CN102956866A - Chargeable alkali metal-sulfur liquid flow battery - Google Patents

Chargeable alkali metal-sulfur liquid flow battery Download PDF

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CN102956866A
CN102956866A CN2011102491697A CN201110249169A CN102956866A CN 102956866 A CN102956866 A CN 102956866A CN 2011102491697 A CN2011102491697 A CN 2011102491697A CN 201110249169 A CN201110249169 A CN 201110249169A CN 102956866 A CN102956866 A CN 102956866A
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electrolyte
anode
alkali metal
sizing agent
sulphur
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CN102956866B (en
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胡勇胜
索鎏敏
李泓
陈立泉
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Institute of Physics of CAS
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Abstract

A chargeable alkali metal-sulfur liquid flow battery comprises a positive electrode chamber portion, a diaphragm and a negative electrode chamber portion, wherein the positive electrode chamber portion comprises a positive electrode reaction chamber and a liquid storage tank communicated with a positive electrode chamber pipeline. The positive reaction chamber comprises a positive electrode collector and positive electrode sizing, and the positive electrode sizing used for a positive electrode circulates between the positive electrode reaction chamber and the liquid storage tank. The negative electrode chamber portion comprises a negative electrode reaction chamber comprising a negative electrode, a negative electrode collector and negative electrode electrolyte, and the diaphragm is a single-ion conductor diaphragm and is arranged between the positive electrode reaction chamber and the negative reaction chamber. Only one working ion rather than any other substances such as non-working ions is guaranteed to conduct between the positive electrode and the negative electrode. The positive electrode sizing is composed of positive electrode electrolyte and positive active matters mixed in the positive electrode electrolyte, and the positive active matters are one or more kinds of MxSy (M=Li or Na; 0(x</=2; 0(y</=12).

Description

A kind of alkali metal-sulphur flow battery that fills
Technical field
The present invention relates to a kind of chemical cell.Be particularly related to a kind of alkali metal-sulphur flow battery.
Background technology
Since lithium ion battery is succeeded in developing since its have that fail safe is good, voltage and specific energy are high, discharge and recharge the advantages such as the life-span is long, thereby are 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, so that have higher requirement as the lithium ion battery of energy and power resources.How discharge performance under the specific capacity that further improves lithium ion battery on the existing basis and large multiplying power has become current hot issue.In addition, how to improve the electronics that adopts the lithium ion battery dynamical system 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 that determines 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 at present commercialization is used mainly is to concentrate on transition metal embedding oxidate for lithium, the oxide and the doped compound thereof that comprise cobalt, iron, nickel, manganese, but this compounds is subjected to the restriction of self theoretical capacity to bring up at most the energy density of 300Wh/Kg, and because this kind material is solid, the charge and discharge process intermediate ion is subjected to diffusion control, thereby high rate performance promotes difficulty and the space is little, in addition since lithium ion therein diffusion process be subjected to influence of temperature change larger, make the lithium ion battery temperature scope of application very limited.Lithium-sulfur cell is because 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 because there is larger technical barrier in this system, still is at present laboratory stage.Its Main Problems is: 1) charging product elemental sulfur S 8With discharging product Li 2S conductivity is similar to insulator, and the conductivity extreme difference if need compound a large amount of electric conducting materials to work as active material, or is reduced to Nano grade or molecule rank with its particle.In addition, the many sulphions of its discharging product are soluble in electrolyte, go out nonconducting elemental sulfur or polysulfide at the conductive agent surface deposition during charging, have increased the resistance that reaches between the conductive agent particle between conductive agent and the collector.And increase along with discharging and recharging number of times, the internal resistance of cell constantly rises, and specific energy descends gradually, and this is the short main cause of lithium-sulfur cell cycle life.2) reaction of positive electrode elemental sulfur charge and discharge process is the multi-step reaction, product Li in the middle of it 2S 8, Li 2S 6, Li 2S 4Very easily be dissolved in electrolyte, the many sulphions that are dissolved in the 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 elemental sulfur of it is discharged and recharged time deposition not affect anodal electric transmission be to improve the key of lithium-sulfur cell cycle life.
Adopt traditional lithium-sulfur cell technique, specific as follows:
The elemental sulfur powder is mixed with weight ratio with porous carbon at 1: 1,155 degree under the argon gas condition, be incubated 24 hours, resulting materials is as positive active material, it is mixed according to weight ratio with acetylene black and Kynoar at 8: 1: 1, be coated on the collector aluminium foil, the baking in 10 hours of 60 degree vacuum obtains anode electrode.
Employing standard button cell CR3032 assembles, and electrolyte adopts 1mol/L LiTFSI to be dissolved as TEGDME, with the lithium sheet as negative pole.
At C/10 multiplying power constant current charge-discharge, first all composite material discharge 612mAh/g, but because strong " effect of shuttling back and forth " overcharges obviously, first all efficient is that the specific capacity conservation rate only has 51% after 137%, 50 week.
Summary of the invention
The problems referred to above for present lithium-sulfur cell exists the object of the invention is to, and proposing to adopt elemental sulfur or alkali metal sulphur compound is positive active material, adopt alkali metal that active material is got up with liquid or slurry form flow circuit-sulphur flow battery.
