheet.

Embodiment 14

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode sizing agent: anode electrolyte: solvent is organic solvent DMSO, electrolyte is sodium salt NaPF 6; Concentration is 1mol/L.The Na that positive active material mol ratio is 1: 1 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Na that active material is concentration 0.1mol/L 2s 2.

Positive conductive material is account for the acetylene black that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Barrier film in the present embodiment is organic polymer sodium ion conductor film: through the Nafion film of sodium process.

Anode chamber part 3:

Electrolyte liquid, solution is organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.

Negative pole 31 is sodium metal sheet.

Embodiment 15

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part:

Anode sizing agent: the solvent of electrolyte is: solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.5mol/L 2s 8.

Positive conductive material is the acetylene black that addition accounts for that anode sizing agent volume ratio is 10%.

Plus plate current-collecting body is 100 object stainless (steel) wires.

Barrier film 2:

Barrier film 2 is inoganic solids pottery lithium ion conductor film (LISICON)-LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent EC: DMC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 16

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode sizing agent: anode electrolyte: solvent is ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate [BMIM] PF 6, electrolyte is lithium salts LiPF 6; Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 9 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.5mol/L 2s 10.

In anode sizing agent, add positive conductive material again, account for the Graphene that anode sizing agent volume ratio is 15%.

Plus plate current-collecting body is 200 object aluminium nets.

Barrier film 2:

Film in the present embodiment is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent THF, electrolysis is matter LiPF 6, concentration is 1mol/L.

Negative pole 31 adopts metal lithium sheet.

Embodiment 17

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 9.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 9, is specially:

Cathode chamber part 1:

Anode electrolyte: solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.

Positive active material S is added in anode electrolyte 8, be mixed into anode sizing agent, adding active material in anode sizing agent is concentration 1mol/L.

The acetylene black as positive conductive material is added again in anode electrolyte.Its addition is be 15% with the volume ratio of anode sizing agent.

Plus plate current-collecting body adopts the aluminium foil of 50 micron thickness.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent PC: DMC=1: 1, electrolyte is LiBF 4, concentration is 1mol/L.Does negative pole 31 adopt metal lithium sheet (without requirements such as thickness?).

Embodiment 18

As shown in Figure 3, liquid stream chargeable lithium-sulphur battery positive pole in the present embodiment is identical with embodiment 1 with membrane portions structure, its difference is that the anode chamber 35 of battery in the present embodiment is connected with negative pole fluid reservoir 34, electrolyte liquid 33 is by being arranged between anode chamber 35 and negative pole fluid reservoir 34, piston pump 36 on the pipeline being communicated with both provides power, circulates between anode chamber 35 and negative pole fluid reservoir 34.

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DMSO, electrolyte is lithium salts LiPF 6.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 1mol/L 2s 8.

Positive conductive material is acetylene black, is specially and 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode: 100 object stainless (steel) wires.

Membrane portions 2:

Barrier film is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 19

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DMSO, electrolyte is lithium salts LiPF 6.Concentration is 1mol/L.In anode electrolyte, add a certain amount of mol ratio of positive active material is the Li of 1: 11 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 1mol/L 2s 12.

A certain amount of positive active material Li 2s: S is dissolved in anode electrolyte according to mol ratio 1: 11, forms the Li of 1mol/L 2s 12.

Positive conductive material is acetylene black, is specially and 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode: 100 object stainless (steel) wires.

Membrane portions 2:

Barrier film is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 20

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DMSO, electrolyte is lithium salts LiPF 6.Concentration is 1mol/L.In anode electrolyte, add a certain amount of mol ratio of positive active material is the Li of 1: 9 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.5mol/L 2s10.

Positive conductive material is acetylene black, is specially and 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode: 100 object stainless (steel) wires.

Membrane portions 2:

Barrier film is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 21

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DMSO, electrolyte is lithium salts LiPF 6.Concentration is 1mol/L.In anode electrolyte, add a certain amount of mol ratio of positive active material is the Li of 1: 5 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.3mol/L 2s 6.

Positive conductive material is acetylene black, is specially and 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode: 100 object stainless (steel) wires.

