CN104733785A - Battery - Google Patents

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Publication number
CN104733785A
CN104733785A CN201310710879.4A CN201310710879A CN104733785A CN 104733785 A CN104733785 A CN 104733785A CN 201310710879 A CN201310710879 A CN 201310710879A CN 104733785 A CN104733785 A CN 104733785A
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China
Prior art keywords
battery
ion
electrolyte
metal
negative pole
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CN201310710879.4A
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CN104733785B (en
Inventor
刘洋
陈璞
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Positec Power Tools Suzhou Co Ltd
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Positec Power Tools Suzhou Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a battery comprising a cathode, an anode, and an electrolyte solution. According to the battery, the cathode comprises a cathode active material capable of realizing reversible deintercalation-intercalation into first metal ions; the electrolyte solution comprises a solvent capable of dissolving and ionizing electrolytes; the electrolytes comprise the first metal ions and second metal ions; in charging processes, the second metal ions are transformed into second metal via reduction, and the second metal is deposited on the anode; and in discharging processes, the second metal can be transformed into the second metal ions via reversible oxidation dissolving. The battery also comprises additives added into the electrolyte solution; and the additives comprise one or a plurality of compounds selected from Tween, tertiary amine compounds, heterocyclic quaternary ammonium salts, and thioamide. The battery is capable of inhibiting generation of gas effectively, so that battery expansion is avoided, and battery safety is improved.

Description

Battery
Technical field
The invention belongs to field of batteries, be specifically related to a kind of battery exchanged based on inner ion.
Background technology
Lead-acid battery, its appearance is super century-old, has ripe battery technology, in occupation of the absolute market share in the energy storage fields such as automobile starting storage battery, electric bicycle, UPS.Although lead-acid battery service life cycle is lower, energy density is also relatively low, has price very cheap, the advantage that cost performance is very high.Therefore, in the last few years, Ni-MH battery, lithium ion battery, sodium-sulphur battery etc., all cannot replace lead-acid battery in energy storage field.
Newly there is a kind of battery exchanged based on inner ion.The operation principle of this battery is, positive pole deviates from-insertion reaction based on the first metal ion, negative pole is based on the deposition-solubilizing reaction of the second metal ion, and electrolyte deviates from containing participating in positive pole-the first metal ion of insertion reaction and participate in the second metal ion of cathode deposition-solubilizing reaction.The theoretical energy density of the type battery is 160Wh/Kg, estimates that actual energy density can reach 50 ~ 80Wh/Kg.In sum, the type battery promises to be the energy-storage battery of future generation of alternative lead-acid battery very much, has great commercial value.
But this battery in use for some time at present, and inside battery can produce a large amount of gas, easily causes battery swell, cause battery to use and there is potential safety hazard; Simultaneously due to the generation of gas, battery performance also can be caused to worsen rapidly.
Summary of the invention
Technical problem to be solved by this invention is, can produce a large amount of gas when ion-exchange battery uses.
The invention provides a kind of battery, comprise positive pole, negative pole and electrolyte, described positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Described electrolyte comprises dissolving electrolyte and makes the solvent that described electrolyte ionizes; Described electrolyte comprises the first metal ion and the second metal ion; Described in charging process, the second reducing metal ions is that the second metal is deposited on described negative pole, and the second metal reversible oxidation is dissolved as described second metal ion in discharge process; Described battery also comprises the additive joined in described electrolyte, and described additive comprises one or more in tween, tertiary amine compound, heterocyclic quaternary ammonium salt and thioamides;
The general formula of described thioamides is as follows:
Wherein, R 1, R 2, R 3, R 4be selected from the one in H, alkyl and phenyl, and R 1, R 2, R 3, R 4be asynchronously H.
Preferably, described alkyl is methyl.
Preferably, described thioamides is selected from one or more in tetramethyl thiourea, N, N-dimethyl sulfourea, N-methylthiourea and rhenocure CA.
Preferably, in the electrolytic solution, the mass percentage of described thioamides is 0.01% ~ 5%.