A kind of alkali metal-sulphur flow battery that fills, described battery comprises cathode chamber part, barrier film and anode chamber part, described cathode chamber partly comprise anodal reative cell and with the fluid reservoir of cathode chamber pipeline communication, described anodal reative cell comprises, positive collector electrode and the anode sizing agent that circulates between anodal reative cell and fluid reservoir that uses as positive pole; Described anode chamber is the negative reaction chamber partly, comprises negative pole, negative collector electrode and negative pole electrolyte; Described barrier film is the single ion conductor film, is arranged between described anodal reative cell and the negative reaction chamber, and guarantees to only have single work ionic conduction between the both positive and negative polarity, and without any mass transfer of other inoperative ion; Described anode sizing agent is made of anode electrolyte and the positive electrode active material that is blended in the anode electrolyte, and described positive active material is MxSy (M=Li or Na; 0＜x≤2; 0＜y≤12) one or more in.
Further, also comprise anodal conductive materials in the described anode sizing agent; Described anodal conductive materials is material with carbon element: one or more mixtures consist of in the carbon that acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen mix.
Further, the addition of described anodal conductive materials is to account for 0～50% of anode electrolyte volume, preferable range: 0%～30%.
Further, described anodal reative cell also comprises the anodal conductive materials that is arranged on the positive collector electrode, and described conductive materials is material with carbon element: one or more mixtures consist of in the carbon that acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen mix.
Further, the concentration range of described positive active material in electrolyte 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 the diffusion of inoperative ion; The 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 the logical organic film of single ion guide is (such as perfluorinated ion-exchange membrane (Nafion) film through lithiumation or sodium processing; Organic/inorganic compound film is that single ion guide is connected with the machine inorganic substances compound membrane.(as depositing the adjustable inorganic Al of a layer thickness by technique for atomic layer deposition at organic (Nafion) film 2O 3
Further, the electrolyte in described positive pole and the negative pole electrolyte is to 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 are natural numbers, LiBFz (CF 3) 4-z, the natural number of z≤4 wherein; 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 the described electrolyte is organic solvent or ionic liquid.
Further, the employed organic solvent of described organic electrolyte 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), carbonic acid diisopropyl ester (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, the 3-dioxolanes (1,3-DOL).
Further, described ionic liquid has one or more formations of following kind, is specially: imidazole type ion liquid such 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 tetrazoliums [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-methylimidazole toluene fulfonate [C 6MIM] OTS, 1-butyl-3-methylimidazole N, the waste propylhomoserin salt of N-dialkyl group [C 4MIM] BDTC, 1-butyl-3-methylimidazole alkyl trithiocarbonate [C 4MIM] TTC, 1-butyl-3-methylimidazole alkoxyl dithiocarbonate [C4MIM] OTDC; Pyridine type ionic liquid such as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; Piperidines type ionic liquid such as N-methyl, the two fluoroform sulfimide salt PP of propyl group piperidines 13TFSI, N-methyl, propyl group piperidines fluoroform sulphonate PP 13OTF, N-methyl, propyl group piperidines hexafluorophosphate PP 13PF 6, the N-methyl, propyl group piperidines bromination PP 13Br; Pyrrolidines type ionic liquid such as N-methyl, the two fluoroform sulfimide salt BMPTf of butyl pyrrolidine 2N, bromination N-methyl, butyl pyrrolidine, chlorination N-methyl, butyl pyrrolidine; Quaternary ammonium type ionic liquid such as TBuA tetrafluoroborate.
Further, described positive and negative electrode collector adopts net or the paper tinsel of the metal such as nickel, stainless steel, titanium, aluminium and alloy composition thereof to make, or metal foam or porous metals take above metal and alloy thereof as base, or carbon class negative material.
Further, carbon class negative material, one or more mixtures such as carbon that graphite, MCMB (MCMB), hard carbon ball, porous carbon, acetylene black, Graphene, carbon nano-tube, carbon fiber, nitrogen mix consist of.
Further, described anode chamber part also comprises the negative pole fluid reservoir that is connected by pipeline with anode chamber.
Further, the material that fluid reservoir uses that anodal part adopts can be metal or its alloy such as aluminium, aluminium alloy, titanium, titanium alloy, stainless steel, also can be other organic polymer material such as polytetrafluoroethylene, and PVP also can use the inorganic ceramic composite material.
The present invention has utilized alkali metal sulphide M xS y(M=Li or Na; 0＜x≤2; 0＜y≤12) at the different solubility of different phase in electrolyte, be about to polysulfide and be dissolved in the organic electrolyte, such as S 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 the electrolyte acquires a certain degree, when polysulfide in discharge when latter stage, alkali metal content raise gradually, the alkali metal polysulfide can occur and separate out phenomenon from electrolyte, whole course of reaction can present liquid-solid intersection hybrid reaction.If the on the one hand suitable controlled discharge degree of depth for example only realizes M by limited capacity 2S 8-M 2S 4Between conversion, then reactant is always liquid form, can improve to a certain extent flowability, improves dynamic performance.On the other hand, if do not control course of reaction, solid active agents is flowed with the form of slurry, reach the purpose of circulation.Therefore, this system is the chemical system that can control course of reaction, and we can pass through the controlled discharge degree of depth, by the Reversible Cycle between the ways such as the limited capacity realization any two kinds of polysulfides of alkali metal or elemental sulfur and the sulfide.