Membrane portions 2:

Barrier film is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 22

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DMSO, electrolyte is lithium salts LiPF 6.Concentration is 1mol/L.In anode electrolyte, add a certain amount of mol ratio of positive active material is the Li of 1: 3 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.2mol/L 2s 4.

Positive conductive material is acetylene black, is specially and 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode: 100 object stainless (steel) wires.

Membrane portions 2:

Barrier film is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 23

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DMSO, electrolyte is lithium salts LiPF 6.Concentration is 1mol/L.In anode electrolyte, add a certain amount of mol ratio of positive active material is the Li of 1: 1 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is concentration 0.1mol/L 2s 2.

Positive conductive material is acetylene black, is specially and 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode: 100 object stainless (steel) wires.

Membrane portions 2:

Barrier film is the nafion117 film after lithiumation.

Anode chamber part 3:

Electrolyte liquid: solvent is EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 is metal lithium sheet.

Embodiment 24

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

A kind of liquid stream chargeable lithium-sulphur battery, adopts scheme 3 detailed process as follows:

Cathode chamber part:

The solvent of electrolyte is: solvent is ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate [EMIM] BF 4, electrolyte is lithium salts LiBF 4; Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 3 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material concentration is 3mol/L 2s 4.

Positive conductive material is the carbon nano-tube be mixed in anode electrolyte, and its addition is 20% of the volume ratio accounting for anode sizing agent.And to this slurry Keep agitation in charge and discharge process.

Plus plate current-collecting body adopts 100 object titanium nets.

Barrier film 2:

Barrier film in the present embodiment is inoganic solids pottery and organic composite lithium ion conductor film, is specially the inorganic Al depositing 3nm 2o 3organic N afion film.

Anode chamber part 3:

Electrolyte liquid: solvent is machine solvent TMSO, and electrolyte is LiTFSI, and concentration is 1mol/L.

Negative pole 31 adopts metal lithium sheet.

Embodiment 25

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part 1:

The solvent of anode electrolyte is: solvent is organic solvent TMSO, and electrolyte is lithium salts LiPF 6; Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, adding active material concentration in anode sizing agent is 1mol/L Li 2s 8.

Positive active material is Graphene, is specially and 100mg Graphene is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode is 100 object stainless (steel) wires.

Barrier film 2:

For isolated sub-conducting organic/inorganic composite film, be specially the Al being provided with a layer thickness 4nm 2o 3organic N afion film.

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 adopts metal lithium sheet.

Embodiment 26

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part 1:

Anode electrolyte: solvent is organic solvent TMSO, electrolyte lithium salt LiPF 6; Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 11 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, adding active material concentration in anode sizing agent is 1mol/L.

Positive active material is Graphene, is specially and 100mg Graphene is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode is 100 object stainless (steel) wires.

Barrier film 2:

For inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 adopts metal lithium sheet.

In the present embodiment, pass through limited reactions concentration in the whole charging and discharging course of reaction of whole battery, only realize Li 2s 12→ Li 2s 4between circulation, ensure that reactive material is in liquid condition.

Embodiment 27

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 18.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 18, is specially:

Cathode chamber part:

Anode electrolyte: solvent is organic solvent TMSO, electrolyte is lithium salts LiPF 6; Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 1mol/L 2s 8.

Positive active material is Graphene, is specially and 100mg Graphene is mixed rear roll extrusion with binding agent PTFE in positive collector electrode with weight ratio 9: 1.

Positive collector electrode is 100 object stainless (steel) wires.

Barrier film 2:

Film in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12) both positive and negative polarity is isolated.

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent EC: DEC=1: 1, electrolyte is LiPF 6, concentration is 1mol/L.

Negative pole 31 adopts metal lithium sheet.

In the present embodiment, pass through limited reactions concentration in the whole charging and discharging course of reaction of whole battery, only realize Li 2s 8→ Li 2s 4between circulation, ensure that reactive material is in liquid condition.

Embodiment 28

As shown in Figure 4, the liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is in the same manner as in Example 8.Difference is between the two the set-up mode of conductive materials 15 and the constituent of electrolyte and active material.In the present embodiment, positive conductive material 15 is mixed with anode sizing agent, and in the course of work of battery, circulate between cathode chamber and positive pole fluid reservoir with anode sizing agent.

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 7 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 0.5mol/L 2s 8.