Preferably, described tertiary amine compound is selected from one or more in triacetamide, triethylamine and triethanolamine; Described heterocyclic quaternary ammonium salt is selected from one or more in N-ethylpyridine hydrochloride, N-benzyl pyridine hydrochloride, N-2-ethoxy pyridine hydrochloride, N-2-hydroxypropyl pyridine hydrochloride and pyridine radicals-N-propane sulfonic acid betaine.
Preferably, in the electrolytic solution, the mass percentage of described tertiary amine compound or heterocyclic quaternary ammonium salt is 0.01% ~ 5%.
Preferably, described tween is selected from polysorbate40.
Preferably, in the electrolytic solution, the mass percentage of described tween is 0.01% ~ 0.1%.
Preferably, described additive also comprises the oxyacid radical ion compound of boron.
Preferably, described electrolyte also comprises one or more in sulfate ion, chloride ion, acetate ion, nitrate ion and alkyl sulfonate ion.
Preferably, described alkyl sulfonate ion is selected from tosylate ion.
Preferably, described battery also comprises the barrier film between positive pole and negative pole.
Preferably, described first metal ion is selected from lithium ion, sodium ion or magnesium ion.
Preferably, described second metal is selected from manganese, iron, copper, zinc, chromium, nickel, tin or lead.
Preferably, the pH value of described electrolyte is 3 ~ 7.
Preferably, described solvent is water or alcohol.
Compared with prior art, the present invention adds additive in the electrolytic solution, effectively inhibits the generation of gas, thus avoids battery swell, enhances the security performance of battery.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
A kind of battery, comprise positive pole, negative pole and electrolyte, described positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Described electrolyte comprises dissolving electrolyte and makes the solvent that described electrolyte ionizes; Described electrolyte comprises the first metal ion and the second metal ion; Described in charging process, the second reducing metal ions is that the second metal is deposited on described negative pole, and the second metal reversible oxidation is dissolved as described second metal ion in discharge process; Described battery also comprises the additive joined in described electrolyte, and described additive comprises one or more in tween, tertiary amine compound, heterocyclic quaternary ammonium salt and thioamides;
The general formula of described thioamides is as follows:
Wherein, R 1, R 2, R 3, R 4be selected from the one in H, alkyl and phenyl, and R 1, R 2, R 3, R 4be asynchronously H.
More preferably, described alkyl is methyl.
The charge-discharge principle of battery of the present invention is: during charging, and positive active material deviates from the first metal ion, simultaneously oxidized with positive active material, and ejected electron; Electronics arrives battery cathode via external circuit, and the second metal ion simultaneously in electrolyte obtains electronics and is reduced on negative pole, and is deposited on negative pole.During electric discharge, the second metal be deposited on negative pole is oxidized, loses electronics and changes the second metal ion into and enter in electrolyte; Electronics arrives positive pole through external circuit, and positive active material accepts electronics and is reduced, and the first metal ion embeds in positive active material simultaneously.
Add tween in the electrolytic solution, effectively inhibit the generation of gas, thus avoid battery swell, enhance the security performance of battery.
Tween (English: tween) for known in those skilled in the art, its main component is polyoxyethylene sorbitan fatty acid ester (being also called for short polysorbate), be the condensation product of Span and oxirane.
Preferably, tween is selected from Tween-40.
Preferably, in the electrolytic solution, the mass percentage of tween is 0.01% ~ 0.1%.
Add tertiary amine compound and heterocyclic quaternary ammonium salt in the electrolytic solution, effectively can not only suppress the generation of gas, thus avoid battery swell, enhance the security performance of battery; And the cycle performance of battery can also be improved simultaneously.
Tertiary amine compound in the present invention, refers to the compound containing the atom N be connected with three C atoms simultaneously.
Preferably, tertiary amine compound is selected from one or more in triacetamide, triethylamine and triethanolamine.
Preferably, heterocyclic quaternary ammonium salt is selected from one or more in N-ethylpyridine hydrochloride, N-benzyl pyridine hydrochloride, N-2-ethoxy pyridine hydrochloride, N-2-hydroxypropyl pyridine hydrochloride and pyridine radicals-N-propane sulfonic acid betaine.