Compared with prior art, the present invention has following remarkable advantage:
(1) high-energy-density
As shown in Table 1, sulphur and the more conventional positive electrode of relevant lithium sulphur compound thereof have the theoretical specific capacity that exceeds several times, even operating voltage is on the low side, as about 2V, still are higher than conventional solid positive electrode far away after the conversion of output energy density.In addition, owing to adopt liquid fluid system, greatly reduced the proportion of collector in system, therefore, conventional lithium-ion battery system, it is large that the energy density room for promotion of battery system becomes.
The existing positive electrode of table 1 and alkali metal sulfenyl material contrast
Figure BDA0000086527760000061
Figure BDA0000086527760000071
(2) long circulation life
Because cathode chamber and anode chamber have realized separation by the single ion conductor film, only has the transmission of single work ion between two Room, and without other liquid and the diffusion of inoperative ion, active material and alkali-metal reaction have effectively been solved, avoided the shuttle back and forth effect of many sulphions between both positive and negative polarity, guaranteed that the enclosed pasture efficient that discharges and recharges approaches absolutely, thereby fundamentally thoroughly solved the poor problem of lithium-sulfur cell cycle performance.
(3) wider serviceability temperature scope
Traditional solid active agents is owing to be subject to the lithium ion diffusion control, and especially along with the decline of temperature, ionic conductance also reduces rapidly thereupon, thereby causes conventional solid electrode material temperature influence larger, the low temperature electrochemical poor-performing.This patent is owing to adopt active material and battery system, and conductivity is acted upon by temperature changes not obvious, therefore has preferably high and low temperature performance.
Description of drawings
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 is that the active material in the battery of the present invention shown in Figure 2 is Li 2S 8, when conductive materials is acetylene black, measured typical first all charging and discharging curve figure;
Fig. 6 is that the active material in the battery of the present invention shown in Figure 4 is Li 2S 8, measured typical first all charging and discharging curve figure.
Embodiment
Embodiment 1
As shown in Figure 1, the filled alkali metal in the present embodiment-sulphur flow battery comprises: cathode chamber part 1, barrier film 2, anode chamber part 3.Wherein, anodal part chamber 1 mainly comprises fluid reservoir 11, anodal reative cell 12 and is arranged on piston pump 13 and the flow valve 14 that is communicated with on fluid reservoir 11 and reative cell 12 pipelines.The anode sizing agent that just very between anodal reative cell 12 and fluid reservoir 11, circulates, anode sizing agent is comprised of anode electrolyte and the positive active material that is blended in the anode electrolyte, and wherein positive active material is M xS y(M=Li or Na; 0＜x≤2; 0＜y≤12) one or more in during work, need by piston pump it to be pumped in the anodal reative cell 12, and the size of flow can be by flow valve 14 controls.Also be provided with conductive materials 15 on the positive collector electrode 16; Conductive materials 15 is concrete dynamic modulus, but conductive materials, by adhesive coated or roll extrusion on collector 16; It act as the response area that increases in the cathode chamber, improves the conductivity of collector electrode, improves the active material reaction efficiency in the anode electrolyte.Barrier film 2 is arranged between the positive and negative electrode as the positive and negative electrode coupling part; This barrier film 2 is the single ion conductor film, and barrier film 2 should guarantee to only have between the both positive and negative polarity single ionic conduction, and without other any mass transfer.Anode chamber 3 is closed reaction chamber; Comprise negative pole 31, collector 32 and be arranged on the interior negative pole electrolyte 33 of anode chamber.
Anodal reative cell 1:
Anode electrolyte: solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiBF 4Concentration is 1mol/L.
Adding positive active material in anode electrolyte is that mol ratio is 1: 7 Li 2S: S is mixed into anode sizing agent, and adding active material concentration in the anode sizing agent is the Li of 0.5mol/L 2S 8
In anodal reative cell, also be provided with anodal conductive materials acetylene black on the collector, its concrete set-up mode is that 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode is 100 purpose 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 negative pole electrolyte 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 that adopts in the present embodiment is different from embodiment 1, is specially:
Anodal reative cell 1:
The anode sizing agent that just very between cathode chamber and fluid reservoir, circulates, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4Concentration is 1mol/L.
Adding positive active material in anode electrolyte is that mol ratio is 1: 11 Li 2S: S is mixed into anode sizing agent, and adding active material concentration in the anode sizing agent is the Li of 1mol/L 2S 12
In anodal reative cell, also be provided with anodal conductive materials acetylene black on the collector, its concrete set-up mode forms in 100 purpose stainless (steel) wire manufacturings for 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE polytetrafluoroethylene with weight ratio at 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 negative pole electrolyte 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 that adopts in the present embodiment is different from embodiment 1, is specially:
Anodal reative cell 1:
The anode sizing agent that just very between cathode chamber and fluid reservoir, circulates, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4Concentration is 1mol/L.Adding positive active material mol ratio is 1: 9 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.5mol/L 2S 10
In anodal reative cell, also be provided with anodal conductive materials acetylene black on the plus plate current-collecting body, 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 at 9: 1.