Positive conductive material is acetylene black, and the volume ratio that its addition accounts for anode sizing agent is 10%.

Plus plate current-collecting body 16 is 100 object stainless (steel) wires.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.Negative pole 31 is metal lithium sheet.

Embodiment 29

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 28.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 28, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 11 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 1mol/L 2s 12.

Positive conductive material is acetylene black, and the volume ratio that its addition accounts for anode sizing agent is 10%.

Plus plate current-collecting body 16 is 100 object stainless (steel) wires.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.Negative pole 31 is metal lithium sheet.

Embodiment 30

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 28.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 28, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 9 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 0.5mol/L 2s 10.

Positive conductive material is acetylene black, and the volume ratio that its addition accounts for anode sizing agent is 10%.

Plus plate current-collecting body 16 is 100 object stainless (steel) wires.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.Negative pole 31 is metal lithium sheet.

Embodiment 31

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 28.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 28, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 5 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 0.3mol/L 2s 6.

Positive conductive material is acetylene black, and the volume ratio that its addition accounts for anode sizing agent is 10%.

Plus plate current-collecting body 16 is 100 object stainless (steel) wires.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.Negative pole 31 is metal lithium sheet.

Embodiment 32

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 28.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 28, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 3 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 0.2mol/L 2s 4.

Positive conductive material is acetylene black, and the volume ratio that its addition accounts for anode sizing agent is 10%.

Plus plate current-collecting body 16 is 100 object stainless (steel) wires.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.Negative pole 31 is metal lithium sheet.

Embodiment 33

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 28.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 28, is specially:

Cathode chamber part:

Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.

The Li that positive active material mol ratio is 1: 1 is added in anode electrolyte 2s: S, be mixed into anode sizing agent, in anode sizing agent, add the Li that active material is 0.2mol/L 2s 4.

Positive conductive material is acetylene black, and the volume ratio that its addition accounts for anode sizing agent is 10%.

Plus plate current-collecting body 16 is 100 object stainless (steel) wires.

Barrier film 2:

Adopt inoganic solids pottery lithium ion conductor film LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1, and electrolyte is LiPF 6, concentration is 1mol/L.Negative pole 31 is metal lithium sheet.

Embodiment 34

Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and battery basic structure is identical with embodiment 28.And the constituent of the anode sizing agent adopted, and the material of other battery structures is different from embodiment 28, is specially:

Cathode chamber part 1:

Anode electrolyte: solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.

In anode electrolyte, add positive active material is Li 2s, is mixed into anode sizing agent, and adding active material concentration in anode sizing agent is 1mol/L.

The acetylene black as positive conductive material is added again in anode electrolyte.Its addition is be 40% with the volume ratio of anode sizing agent.

Plus plate current-collecting body adopts the aluminium foil of 100 microns.

Barrier film 2:

Barrier film in the present embodiment is inoganic solids pottery lithium ion conductor film (LISICON) LiCGC (Li 1+x+yal xti 2-xsi yp 3-yo 12).

Anode chamber part 3:

Electrolyte liquid: solvent is organic solvent is EC: DEC=1: 1; Electrolyte is LiPF 6; Concentration is 1mol/L.Negative pole 31 adopts metal lithium sheet.

The first Zhou Fang electricity of each battery of the above embodiment of table 2 fits capacity and 50 weeks capability retentions

Illustration First Zhou Fang electricity is against capacity (mAh/g) 50 weeks capability retentions (%) Embodiment 1 938 97% Embodiment 2 1064 96% Embodiment 3 1015 94% Embodiment 4 798 92% Embodiment 5 712 89% Embodiment 6 498 84% Embodiment 7 935 96%

Embodiment 8 945 94% Embodiment 9 899 94% Embodiment 10 969 92% Embodiment 11 815 88% Embodiment 12 723 87% Embodiment 13 569 82% Embodiment 14 452 80% Embodiment 15 956 95% Embodiment 16 867 91% Embodiment 17 986 78% Embodiment 18 945 86% Embodiment 19 1040 95% Embodiment 20 802 92% Embodiment 21 732 90% Embodiment 22 785 89% Embodiment 23 446 82% Embodiment 24 653 85% Embodiment 25 952 94% Embodiment 26 258 96% Embodiment 27 194 97% Embodiment 28 909 93% Embodiment 29 1012 89% Embodiment 30 986 85% Embodiment 31 803 82%