Preferably, in the electrolytic solution, the mass percentage of tertiary amine compound or heterocyclic quaternary ammonium salt is 0.01% ~ 5%; Be more preferably 0.1% ~ 0.5%.
Add thioamides in the electrolytic solution, effectively inhibit the generation of gas, thus avoid battery swell, enhance the security performance of battery; And thioamides significantly can also improve the cycle performance of battery simultaneously.
Particularly preferably, thioamides is selected from one or more in tetramethyl thiourea, N, N-dimethyl sulfourea, N-methylthiourea and phenylthiourea.
Wherein, tetramethyl thiourea, i.e. R in general formula 1, R 2, R 3, R 4be thioamides during methyl; N, N-dimethyl sulfourea, i.e. R in general formula 1with R 3be methyl, and R 2with R 4be thioamides during H; N-methylthiourea, i.e. R in general formula 1, R 2, R 3, R 4in one of be methyl, thioamides when all the other are H; Rhenocure CA, i.e. R in general formula 1with R 3be phenyl, and R 2with R 4be thioamides during H.
Preferably, in the electrolytic solution, the mass percentage of thioamides is 0.01% ~ 5%; Be more preferably 0.1% ~ 0.5%.
In order to promote the performance of battery further, additive can also comprise the oxyacid radical ion compound of boron.
The oxyacid radical ion compound of boron of the present invention, refers in compound containing the acid ion that boron atom and oxygen atom ligand are formed.Such as containing compound, the compound containing metaboric acid radical ion, the compound containing many borate ions, the compound containing perboric acid ion of ortho-boric acid radical ion.
Preferably, the oxyacid radical ion compound of boron is selected from one or more in boric acid, borate and perborate.
Wherein, boric acid includes but not limited to ortho-boric acid, metaboric acid or many boric acid.
Borate includes but not limited to ortho-borate, metaborate or multi-borate.Preferably, borate is selected from one or more of Boratex, kodalk, magnesium metaborate, calcium metaborate or barium metaborate.
Perborate includes but not limited to sodium perborate, perboric acid lithium, perboric acid rubidium, potassium perborate, perboric acid caesium, calcium perborate or perboric acid barium.
More preferably, additive is selected from boric acid and borate.Boric acid and borate can be combined to form soda acid cushioning liquid, can the pH value of better stable cell electrolyte, improve the stability of battery.
In the electrolytic solution, with the total weight of electrolyte for benchmark, the mass percentage of the oxyacid radical ion compound of boron is preferably 0.01% ~ 2%.
Additive is dispersed in the electrolytic solution.
Additive adds the mode in electrolyte, (adds solvent together with electrolyte) when can be electrolyte dissolution; Or before electrolyte dissolution also or after electrolyte dissolution, additive is joined in solvent.
Wherein, in electrolyte, the object of solvent dissolves electrolyte, and electrolyte is ionized in a solvent, finally generates the cation that can move freely and anion in the electrolytic solution.
Solvent includes but not limited to water and alcohol, and alcohol includes but not limited to methyl alcohol or ethanol.
Wherein, the first metal ion in electrolyte, reversiblely can deviate from-embeds at positive pole in charge and discharge process.Namely, when battery discharge, the first metal ion in electrolyte embeds in positive active material; When battery charges, the first metal ion is deviate from from positive active material, enters electrolyte.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion, is more preferably lithium ion.
Wherein, the second metal ion in electrolyte, the second metal ion is deposited as the second metal at described cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion; Namely can reduce at negative pole in charge and discharge process and be deposited as the second metal and the second metal energy reversible oxidation dissolving.
Preferably, the second metal ion is selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion; Be more preferably zinc ion.
Under a preferred embodiment, the first metal ion of the present invention is selected from lithium ion, and the second metal ion is selected from zinc ion simultaneously, and namely electrolyte cationic is lithium ion and zinc ion.
Anion in electrolyte can be any anion substantially not affecting both positive and negative polarity reaction and electrolyte dissolving in a solvent.Can be such as sulfate ion, chloride ion, nitrate ion, acetate ion, formate ion, phosphate anion and mixing thereof etc.