Plus plate current-collecting body is 100 purpose 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 negative pole electrolyte 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 that adopts in the present embodiment is different from embodiment 1, is specially:
Anodal reative cell 1:
The anode sizing agent that just very between cathode chamber and fluid reservoir, circulates, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4Concentration is 1mol/L.Adding positive active material mol ratio is 1: 5 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.3mol/L 2S 6
In anodal reative cell, also be provided with anodal conductive materials acetylene black on the plus plate current-collecting body, 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 at 9: 1.
Plus plate current-collecting body is 100 purpose 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 negative pole electrolyte 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 that adopts in the present embodiment is different from embodiment 1, is specially:
Anodal reative cell 1:
The anode sizing agent that just very between cathode chamber and fluid reservoir, circulates, anode electrolyte wherein: its solvent is organic solvent DOL: DME=1: 1, electrolyte is lithium salts LiBF 4Concentration is 1mol/L.Adding positive active material mol ratio is 1: 3 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.2mol/L 2S 4
In anodal reative cell, also be provided with anodal conductive materials acetylene black on the plus plate current-collecting body, 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 at 9: 1.
Plus plate current-collecting body is 100 purpose 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 negative pole electrolyte 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 that adopts in the present embodiment is different from embodiment 1, is specially:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiBF 4Concentration is 1mol/L.Adding positive active material mol ratio is 1: 1 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 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 that adopts 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 are lithium salts LiTFSI; Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.5mol/L 2S 8
Also be provided with anodal conductive materials on the plus plate current-collecting body: porous carbon is specially the 100mg porous carbon is mixed rear roll extrusion with binding agent PTFE on nickel foam with weight ratio at 9: 1.
Barrier film 2:
Barrier film 2 is the nafion117 film after the lithiumation.Concrete lithiumation process is:
A. be 80 degrees centigrade with the nafion117 film being immersed in temperature, concentration is 3%H 2O 2Hydrogen peroxide solution in, processed 1 hour;
B. use deionized water rinsing 3 times;
C. the nafion117 film being immersed in temperature is 80 degree, and concentration is 3% H 2O 2In the hydrogen peroxide solution, processed 1 hour;
D. the nafion117 film being immersed in temperature is 80 degree, and concentration is 10% HNO 3In the aqueous solution, processed 1 hour;
E. use deionized water rinsing 3 times
F. the nafion117 film being immersed in temperature is 80 degrees centigrade, and concentration is that 3M (in/L) the LiOH lithium hydroxide aqueous solution, processed 24 hours;
G. use deionized water rinsing 3 times, at 50 degrees centigrade of vacuum dryings, until remove moisture on the nafion117 film fully, can use.
Anode chamber part 3:
Negative pole electrolyte: solvent is that 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, employing scheme 1 detailed process is as follows:
Battery structure in the present embodiment is substantially the same manner as Example 1, the constituent of the anode sizing agent that adopts 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, and electrolyte is lithium salts LiBF 4, concentration is 1mol/L.Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.5mol/L 2S 8
Also be provided with anodal conductive materials on the plus plate current-collecting body: the carbon that nitrogen mixes is specially: the carbon that 100mg nitrogen is mixed mixes rear roll extrusion at 100 purpose stainless (steel) wires with binding agent PTFE with weight ratio at 9: 1.
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:
Negative pole electrolyte: solvent is organic solvent PC: DMC=1: 1, and 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 is identical among battery basic structure and the embodiment 1.Difference between the two is in the present embodiment anodal conductive materials 15 is mixed in the anode sizing agent and uses, and circulates between fluid reservoir and anodal reative cell with anode sizing agent.
Cathode chamber part 1:
Anode sizing agent is positive active material and the anodal conductive materials that is mixed in the anode electrolyte.
Anode electrolyte: solvent is organic solvent DMSO, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Adding positive active material mol ratio is 1: 7 Na in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Na of concentration 1mol/L 2S 8
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 15% acetylene black.
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 processing.
The concrete sodium process of above-mentioned Nafion film is:
A. the Nafion film being immersed in temperature is 80 degrees centigrade, and concentration is 3%H 2O 2Aqueous hydrogen peroxide solution in, processed 1 hour;
B. with deionized water rinsing 3 times of Nafion film;
C. the Nafion film being immersed in temperature is 80 degrees centigrade, and concentration is 3%H 2O 2Aqueous hydrogen peroxide solution in, 1 hour;
D. the Nafion film being immersed in temperature is 80 degrees centigrade, is concentration 0.5M (0.5M/L?) H 2SO 4In the aqueous solution, processed 1 hour;
E. with deionized water rinsing 3 times of Nafion film;
F. film being immersed in temperature is 80 degrees centigrade, and concentration is in the NaOH sodium hydrate aqueous solution of 5M/L, processes 4 hours;
G. deionized water rinsing is 3 times, under 50 degree conditions the Nafion film is carried out vacuum drying, can use after removing the moisture on it.
Anode chamber part 3:
Negative pole electrolyte, solution are organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.
Negative pole 31 is the sodium metal sheet.
Embodiment 10
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 9, is specially:
Cathode chamber part 1:
Anode sizing agent is positive active material and the anodal conductive materials that is mixed in the anode electrolyte.
Anode electrolyte: solvent is organic solvent DMSO, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Adding positive active material mol ratio is 1: 11 Na in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Na of concentration 1mol/L 2S 12
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 15% acetylene black.
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 processing.