Embodiment 32 756 79% Embodiment 33 452 75% Embodiment 34 823 79%

Adopt traditional lithium-sulfur cell technique, the standard button cell CR3032 obtained assembles, and wherein electrolyte adopts 1mol/L LiTFSI to be dissolved as TEGDME, using lithium sheet as negative pole.At C/10 multiplying power constant current charge-discharge, first all composite material electric discharge 612mAh/g, but overcharge obviously due to strong " effect of shuttling back and forth ", first all efficiency is 137%, and after 50 weeks, specific capacity conservation rate only has 51%.

In addition, Fig. 5, for adopting battery structure of the present invention shown in Fig. 1, uses Li 2s 8when being acetylene black as active material, conductive materials, the first all charging and discharging curve figure of measured typical case.Fig. 6 is battery structure of the present invention shown in Fig. 2, and adopts Li 2s 8when being acetylene black as active material, conductive materials, the first all charging and discharging curve figure of measured typical case.In Fig. 6, dotted portion is the head week charging and discharging curve of traditional lithium-sulfur cell.Fig. 7 is battery structure of the present invention shown in Fig. 4, adopts Li 2s 8as active material, the first all charging and discharging curve figure of measured typical case, in figure, dotted portion is the head week charging and discharging curve without conductive additive, and solid line is the head week charging and discharging curve that with the addition of 20% acetylene black.By to the two contrast, add conductive additive and form slurry, greatly can improve the electron conduction of reaction system, greatly reduce discharge and recharge polarization, significantly improve first all charge/discharge capacities.

Electrolyte, conductive materials, positive collector electrode material that anode portion in the present invention in disclosed liquid stream chargeable lithium-sulphur battery uses, barrier film material, bath composition in negative pole and concentration, negative pole material and negative collector electrode material, except disclosed in above-described embodiment, also can be respectively:

Solvent in the solvent solution that anode electrolyte adopts is: organic solvent or ionic liquid, wherein organic solvent is propylene carbonate (PC), vinyl carbonate (EC), butylene carbonic ester (BC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), carbonic acid di-n-propyl ester (DPC), diisopropyl carbonate (DIPC), ethyl propyl carbonic acid ester (EPC), ethylene isopropyl ester (EIPC), dimethoxy-ethane (DME), oxolane (THF), 2-methyltetrahydrofuran (MeTHF), diglycol ethylene dimethyl ether (DGM), contracting TRIGLYME (TGM), contracting tetraethyleneglycol dimethyl ether (TEGM), dimethyl sulfoxide (DMSO) (DMSO), sulfolane (TMSO), dimethyl sulfone (MSM), 1, 3-dioxolanes (1, 3-DOL).By following kind, one or more are formed ionic liquid, are specially: imidazole type ion liquid is as 1-ethyl-3-methylimidazole tetrafluoroborate [EMIM] BF 4, 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM] BF 4, 1-ethyl-3-methylimidazole three cyanogen first salt (two fluoroform sulfimide salt [EMIM] Tf of [EMIM] TCCN, 1-ethyl-3-methylimidazole 2n, three hexyl myristyl phosphorus tetrazolium [P66614] [Tetz], three hexyl myristyl phosphorus imidazole salts [P66614] [Im], 1-ethyl-3-methylimidazole tetrazolium [EMIM] [Tetz], two fluoroform sulfimide salt [BMIM] Tf of 1-butyl-3-methylimidazole 2n, 1-butyl-3-methylimidazole hexafluorophosphate [BMIM] PF 6, two fluoroform sulfimide salt [C8MIM] Tf of 1-butyl-3-methylimidazole fluoroform sulphonate [BMIM] OTF, 1-butyl-3-methylimidazole dicyandiamide salt [BMIM] DCN, 1-octyl group-3-methylimidazole 2n, 1-hexyl-3-methylimidazolium tosylate [C6MIM] OTS, 1-butyl-3-methylimidazole N, waste propylhomoserin salt [C4MIM] BDTC, 1-butyl of N-dialkyl group-3-methylimidazolidinyl trithiocarbonate [C4MIM] TTC, 1-butyl-3-methylimidazole alkoxyl dithiocarbonate [C4MIM] OTDC; Pyridine type ionic liquid is as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; Piperidines type ionic liquid as N-methyl, propylpiperdine two fluoroform sulfimide salt PP13TFSI, N-methyl, propylpiperdine fluoroform sulphonate PP13OTF, N-methyl, propylpiperdine hexafluorophosphate PP13PF 6, N-methyl, propylpiperdine bromination PP13Br; Pyrrolidines type ionic liquid as N-methyl, the two fluoroform sulfimide salt BMPTf of butyl pyrrolidine 2n, ethanaminium, N-methvl, butyl pyrrolidine, chlorination N-methyl, butyl pyrrolidine; Quaternary ammonium type ionic liquid is as TBuA tetrafluoroborate etc.