Under a preferred implementation, in electrolyte, anion comprises one or more in sulfate ion, chloride ion, acetate ion and nitrate ion.
The concentration of each ion in electrolyte, can carry out change allotment according to different situations such as the applications of different electrolyte, solvent and battery.
Preferably, in the electrolytic solution, the concentration of the first metal ion is 0.1 ~ 10mol/L.
Preferably, in the electrolytic solution, the concentration of the second metal ion is 0.5 ~ 15mol/L.
In order to make battery performance more optimize, the pH value range of electrolyte is preferably 3 ~ 7.
The pH value range of electrolyte is 3 ~ 7, so both effectively can ensure the concentration of the second metal ion in electrolyte, thus ensures capacity and the multiplying power discharging property of battery, can also avoid the problem that proton embeds altogether.
Below to positive pole of the present invention, be described in detail and illustrate.
Wherein, the positive active material in positive pole participates in positive pole reaction, and reversiblely can deviate from-embed the first metal ion.
Concrete, positive active material has spinel structure, layer structure or olivine structural.
Concrete, lithium ion, sodium ion or magnesium ion can deviate from-embedded to positive active material reversiblely.
Positive active material can be meet general formula Li 1+xmn ym zo kcan the reversible compound deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, Ni.Preferably, positive active material contains LiMn 2o 4.Preferred, positive active material contains the LiMn through overdoping or coating modification 2o 4.
Positive active material can be meet general formula Li 1+xm ym ' zm " co 2+ncan the reversible compound deviating from-embed the layer structure of lithium ion, wherein,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material contains LiCoO 2.
Positive active material can be meet general formula Li xm 1-ym ' y(XO 4) ncan the reversible compound deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO 4.
In current battery industry, nearly all positive active material all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn 2o 4can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li 1+xmn ym zo kbe as the criterion, comprise the LiMn through various modification widely 2o 4positive active material.Same, LiFePO 4and LiCoO 2also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively xm 1-ym ' y(XO 4) nand Li 1+xm ym ' zm " co 2+npositive active material.
Positive active material be lithium ion deviate from-inlaid scheme time, can select as LiMn 2o 4, LiFePO 4, LiCoO 2, LiM xpO 4, LiM xsiO ycompounds such as (wherein M are a kind of variable valency metal).
In addition, the compound N aVPO of sodium ion can be deviate from-embed 4f, can deviate from-embed the compound Mg M of magnesium ion xo y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and have similar functions, the compound can deviating from-embed the first metal ion can as the positive active material of battery of the present invention.
Concrete, positive pole also comprises the plus plate current-collecting body of load positive active material, plus plate current-collecting body is only as the carrier of electrical conductivity and collection, do not participate in electrochemical reaction, namely within the scope of battery operating voltage, plus plate current-collecting body can be stable be present in electrolyte and substantially side reaction do not occur, thus ensure that battery has stable cycle performance.
The material of plus plate current-collecting body is selected from the one in carbon-based material, metal or alloy.
Carbon-based material is selected from the one in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In a particular embodiment, plus plate current-collecting body is graphite, and as the paper tinsel that business-like graphite is suppressed, the part by weight scope wherein shared by graphite is 90-100%.
Metal comprises Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.
Alloy comprises stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned metal of Passivation Treatment.
Stainless steel comprises stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Preferably, carry out Passivation Treatment to plus plate current-collecting body, its main purpose is, make the surface of plus plate current-collecting body form the oxide-film of one deck passivation, thus in battery charge and discharge process, stable collection and the effect of conduction electron can be played, and cell reaction can not be participated in, ensure that battery performance is stablized.Plus plate current-collecting body deactivating process for the treatment of comprises chemical passivation process or electrochemical passivation process.
Chemical passivation process comprises by oxidizing plus plate current-collecting body, makes anode collection surface form passivating film.The principle that oxidant is selected is that oxidant can make anode collection surface form one deck passivating film and can not dissolve plus plate current-collecting body.Oxidant is selected from but is not limited only to red fuming nitric acid (RFNA) or ceric sulfate (Ce (SO 4) 2).