Anode chamber part 3:
Negative pole electrolyte, solution are organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.
Negative pole 31 is the sodium metal sheet.
Embodiment 11
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 9, is specially:
Cathode chamber part 1:
Anode sizing agent is positive active material and the anodal conductive materials that is mixed in the anode electrolyte.
Anode electrolyte: solvent is organic solvent DMSO, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Anode electrolyte: solvent is organic solvent DMSO, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Adding positive active material mol ratio is 1: 9 Na in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Na of concentration 0.5mol/L 2S 10
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 15% acetylene black.
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 processing.
Anode chamber part 3:
Negative pole electrolyte, solution are organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.
Negative pole 31 is the sodium metal sheet.
Embodiment 12
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, 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, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Adding positive active material mol ratio is 1: 5 Na in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Na of concentration 0.3mol/L 2S 6
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 15% acetylene black.
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 processing.
Anode chamber part 3:
Negative pole electrolyte, solution are organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.
Negative pole 31 is the sodium metal sheet.
Embodiment 13
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, 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, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Adding positive active material mol ratio is 1: 3 Na in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Na of concentration 0.2mol/L 2S 4
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 15% acetylene black.
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 processing.
Anode chamber part 3:
Negative pole electrolyte, solution are organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.
Negative pole 31 is the sodium metal sheet.
Embodiment 14
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, 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, and electrolyte is sodium salt NaPF 6Concentration is 1mol/L.Adding positive active material mol ratio is 1: 1 Na in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Na of concentration 0.1mol/L 2S 2
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 15% acetylene black.
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 processing.
Anode chamber part 3:
Negative pole electrolyte, solution are organic solvent DMSO, and electrolyte is NaPF 6, concentration is 1mol/L.
Negative pole 31 is the sodium metal sheet.
Embodiment 15
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 9, is specially:
The cathode chamber part:
Anode sizing agent: the solvent of electrolyte is: solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.5mol/L 2S 8
Anodal conductive materials is that to account for the anode sizing agent volume ratio be 10% acetylene black to addition.
Plus plate current-collecting body is 100 purpose 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:
Negative pole electrolyte: solvent is organic solvent EC: DMC=1: 1, and 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 is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, 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 6Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 9 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.5mol/L 2S 10
In anode sizing agent, add again anodal conductive materials, account for the anode sizing agent volume ratio and be 15% Graphene.
Plus plate current-collecting body is 200 purpose aluminium nets.
Barrier film 2:
Film in the present embodiment is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is organic solvent THF, and 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 is identical among battery basic structure and the embodiment 9.And the constituent of the anode sizing agent that adopts, 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, and electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.
In anode electrolyte, add positive active material S 8, being mixed into anode sizing agent, adding active material in the anode sizing agent is concentration 1mol/L.
Add again the acetylene black as anodal conductive materials in the anode electrolyte.Its addition is 15% for the volume ratio with 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:
Negative pole electrolyte: solvent is organic solvent PC: DMC=1: 1, and 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 in the present embodiment is anodal identical with embodiment 1 with the membrane portions structure, its difference is that the anode chamber 35 of battery in the present embodiment links to each other with negative pole fluid reservoir 34, negative pole electrolyte 33 is by being arranged between anode chamber 35 and the negative pole fluid reservoir 34, the piston pump 36 that is used on both pipelines of connection provides power, circulation between anode chamber 35 and negative pole fluid reservoir 34.
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 1mol/L 2S 8
Anodal conductive materials is acetylene black, is specially 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode: 100 purpose stainless (steel) wires.
Membrane portions 2:
Barrier film is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.A certain amount of mol ratio of adding positive active material is 1: 11 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 1mol/L 2S 12
A certain amount of positive active material Li 2S: S is dissolved in the anode electrolyte according to mol ratio at 1: 11, forms the Li of 1mol/L 2S 12
Anodal conductive materials is acetylene black, is specially 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode: 100 purpose stainless (steel) wires.
Membrane portions 2:
Barrier film is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.A certain amount of mol ratio of adding positive active material is 1: 9 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.5mol/L 2S10.
Anodal conductive materials is acetylene black, is specially 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode: 100 purpose stainless (steel) wires.
Membrane portions 2:
Barrier film is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.A certain amount of mol ratio of adding positive active material is 1: 5 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.3mol/L 2S 6
Anodal conductive materials is acetylene black, is specially 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode: 100 purpose stainless (steel) wires.
Membrane portions 2:
Barrier film is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.A certain amount of mol ratio of adding positive active material is 1: 3 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.2mol/L 2S 4
Anodal conductive materials is acetylene black, is specially 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode: 100 purpose stainless (steel) wires.
Membrane portions 2:
Barrier film is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.A certain amount of mol ratio of adding positive active material is 1: 1 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of concentration 0.1mol/L 2S 2
Anodal conductive materials is acetylene black, is specially 100mg acetylene black is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode: 100 purpose stainless (steel) wires.
Membrane portions 2:
Barrier film is the nafion117 film after the lithiumation.
Anode chamber part 3:
Negative pole electrolyte: solvent is EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
A kind of liquid stream chargeable lithium-sulphur battery, employing scheme 3 detailed processes are as follows:
The 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 4Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 3 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material concentration in the anode sizing agent is the Li of 3mol/L 2S 4
Anodal conductive materials is the carbon nano-tube that is mixed in anode electrolyte, its addition be account for anode sizing agent volume ratio 20%.And in charge and discharge process, this slurry is continued to stir.