Positive active material can adopt M xs yin one or more, wherein, M=Li or Na; 0 < x≤2; 0 < y≤12; Positive active material can be liquid state also can be solid-state or the mixed phase of the two composition; The concentration 0.01-10mol/L of positive active material in anode electrolyte, preferable range: 0.1-3mol/L.

The organic electrolyte of both positive and negative polarity be used as electrolyte be selected from following one or more wherein lithium salts be: LiPF 6, LiAsF 6, LiSbF 6, LiBF 4, LiClO 4, LiAlCl 4, LiGaCl 4, LiB 10cl 10, LiCF 3sO 3, LiC4F9SO3, LiN (CxF2x+1SO2) (CyF2y+1SO2), wherein, x and y is natural number, LiBF z(CF 3) 4-z, the wherein natural number of z≤4; Sodium salt is: NaPF 6, NaBF 4, NaClO 4, NaAlCl 4, NaCF 3sO 3, NaC 4f 9sO 3, in electrolyte, the concentration of lithium salts is 0.5 ~ 5.0mol/L.

Positive conductive material has two kinds of existence forms in the battery, exists with positive pole reative cell shown in Fig. 1,3 for it is fixing, in this case, can by carbon by adhesive coated or roll extrusion on the collector made with metal or its alloy.As shown in Figure 2,4, positive conductive material also can be blended in anode sizing agent, with anode sizing agent in cell operations, circulates between cathode chamber and positive pole fluid reservoir, the addition of this positive conductive material is the 0-50% of electrolyte system volume, preferable range: 0%-30%.

Electrolyte liquid is non-water organic electrolyte.

Negative pole (active material in negative pole is negative pole) adopts lithium metal or sodium metal or its alloy: lithium silicon, lithium-tin alloy.

Positive and negative electrode collector can be the net of the metals such as nickel, stainless steel, titanium, aluminium and alloy composition thereof or paper tinsel wherein net be 20-500 order, or with above metal and alloy thereof be base metal foam or porous metals, also can be that carbon class negative material such as one or more mixtures such as the carbon of graphite, MCMB (MCMB), hard carbon ball, porous carbon, acetylene black, Graphene, carbon nano-tube, carbon fiber, N doping are formed.

Positive and negative electrode material that fluid reservoir uses can be metal or its alloy as aluminium, aluminium alloy, titanium, titanium alloy, stainless steel, also can be other organic polymer material as polytetrafluoroethylene, PVP, also can use inorganic ceramic composite material.

Battery disclosed in the present invention has that energy density is high, specific capacity large, have extended cycle life, cost is low, energy utilization efficiency high, the extensive energy storage device needed for clean energy resource solar energy, wind-force can be widely used in, and the field such as intelligent grid peak regulation, distribution power station, back-up source, communication base station, especially be suitable as extensive energy storage device, but scope is not restricted to this.

Claims (19)