Electrochemical passivation process comprises and aligns pole collector and carry out electrochemical oxidation or carry out discharge and recharge process to the battery containing plus plate current-collecting body, makes anode collection surface form passivating film.
Be more preferably, positive pole also comprises the composite current collector of load positive active material, and composite current collector comprises plus plate current-collecting body and is coated on plus plate current-collecting body upper conductive film.
The selection of conducting film must to meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, do not occur swelling, high voltage can not oxidized, be easy to be processed into densification, the waterproof and film of conduction.On the one hand, conducting film can play a protective role to plus plate current-collecting body, avoids aqueous electrolyte to the corrosion of plus plate current-collecting body.On the other hand, be conducive to reducing the contact internal resistance between positive plate and plus plate current-collecting body, improve the energy of battery.
Preferably, the thickness of conducting film is 10 μm of-2mm, and conducting film effectively can not only play the effect of protection plus plate current-collecting body, and is conducive to reducing the contact internal resistance between positive active material and plus plate current-collecting body, improves the energy of battery.
Plus plate current-collecting body has the first surface and second that are oppositely arranged, and preferably, the first surface of plus plate current-collecting body and second are all coated with conducting film.
Conducting film comprises the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50-95%, and preferably, polymer is selected from thermoplastic polymer.In order to enable conducting film conduct electricity, there is the form that two kinds feasible: (1) polymer is conducting polymer; (2) except polymer, conducting film also comprises conductive filler.
Conducting polymer choice requirement, namely can not as the ionic conduction of charge transfer medium for having conductive capability but electrochemicaUy inert.Concrete, conducting polymer includes but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and any mixture thereof.Conducting polymer inherently has conductivity, but can also adulterate to conducting polymer or modification to improve its conductive capability further.Consider from the stable use electric conductivity and battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler be surface area little, be difficult to oxidation, degree of crystallinity high, there is conductivity but electrochemicaUy inert, namely can not as the ionic conduction of charge transfer medium.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler mass percent scope is in the conductive film 5-50%.The average grain diameter of conductive filler is not particularly limited, usual scope at 100nm to 100 μm.
When comprising conductive filler in conducting film, the polymer in conducting film preferably comprises the non-conductive polymer played in conjunction with conductive filler effect, and non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.
Concrete, thermoplastic polymer includes but are not limited to polyolefin as polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, polyolefin, polyamide and Kynoar is preferably.These polymer are easily melted by heat, and therefore easy and plus plate current-collecting body is combined with each other.In addition, these polymer have large potential window, thus make positive stabilizer pole be also battery output density saving in weight.
Preferably, conducting film is attached on plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.
In a particular embodiment, when preparing positive pole, except positive active material, according to actual conditions, may also need interpolation positive conductive agent and positive electrode binder to promote the performance of positive pole.
Positive conductive agent be selected from conducting polymer, activated carbon, Graphene, carbon black, graphite, carbon fiber, metallic fiber, metal dust and sheet metal one or more.
Positive electrode binder can be selected from polyethylene oxide, polypropylene oxide, the mixture of a kind of or above-mentioned polymer in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, poly-divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates and derivative.More preferably, positive electrode binder is selected from polytetrafluoroethylene (PTFE), Kynoar (PVDF) or butadiene-styrene rubber (SBR).
Below to negative pole of the present invention, be described in detail and illustrate.
The negative pole of battery, it is the second metal that the material of electrochemical reaction occurs, and the second metal can be the second metal ion and the second metal ion energy reversible reduction is deposited as the second metal by oxidation dissolution.
Preferably, the second metal is manganese, iron, copper, zinc, chromium, nickel, tin or lead.
Negative pole, according to the difference of its structure and effect, can be following three kinds of different forms:
In the first preferred embodiment, negative pole only comprises negative current collector, and negative current collector is only as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.