Plus plate current-collecting body adopts 100 purpose 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 that deposits 3nm 2O 3Organic Nafion film.
Anode chamber part 3:
Negative pole electrolyte: 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, 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 6Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material concentration in the anode sizing agent is 1mol/L Li 2S 8
Positive active material is Graphene, is specially the 100mg Graphene is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode is 100 purpose stainless (steel) wires.
Barrier film 2:
For single ion guide is connected with the machine inorganic substances compound membrane, be specially the Al that is provided with a layer thickness 4nm on it 2O 3Organic Nafion film.
Anode chamber part 3:
Negative pole electrolyte: solvent is organic solvent EC: DEC=1: 1, and 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 is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, 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 6Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 11 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material concentration in the anode sizing agent is 1mol/L.
Positive active material is Graphene, is specially the 100mg Graphene is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode is 100 purpose 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:
Negative pole electrolyte: solvent is that 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, guarantee that reactive material is in liquid condition.
Embodiment 27
Liquid stream in the present embodiment can fill alkali metal-sulphur battery, and is identical among battery basic structure and the embodiment 18.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 18, is specially:
The cathode chamber part:
Anode electrolyte: solvent is organic solvent TMSO, and electrolyte is lithium salts LiPF 6Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 1mol/L 2S 8
Positive active material is Graphene, is specially the 100mg Graphene is mixed rear roll extrusion with binding agent PTFE on positive collector electrode with weight ratio at 9: 1.
Positive collector electrode is 100 purpose 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:
Negative pole electrolyte: solvent is organic solvent 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 8→ Li 2S 4Between circulation, guarantee 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 is identical among battery basic structure and the embodiment 8.Difference between the two is the constituent of set-up mode and electrolyte and the active material of conductive materials 15.In the present embodiment, anodal conductive materials 15 is mixed with anode sizing agent, and in the course of work of battery, circulate between cathode chamber and anodal fluid reservoir with anode sizing agent.
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 7 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 0.5mol/L 2S 8
Anodal conductive materials 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 purpose 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:
Negative pole electrolyte: solvent is that 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 is identical among battery basic structure and the embodiment 28.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 28, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 11 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 1mol/L 2S 12
Anodal conductive materials 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 purpose 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:
Negative pole electrolyte: solvent is that 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 is identical among battery basic structure and the embodiment 28.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 28, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 9 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 0.5mol/L 2S 10
Anodal conductive materials 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 purpose 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:
Negative pole electrolyte: solvent is that 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 is identical among battery basic structure and the embodiment 28.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 28, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 5 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 0.3mol/L 2S 6
Anodal conductive materials 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 purpose 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:
Negative pole electrolyte: solvent is that 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 is identical among battery basic structure and the embodiment 28.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 28, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 3 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 0.2mol/L 2S 4
Anodal conductive materials 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 purpose 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:
Negative pole electrolyte: solvent is that 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 is identical among battery basic structure and the embodiment 28.And the constituent of the anode sizing agent that adopts, and the material of other battery structures is different from embodiment 28, is specially:
The cathode chamber part:
Anode electrolyte: its solvent is organic solvent DOL: DME=1: 1, and electrolyte is lithium salts LiTFSI.Concentration is 1mol/L.
Adding positive active material mol ratio is 1: 1 Li in anode electrolyte 2S: S is mixed into anode sizing agent, and adding active material in the anode sizing agent is the Li of 0.2mol/L 2S 4
Anodal conductive materials 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 purpose 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:
Negative pole electrolyte: solvent is that 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 is identical among battery basic structure and the embodiment 28.And the constituent of the anode sizing agent that adopts, 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, and electrolyte is lithium salts LiTFSI; Concentration is 1mol/L.
Adding positive active material in anode electrolyte is Li 2S is mixed into anode sizing agent, and adding active material concentration in the anode sizing agent is 1mol/L.
Add again the acetylene black as anodal conductive materials in the anode electrolyte.Its addition is 40% for the volume ratio with anode sizing agent.
Plus plate current-collecting body adopts 100 microns aluminium foil.
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:
Negative pole electrolyte: solvent is that organic solvent is EC: DEC=1: 1; Electrolyte is LiPF 6Concentration is 1mol/L.Negative pole 31 adopts metal lithium sheet.
The suitable capacity of the first Zhou Fangdian of each battery of the above embodiment of table 2 and 50 all capability retentions
Illustration The contrary capacity (mAh/g) of first Zhou Fangdian 50 all 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 that obtains assembles, and wherein electrolyte adopts 1mol/L LiTFSI to be dissolved as TEGDME, with the lithium sheet as negative pole.At C/10 multiplying power constant current charge-discharge, first all composite material discharge 612mAh/g, but because strong " effect of shuttling back and forth " overcharges obviously, and first all efficient is 137%, and the specific capacity conservation rate only has 51% after 50 weeks.