1. one kind can be filled alkali metal-sulphur flow battery, it is characterized in that, described battery cathode chamber part, barrier film and anode chamber part, described cathode chamber part comprises positive pole reative cell and the fluid reservoir with cathode chamber pipeline communication, described positive pole reative cell comprises, positive collector electrode and the anode sizing agent circulated between positive pole reative cell and fluid reservoir used as positive pole; Described anode chamber part is negative reaction room, comprises negative pole, negative collector electrode and electrolyte liquid; Described barrier film is single ion conductor film, is arranged between described positive pole reative cell and negative reaction room, and ensures to only have single work ionic conduction between both positive and negative polarity, and without any mass transfer of other inoperative ion; Described anode sizing agent is made up of anode electrolyte and the positive active material be blended in anode electrolyte, and described positive active material is M xs yin one or more, wherein M is element Li or Na, 0<x≤2; 0<y≤12.
2. one according to claim 1 can fill alkali metal-sulphur flow battery, it is characterized in that, also comprises positive conductive material in described anode sizing agent; Described positive conductive material is material with carbon element: in the carbon of acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, N doping, one or more mixtures are formed.
3. one according to claim 2 can fill alkali metal-sulphur flow battery, it is characterized in that, the addition of described positive conductive material is account for anode electrolyte volume 0 ~ 50%.
4. one according to claim 3 can fill alkali metal-sulphur flow battery, it is characterized in that, the addition of described positive conductive material is account for anode electrolyte volume 0% ~ 30%.
5. according to claim 1ly fill alkali metal-sulphur flow battery, it is characterized in that, described positive pole reative cell also comprises the positive conductive material be arranged in positive collector electrode, and described conductive materials is material with carbon element: in the carbon of acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, N doping, one or more mixtures are formed.
6. according to claim 1ly fill alkali metal-sulphur flow battery, it is characterized in that, described positive active material concentration range in the electrolytic solution exists: 0.01 ~ 10mol/L.
7. according to claim 6ly fill alkali metal-sulphur flow battery, it is characterized in that, described positive active material concentration range in the electrolytic solution exists: 0.1 ~ 3mol/L.
8. according to claim 1ly fill alkali metal-sulphur flow battery, it is characterized in that, described negative pole is lithium metal or sodium metal or its alloy.
9. according to claim 1ly fill alkali metal-sulphur flow battery, it is characterized in that, described single ion conductor film only allows the transmission of single work ion, and without other liquid and inoperative ion diffuse; Single ion conductor film is inorganic ceramic membrane, organic polymer films or inorganic/organic composite ceramic membrane.
10. according to claim 9ly fill alkali metal-sulphur flow battery, it is characterized in that, described inorganic ceramic membrane is single ion conductor inorganic ceramic membrane; Described single ion conductor inorganic ceramic membrane is xLi 2s+ySiS 2+ zLi 3pO 4, iLi 2s+mGeS 2+ nP 2s 5, hLi 2s+kSiS 2+ jP 2s 5or aLi 2o+bSiO 2+ cTiO 2+ dAl 2o 3+ eP 2o 5, wherein 0<x≤1,0<y≤1,0<z≤1,0<i≤1,0<m≤1,0<n≤1,0<h≤1,0<k≤1,0<j≤1,0<a≤1,0<b≤1,0<c≤1,0≤d≤1,0<e≤1; Described organic polymer films is isolated sub-conducting organic film; Organic/inorganic compound film is isolated sub-conducting organic/inorganic compound film.
11. according to claim 10ly fill alkali metal-sulphur flow battery, and it is characterized in that, described isolated sub-conducting organic/inorganic compound film is be provided with the adjustable inorganic Al of a layer thickness 2o 3organic N afion film; Described isolated sub-conducting organic film is the perfluorinated ion-exchange membrane through lithiumation or sodium process.