Material selected from metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al of negative current collector or at least one in the above-mentioned metal of Passivation Treatment, or elemental silicon, or carbon-based material; Wherein, carbon-based material comprises graphite material, and the paper tinsel of such as business-like graphite compacting, the part by weight scope wherein shared by graphite is 90 ~ 100%.The material of negative current collector can also be selected from stainless steel or the stainless steel through Passivation Treatment.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, same, and stainless model can be the stainless steel of 300 series, as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.In addition, negative current collector can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, alloy, or at least one in oxide.The thickness range of plating/coating is 1 ~ 1000nm.Such as: tin, lead or silver-colored on the negative current collector plated surface of Copper Foil or graphite foil.
In the second preferred implementation, negative pole, except negative current collector, also comprises the negative electrode active material of load on negative current collector.Negative electrode active material is the second metal.
Negative current collector with reference to the first preferred implementation, could not repeat them here wherein!
Second metal is with sheet or Powdered existence.
When employing second sheet metal is as negative electrode active material, the second sheet metal and negative current collector form composite bed.
When employing second metal dust is as negative electrode active material, the second metal dust is made slurry, then slurry is coated on negative current collector and makes negative pole.
In a particular embodiment, when preparing negative pole, except negative electrode active material second metal dust, according to actual conditions, also interpolation cathode conductive agent and negative electrode binder promote the performance of negative pole as required.
In the 3rd preferred implementation, directly adopt the second sheet metal as negative pole, the second sheet metal, both as negative current collector, is also negative electrode active material simultaneously.
Battery can not contain barrier film.Certainly, in order to provide better security performance, preferably between positive pole and negative pole, also barrier film is provided with in the electrolytic solution.The short circuit that the both positive and negative polarity that barrier film can avoid other unexpected factors to cause is connected and causes.
Barrier film does not have particular/special requirement, as long as allow electrolyte to pass through and the barrier film of electronic isolation.The various barrier films that organic system lithium ion battery adopts, all go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.
Under a preferred implementation, barrier film is barrier film electrolyte being divided into anode electrolyte and electrolyte liquid.Be limited in anode electrolyte by the first metal ion, the second metal ion is limited in electrolyte liquid, and such barrier film can stop the mutual pollution of both positive and negative polarity electrolyte, can select the electrolyte being more applicable to negative or positive electrode, but not affect ionic charge transmission.Such as adopt anion-exchange membrane or hydrogen ion exchange membrane as barrier film, be arranged in anode electrolyte first metal ion not by barrier film, so electrolyte liquid can not be entered, can only be limited in anode electrolyte; Be arranged in electrolyte liquid second metal ion by barrier film, so can not anode electrolyte be entered, can only to be limited in electrolyte liquid.But anion or hydrogen ion can freely pass through in electrolyte, therefore do not affect electrolyte intermediate ion charge transfer.
When electrolyte is divided into anode electrolyte and electrolyte liquid, preferable additives only adds electrolyte liquid, thus additive can be avoided the impact of positive pole.
Battery of the present invention, owing to the addition of additive in electrolyte, effectively inhibits the generation of gas, thus avoids battery swell, and battery performance worsens, and enhances the security performance of battery.
Below in conjunction with specific embodiment, the present invention will be further elaborated and explanation.
Embodiment 1.1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (corrosion resistant plates of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6cm × 6cm size, make positive plate.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
The methanesulfonic acid lithium, the methanesulfonic acid zinc that take certain mass are dissolved in deionized water, then add N-methylthiourea, make 2mol/L methanesulfonic acid lithium, 3mol/L methanesulfonic acid zinc, N-methylthiourea content be the electrolyte of 0.5wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as A1.
Embodiment 1.2
That replace N-methylthiourea with tetramethyl thiourea, other parts, with embodiment 1.1, obtain battery, are denoted as A2 with embodiment 1.1 difference.
Embodiment 1.3
That replace the N-methylthiourea of 0.5wt% with the rhenocure CA of 0.01wt%, other parts, with embodiment 1.1, obtain battery, are denoted as A3 with embodiment 1.1 difference.