In addition, Fig. 5 uses Li for adopting battery structure of the present invention shown in Figure 1 2S 8As active material, when conductive materials is acetylene black, measured typical first all charging and discharging curve figure.Fig. 6 is battery structure of the present invention shown in Figure 2, and adopts Li 2S 8As active material, when conductive materials is acetylene black, measured typical first all charging and discharging curve figure.Dotted portion is first all charging and discharging curves of traditional lithium-sulfur cell among Fig. 6.Fig. 7 is battery structure of the present invention shown in Figure 4, adopts Li 2S 8As active material, measured typical first all charging and discharging curve figure, dotted portion is the first all charging and discharging curves without conductive additive among the figure, and solid line is the first all charging and discharging curves that added 20% acetylene black.By to the two contrast, add conductive additive and form slurry, can greatly improve the electron conduction of reaction system, greatly reduce and discharge and recharge polarization, significantly improved first all charge/discharge capacities.
The employed electrolyte of anodal part, conductive materials, positive collector electrode material among the present invention in the disclosed liquid stream chargeable lithium-sulphur battery, the barrier film material, bath composition in the negative pole and concentration negative pole material and negative collector electrode material are 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), carbonic acid diisopropyl ester (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, the 3-dioxolanes (1,3-DOL).One or more consist of ionic liquid by following kind, are specially: imidazole type ion liquid such 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 tetrazoliums [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-methylimidazole toluene fulfonate [C6MIM] OTS, 1-butyl-3-methylimidazole N, waste propylhomoserin salt [C4MIM] BDTC of N-dialkyl group, 1-butyl-3-methylimidazole alkyl trithiocarbonate [C4MIM] TTC, 1-butyl-3-methylimidazole alkoxyl dithiocarbonate [C4MIM] OTDC; Pyridine type ionic liquid such as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; Piperidines type ionic liquid such as N-methyl, the two fluoroform sulfimide salt PP13TFSI of propyl group piperidines, N-methyl, propyl group piperidines fluoroform sulphonate PP13OTF, N-methyl, propyl group piperidines hexafluorophosphate PP13PF 6, the N-methyl, propyl group piperidines bromination PP13Br; Pyrrolidines type ionic liquid such as N-methyl, the two fluoroform sulfimide salt BMPTf of butyl pyrrolidine 2N, bromination N-methyl, butyl pyrrolidine, chlorination N-methyl, butyl pyrrolidine; Quaternary ammonium type ionic liquid such 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 that liquid state also can be solid-state or the mixing phase composition of the two; The concentration 0.01-10mol/L of positive active material in anode electrolyte, preferable range: 0.1-3mol/L.
The organic electrolyte use of both positive and negative polarity 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 are natural numbers, LiBF z(CF 3) 4-z, the natural number of z≤4 wherein; Sodium salt is: NaPF 6, NaBF 4, NaClO 4, NaAlCl 4, NaCF 3SO 3, NaC 4F 9SO 3, the concentration of lithium salts is 0.5～5.0mol/L in the electrolyte.
Anodal conductive materials has two kinds of existence forms in battery, shown in Fig. 1,3 exist for it is fixing and anodal reative cell in, in this case, can with carbon by adhesive coated or roll extrusion on the collector made from metal or its alloy.Shown in Fig. 2,4, anodal conductive materials also can be blended in the anode sizing agent, with anode sizing agent, circulates between cathode chamber and anodal fluid reservoir in battery operated process, the addition of this anodal conductive materials is the 0-50% of electrolyte system volume, preferable range: 0%-30%.
Negative pole electrolyte is non-water organic electrolyte.
Negative pole (active material in the negative pole is negative pole) adopts lithium metal or sodium metal or its alloy: lithium silicon, lithium-tin alloy.
The 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 the 20-500 order, or take above metal and alloy thereof metal foam or the porous metals as base, also can be that one or more mixtures such as carbon that carbon class negative material such as graphite, MCMB (MCMB), hard carbon ball, porous carbon, acetylene black, Graphene, carbon nano-tube, carbon fiber, nitrogen mix consist of.
Positive and negative electrode material that fluid reservoir uses can be metal or its alloy such as aluminium, aluminium alloy, titanium, titanium alloy, stainless steel, also can be other organic polymer material such as polytetrafluoroethylene, and PVP also can use the inorganic ceramic composite material.
Among the present invention disclosed battery have energy density height, specific capacity large, have extended cycle life, cost is low, the energy utilization efficiency high, can be widely used in clean energy resource solar energy, the required extensive energy storage device of wind-force, 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 (16)

1. one kind can be filled alkali metal-sulphur flow battery, it is characterized in that, described battery comprises cathode chamber part, barrier film and anode chamber part, described cathode chamber partly comprise anodal reative cell and with the fluid reservoir of cathode chamber pipeline communication, described anodal reative cell comprises, positive collector electrode and the anode sizing agent that circulates between anodal reative cell and fluid reservoir that uses as positive pole; Described anode chamber is the negative reaction chamber partly, comprises negative pole, negative collector electrode and negative pole electrolyte; Described barrier film is the single ion conductor film, is arranged between described anodal reative cell and the negative reaction chamber, and guarantees to only have single work ionic conduction between the both positive and negative polarity, and without any mass transfer of other inoperative ion; Described anode sizing agent is made of anode electrolyte and the positive electrode active material that is blended in the anode electrolyte, and described positive active material is M xS y(M=Li or Na; 0＜x≤2; 0＜y≤12) one or more in.