12. can fill alkali metal-sulphur flow battery according to claim 1, it is characterized in that, the electrolyte in described positive pole and electrolyte liquid be selected from following one or more wherein lithium salts be: LiPF 6, LiAsF 6, LiSbF 6, LiBF 4, LiClO 4, LiAlCl 4, LiGaCl 4, LiB 10cl 10, LiCF 3sO 3, LiC 4f 9sO 3, LiN (C xf 2x+1sO 2) (C yf 2y+1sO 2), wherein, x and y is natural number, LiBF z(CF 3) 4-z, wherein z≤4 and be natural number; Sodium salt is: NaPF 6, NaBF 4, NaClO 4, NaAlCl 4, NaCF 3sO 3, NaC 4f 9sO 3, described electrolytical concentration is 0.5 ~ 5.0mol/L.
13. according to claim 1ly fill alkali metal-sulphur flow battery, and it is characterized in that, the solvent in described electrolyte is organic solvent or ionic liquid.
14. according to filling alkali metal-sulphur flow battery described in claim 13, it is characterized in that, the organic solvent that described organic electrolyte uses is selected from following one or more: propylene carbonate, vinyl carbonate, butylene carbonic ester, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid di-n-propyl ester, diisopropyl carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, dimethoxy-ethane, oxolane, 2-methyltetrahydrofuran, diglycol ethylene dimethyl ether, contracting TRIGLYME, contracting tetraethyleneglycol dimethyl ether, dimethyl sulfoxide (DMSO), sulfolane, dimethyl sulfone, 1, 3-dioxolanes.
15. according to filling alkali metal-sulphur flow battery described in claim 13, it is characterized in that, described ionic liquid is made up of one or more in imidazole type ion liquid, pyridine type ionic liquid, piperidines type ionic liquid, pyrrolidines type ionic liquid, quaternary ammonium type ionic liquid; Wherein,
Imidazole type ion liquid is 1-ethyl-3-methylimidazole tetrafluoroborate [EMIM] BF 4, 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM] BF 4, two fluoroform sulfimide salt [EMIM] Tf of 1-ethyl-3-methylimidazole three cyanogen first salt [EMIM] TCCN, 1-ethyl-3-methylimidazole 2n, three hexyl myristyl phosphorus tetrazolium [P66614] [Tetz], three hexyl myristyl phosphorus imidazole salts [P66614] [Im], 1-ethyl-3-methylimidazole tetrazolium [EMIM] [Tetz], two fluoroform sulfimide salt [BMIM] Tf of 1-butyl-3-methylimidazole 2n, 1-butyl-3-methylimidazole hexafluorophosphate [BMIM] PF 6, two fluoroform sulfimide salt [C8MIM] Tf of 1-butyl-3-methylimidazole fluoroform sulphonate [BMIM] OTF, 1-butyl-3-methylimidazole dicyandiamide salt [BMIM] DCN, 1-octyl group-3-methylimidazole 2n, 1-hexyl-3-methylimidazolium tosylate [C6MIM] OTS, 1-butyl-3-methylimidazole N, waste propylhomoserin salt [C4MIM] BDTC, 1-butyl of N-dialkyl group-3-methylimidazolidinyl trithiocarbonate [C4MIM] TTC or 1-butyl-3-methylimidazole alkoxyl dithiocarbonate [C4MIM] OTDC;
Pyridine type ionic liquid is N-ethylpyridine tetrafluoroborate or N-ethylpyridine hexafluorophosphate;
Piperidines type ionic liquid is N-methyl, propylpiperdine two fluoroform sulfimide salt PP13TFSI, N-methyl, propylpiperdine fluoroform sulphonate PP13OTF, N-methyl, propylpiperdine hexafluorophosphate PP13PF 6or N-methyl, propylpiperdine bromination PP13Br;
Pyrrolidines type ionic liquid is N-methyl, the two fluoroform sulfimide salt BMPTf of butyl pyrrolidine 2n, ethanaminium, N-methvl, butyl pyrrolidine, chlorination N-methyl, butyl pyrrolidine;
Quaternary ammonium type ionic liquid is TBuA tetrafluoroborate.
16. according to claim 1ly fill alkali metal-sulphur flow battery, it is characterized in that, described positive and negative electrode collector adopts the net of nickel, stainless steel, titanium, aluminum metal and alloy composition thereof or paper tinsel to make, wherein net is 20 ~ 500 orders, or with above metal and alloy thereof be base metal foam or porous metals, or carbon class negative material.
17. according to claim 16ly fill alkali metal-sulphur flow battery, it is characterized in that, carbon class negative material, one or more mixtures such as the carbon of graphite, MCMB, hard carbon ball, porous carbon, acetylene black, Graphene, carbon nano-tube, carbon fiber, N doping are formed.
18. can fill alkali metal-sulphur flow battery according to described in above-mentioned arbitrary claim, it is characterized in that, described anode chamber part also comprises the negative pole fluid reservoir be connected by pipeline with anode chamber.
19. according to claim 1ly fill alkali metal-sulphur flow battery, it is characterized in that the material that fluid reservoir uses that anode portion adopts is aluminium, aluminium alloy, titanium, titanium alloy, stainless steel; Or polytetrafluoroethylene, PVP organic polymer material, or inorganic ceramic composite material.
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