Embodiment 1.4
With embodiment 1.1 difference be, the methanesulfonic acid lithium, the methanesulfonic acid zinc that take certain mass are dissolved in deionized water, then add N-methylthiourea and boric acid, make 2mol/L methanesulfonic acid lithium, 3mol/L methanesulfonic acid zinc, N-methylthiourea content be 0.5wt%, the content of boric acid is the electrolyte of 1wt%.
Other parts, with embodiment 1.1, obtain battery, are denoted as A4.
Embodiment 2.1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (corrosion resistant plates of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6cm × 6cm size, make positive plate.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
Take the zinc sulfate of certain mass, lithium sulfate, be added to the water dissolving, then add triacetamide, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is 1mol/L, the content of triacetamide is the electrolyte of 0.5wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as B1.
Embodiment 2.2
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (corrosion resistant plates of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6cm × 6cm size, make positive plate.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
The methanesulfonic acid lithium, the methanesulfonic acid zinc that take certain mass are dissolved in deionized water, then add triacetamide, make 2mol/L methanesulfonic acid lithium, 3mol/L methanesulfonic acid zinc, triacetamide content be the electrolyte of 0.5wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as B2.
Embodiment 2.3
Be replace triacetamide with triethylamine with embodiment 2.2 difference, other parts, with embodiment 2.2, obtain battery, are denoted as B3.
Embodiment 3.1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (corrosion resistant plates of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6cm × 6cm size, make positive plate.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
Take the zinc sulfate of certain mass, lithium sulfate, be added to the water dissolving, then add polysorbate40, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is 1mol/L, the content of polysorbate40 is the electrolyte of 0.1wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as C1.
Comparative example 1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (corrosion resistant plates of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6cm × 6cm size, make positive plate.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
Take the zinc sulfate of certain mass, lithium sulfate, be added to the water dissolving, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is the electrolyte of 1mol/L.
Positive pole, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as AC1.
Comparative example 2
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (corrosion resistant plates of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6cm × 6cm size, make positive plate.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
Take the methanesulfonic acid zinc of certain mass, methanesulfonic acid lithium, be added to the water dissolving, be configured to that methanesulfonic acid zinc concentration is 2mol/L, methanesulfonic acid lithium concentration is the electrolyte of 3mol/L.
Positive pole, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as AC2.
Performance test:
Gas content is tested:
Weigh 5g zinc powder, add respectively in the electrolyte of 20ml battery A1, then seal, place 4 days at 50 DEG C, record the gas flow produced every day.Test result is in table 1.
Table 1 is the gas production that at 50 DEG C, zinc powder leaves standstill at the electrolyte of A1 and AC2
As can be seen from Table 1, battery A1 obviously reduces for the gas production of AC2 relatively, and this illustrates that additive methylthiourea effectively can suppress the side reaction between mesylate electrolyte and negative pole zinc powder, thus effectively suppresses the aerogenesis of battery.
Weigh 5g zinc powder, add respectively in the electrolyte of 20ml battery B1, AC1, then seal, place 10 days at 50 DEG C, the gas flow that record the 1st, 3,5,10 day same day produce.Test result is in table 2.
Table 2 is the gas production that at 50 DEG C, zinc powder leaves standstill at the electrolyte of B1 and AC1
As can be seen from Table 2, battery B1 obviously reduces for the gas production of AC1 relatively, and this illustrates that additive triacetamide effectively can suppress the side reaction between stannous sulphate electrolyte and negative pole zinc powder, thus effectively suppresses the aerogenesis of battery.
Battery B2, AC2 are full of electricity, then negative pole zinc paper tinsel are taken out, to add respectively in the electrolyte of new 20ml battery B2, AC2 afterwards, then seal, at 50 DEG C, place a couple of days, the gas flow that record produces every day.Test result is in table 3.
Table 3 is the gas production that at 50 DEG C, zinc paper tinsel leaves standstill at the electrolyte of B2 and AC2
As can be seen from Table 3, battery B2 obviously reduces for the gas production of AC2 relatively, and this illustrates that additive triacetamide effectively can suppress the side reaction between mesylate electrolyte and negative pole zinc paper tinsel, thus effectively suppresses the aerogenesis of battery.