2. a kind of alkali metal-sulphur flow battery that fills according to claim 1 is characterized in that, also comprises anodal conductive materials in the described anode sizing agent; Described anodal conductive materials is material with carbon element: one or more mixtures consist of in the carbon that acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen mix.
3. a kind of alkali metal-sulphur flow battery that fills according to claim 2 is characterized in that the addition of described anodal conductive materials is to account for 0～50% of anode electrolyte volume, preferable range: 0%～30%.
4. alkali metal-sulphur the flow battery that fills according to claim 1, it is characterized in that, described anodal reative cell also comprises the anodal conductive materials that is arranged on the positive collector electrode, and described conductive materials is material with carbon element: one or more mixtures consist of in the carbon that acetylene black, graphite, Graphene, porous carbon, carbon nano-tube, carbon fiber, nitrogen mix.
5. alkali metal-sulphur the flow battery that fills according to claim 1 is characterized in that the concentration range of described positive active material in electrolyte exists: 0.01～10mol/L, preferable range: 0.1～3mol/L.
6. a kind of New stream according to claim 1 can fill alkali metal-sulphur battery, it is characterized in that, described negative pole is lithium metal or sodium metal or its alloy.
7. alkali metal-sulphur the flow battery that fills according to claim 1 is characterized in that described single ion conductor film only allows the transmission of single work ion, and without other liquid and the diffusion of inoperative ion; The single ion conductor film is inorganic ceramic membrane, organic polymer films or inorganic/organic composite ceramic membrane.
8. alkali metal-sulphur the flow battery that fills according to claim 7 is characterized in that, 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 the logical organic film of single ion guide is (such as perfluorinated ion-exchange membrane (Nafion) film through lithiumation or sodium processing; Organic/inorganic compound film is that single ion guide is connected with the machine inorganic substances compound membrane (as depositing the adjustable inorganic Al of a layer thickness by technique for atomic layer deposition at organic (Nafion) film 2O 3
9. the described alkali metal-sulphur flow battery that fills according to claim 1 is characterized in that, the electrolyte in described positive pole and the negative pole 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, LiC 4F 9SO 3, LiN (C xF 2x+1SO 2) (C yF 2y+1SO 2), wherein, x and y are natural numbers, LiBF z(CF 3) 4-z, the natural number of z≤4 wherein; 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.
10. alkali metal-sulphur the flow battery that fills according to claim 1 is characterized in that the solvent in the described electrolyte is organic solvent or ionic liquid.
11. the described alkali metal-sulphur flow battery that fills according to claim 10, it is characterized in that, the employed organic solvent of described organic electrolyte 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), carbonic acid diisopropyl ester (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, the 3-dioxolanes (1,3-DOL).
12. the described alkali metal-sulphur flow battery that fills is characterized in that described ionic liquid has one or more formations of following kind, is specially: imidazole type ion liquid such as 1-ethyl-3-methylimidazole tetrafluoroborate [EMIM] BF according to claim 10 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 tetrazoliums [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-methylimidazole toluene fulfonate [C6MIM] OTS, 1-butyl-3-methylimidazole N, waste propylhomoserin salt [C4MIM] BDTC of N-dialkyl group, 1-butyl-3-methylimidazole alkyl trithiocarbonate [C4MIM] TTC, 1-butyl-3-methylimidazole alkoxyl dithiocarbonate [C4MIM] OTDC; Pyridine type ionic liquid such as N-ethylpyridine tetrafluoroborate, N-ethylpyridine hexafluorophosphate; Piperidines type ionic liquid such as N-methyl, the two fluoroform sulfimide salt PP13TFSI of propyl group piperidines, N-methyl, propyl group piperidines fluoroform sulphonate PP13OTF, N-methyl, propyl group piperidines hexafluorophosphate PP13PF 6, the N-methyl, propyl group piperidines bromination PP13Br; Pyrrolidines type ionic liquid such as N-methyl, the two fluoroform sulfimide salt BMPTf of butyl pyrrolidine 2N, bromination N-methyl, butyl pyrrolidine, chlorination N-methyl, butyl pyrrolidine; Quaternary ammonium type ionic liquid such as TBuA tetrafluoroborate.
13. a kind of New stream according to claim 1 can fill alkali metal-sulphur battery, it is characterized in that, described positive and negative electrode collector adopts net or the paper tinsel of the metal such as nickel, stainless steel, titanium, aluminium and alloy composition thereof to make, wherein net is 20～500 orders, or take above metal and alloy thereof metal foam or the porous metals as base, or carbon class negative material
14. the alkali metal-sulphur flow battery that fills according to claim 13, it is characterized in that, carbon class negative material, one or more mixtures such as carbon that graphite, MCMB (MCMB), hard carbon ball, porous carbon, acetylene black, Graphene, carbon nano-tube, carbon fiber, nitrogen mix consist of.
15. 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 that is connected by pipeline with anode chamber.
16. according to claim 1,15 described a kind of New streams can fill alkali metal-sulphur battery, it is characterized in that material that fluid reservoir uses that anodal part adopts can be metal or its alloy such as aluminium, aluminium alloy, titanium, titanium alloy, stainless steel, also can be other organic polymer material such as polytetrafluoroethylene, PVP also can use the inorganic ceramic composite material.
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