Battery C1, AC1 are full of electricity, then negative pole zinc paper tinsel are taken out, to add respectively in the electrolyte of new 20ml battery C1, AC1 afterwards, then seal, at 50 DEG C, place a couple of days, the gas flow that record produces every day.Test result is in table 4.
Table 4 is the gas production that at 50 DEG C, zinc paper tinsel leaves standstill at the electrolyte of C1 and AC1
As can be seen from Table 4, battery C1 obviously reduces for the gas production of AC1 relatively, and this illustrates that additive tween effectively can suppress the side reaction between stannous sulphate electrolyte and negative pole zinc paper tinsel, thus effectively suppresses the aerogenesis of battery.
Cycle performance of battery is tested:
Carry out charge and discharge cycles 20 times to battery A1-A3, B2-B3 and AC2, test its cycle performance, result is shown in table 5.
Table 5 is cycle performance of battery test result
From table 5, can find out that the capability retention after battery A1-A4, B2-B3 20 times has had the lifting of first mate, this illustrates additive of the present invention, effectively can improve the cycle performance of battery.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (16)

1. a battery, is characterized in that, described battery positive pole, negative pole and electrolyte, and described positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Described electrolyte comprises dissolving electrolyte and makes the solvent that described electrolyte ionizes; Described electrolyte comprises the first metal ion and the second metal ion; Described in charging process, the second reducing metal ions is that the second metal is deposited on described negative pole, and the second metal reversible oxidation is dissolved as described second metal ion in discharge process; Described battery also comprises the additive joined in described electrolyte, and described additive comprises one or more in tween, tertiary amine compound, heterocyclic quaternary ammonium salt and thioamides;
The general formula of described thioamides is as follows:
Wherein, R 1, R 2, R 3, R 4all be selected from the one in H, alkyl and phenyl, and R 1, R 2, R 3, R 4be asynchronously H.
2. battery according to claim 1, is characterized in that: described alkyl is methyl.
3. battery according to claim 1, is characterized in that: described thioamides is selected from one or more in tetramethyl thiourea, N, N-dimethyl sulfourea, N-methylthiourea and rhenocure CA.
4. battery according to claim 1, is characterized in that: in the electrolytic solution, and the mass percentage of described thioamides is 0.01% ~ 5%.
5. battery according to claim 1, is characterized in that: described tertiary amine compound is selected from one or more in triacetamide, triethylamine and triethanolamine; Described heterocyclic quaternary ammonium salt is selected from one or more in N-ethylpyridine hydrochloride, N-benzyl pyridine hydrochloride, N-2-ethoxy pyridine hydrochloride, N-2-hydroxypropyl pyridine hydrochloride and pyridine radicals-N-propane sulfonic acid betaine.
6. battery according to claim 1, is characterized in that: in the electrolytic solution, and the mass percentage of described tertiary amine compound or heterocyclic quaternary ammonium salt is 0.01% ~ 5%.
7. battery according to claim 1, is characterized in that: described tween is selected from polysorbate40.
8. battery according to claim 1, is characterized in that: in the electrolytic solution, and the mass percentage of described tween is 0.01% ~ 0.1%.
9. battery according to claim 1, is characterized in that: described additive also comprises the oxyacid radical ion compound of boron.
10. battery according to claim 1, is characterized in that: described electrolyte also comprises one or more in sulfate ion, chloride ion, acetate ion, nitrate ion and alkyl sulfonate ion.
11. batteries according to claim 10, is characterized in that: described alkyl sulfonate ion is selected from tosylate ion.
12. batteries according to claim 1, is characterized in that: described battery also comprises the barrier film between positive pole and negative pole.
13. batteries according to claim 1, is characterized in that: described first metal ion is selected from lithium ion, sodium ion or magnesium ion.
14. batteries according to claim 1, is characterized in that: described second metal is selected from manganese, iron, copper, zinc, chromium, nickel, tin or lead.
15. batteries according to claim 1, is characterized in that: the pH value of described electrolyte is 3 ~ 7.
16. batteries according to claim 1, is characterized in that: described solvent is water or alcohol.
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