CN104752754A - Electrolyte solution and battery - Google Patents

Electrolyte solution and battery Download PDF

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Publication number
CN104752754A
CN104752754A CN201410829521.8A CN201410829521A CN104752754A CN 104752754 A CN104752754 A CN 104752754A CN 201410829521 A CN201410829521 A CN 201410829521A CN 104752754 A CN104752754 A CN 104752754A
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electrolyte
ion
battery
metal
zinc
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蔡荆
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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Priority to CN201410829521.8A priority Critical patent/CN104752754A/en
Publication of CN104752754A publication Critical patent/CN104752754A/en
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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides an electrolyte solution used for a battery. The electrolyte solution comprises electrolyte and at least one solvent capable of dissolving the electrolyte and ionizing the electrolyte; the electrolyte solution comprises first metal ions; in a charging/discharging process, the first metal ions can be reduced and deposited into first metal on the negative electrode, and the first metal also can be reversibly oxidized and dissolved into the first metal ions; the electrolyte solution further comprises ions which participate in a positive electrode oxidation reduction reaction in the charging/discharging process; and the electrolyte solution further comprises an additive, and the additive comprises second metal ions with a hydrogen inhibiting effect and alkyl quaternary ammonium ions. The second metal ions and the alkyl quaternary ammonium ions are synergetic, so that a good hydrogen evolution inhibiting effect is realized. The invention further relates to the battery containing the electrolyte solution.

Description

Electrolyte and battery
Technical field
The present invention relates to a kind of electrolyte for battery, and utilize the battery of this electrolyte.
Background technology
Lead-acid battery, its appearance is super century-old, has definitely 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, flow battery etc., all cannot replace lead-acid battery in energy storage field.
A kind of Novel ion communicating battery of new appearance is expected to the general layout changing energy storage field recently.The operation principle of this ion-exchange 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 contains and participates in positive pole and deviates from-the first metal ion of insertion reaction and participate in the second metal ion of cathode deposition solubilizing reaction.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 the problems such as the distortion that zinc electrode exists, dendrite, corrosion and passivation, be present in ion-exchange battery equally, the liberation of hydrogen problem brought by zine corrosion is also a difficult problem of zinc electrode battery always.Due to the inhomogeneities of zinc surface, the electro-chemical activity of each point has larger difference, and some region becomes the anode of corrosion micro cell because current potential is lower, other region is then as its negative electrode, thus form the various micro cell system of number, cause zinc corrosion certainly in the battery.Not only consume active material zinc from corrosion, reduce capacity of negative plates, and the generation of gas adds inner pressure of battery, likely cause the problems such as electrolyte leakage, cell expansion and reduction in useful life.Therefore should reduce the corrosion of zinc load in battery as far as possible, suppress the generation of gas.
At present, though have various additive for suppressing the corrosion liberation of hydrogen of zinc load, but desirable effect is not all had.Thus, need a kind of method of zinc load corrosion and liberation of hydrogen that suppresses to overcome the problems referred to above.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of electrolyte for battery, and this electrolyte effectively can suppress corrosion and the liberation of hydrogen problem of zinc load.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows: a kind of electrolyte for battery, and it comprises electrolyte and at least one can be dissolved electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte comprise in charge and discharge process negative pole can reduce be deposited as the first metal and first metal energy reversible oxidation dissolve the first metal ion; Described electrolyte also comprises in charge and discharge process the ion participating in positive pole redox reaction; Described electrolyte also comprises additive, and described additive comprises the second metal ion and quaternary ammonium alkyl radical ion; Described second metal ion be selected from tin ion, indium ion, bismuth ion one or several.
Preferably, described metal ion content accounts for 0.01% ~ 5% of electrolyte total weight.
Preferably, the concentration of described quaternary ammonium alkyl radical ion is 0.0001 ~ 0.5mol/L.
Preferably, described first metal ion is zinc ion.
Preferably, described second metal ion is tin ion, and described quaternary ammonium alkyl radical ion is cetyltrimethylammonium ion.
The source of tin ion can be, one or several in the oxide of tin, acetate, carbonate, sulfate, nitrate.
Preferably, described additive also comprises polyoxyethylene type organic.
Preferably, described polyoxyethylene type organic is APES.
Preferably, the organic concentration of described polyoxyethylene is 10 ~ 40ppm.
Preferably, the pH value of described electrolyte is 3 ~ 7.
Present invention also offers a kind of battery, described battery positive pole, negative pole and electrolyte as above.
The beneficial effect of this programme is: compared with prior art, and electrolyte of the present invention effectively can suppress the generation of negative gas, reduces the corrosion of battery.
Accompanying drawing explanation
Fig. 1 is the comparison diagram that A1, AC1, AC2, AC3, AC4 and AC5 electrolyte produces gas;
Fig. 2 is the battery capacity of B1, B2, BC1 and BC3 battery and the comparison diagram of cycle-index;
Fig. 3 is the charging and discharging curve of B1 battery;
Fig. 4 is the charging and discharging curve of B2 battery;
Embodiment
Below in conjunction with the drawings and the specific embodiments, the present invention is described in further detail.
For an electrolyte for battery, described electrolyte comprises electrolyte and at least one can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte comprise in charge and discharge process negative pole can reduce be deposited as the first metal and first metal energy reversible oxidation dissolve the first metal ion; Electrolyte also comprises in charge and discharge process the ion participating in positive pole redox reaction; Electrolyte also comprises additive, and additive comprises the second metal ion and quaternary ammonium alkyl radical ion; Second metal ion be selected from tin ion, lead ion, indium ion, bismuth ion one or several.
In electrode or electrolyte, add a kind of additive separately, at present existing multiple method, but most of effect is general.The present invention utilizes the synergy of inorganic additive and organic additive, adds inorganic additive and organic additive in the electrolytic solution simultaneously, reaches the effect increasing and suppress zinc load corrosion.
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 of the present invention is preferably water and/or alcohol.Wherein alcohol includes but not limited to methyl alcohol or ethanol.
The first metal ion in electrolyte, can reduce at negative pole in charging process and be deposited as the first metal, in discharge process, the first metal reversible oxidation is the first metal ion.Namely, when battery charges, the first reducing metal ions in electrolyte becomes the first metallized metal, is deposited on negative pole; When battery discharge, the first metallized metal is oxidized into the first metal ion and from stripping negative pole, enters electrolyte.Preferably, the first metal ion is zinc ion.
In a preferred embodiment, a kind of ion occurring to embed and deviate from anode is also comprised in electrolyte.When battery charges, this ion in electrolyte is embedded in positive electrode; During battery discharge, this ion embedded during charging is deviate from again in electrolyte from positive electrode.Preferably, this ion is selected from one in lithium ion, sodium ion or two kinds, more preferably lithium ion.
In a preferred embodiment, a kind of ion in anode generation redox reaction is also comprised in electrolyte.When battery charges, this ion in electrolyte is oxidized; During battery discharge, active material oxidized during charging is reduced again.Preferably, this ion is selected from one in bromide ion, vanadium ion or two kinds.
Under a preferred implementation, electrolyte comprises zinc ion and lithium ion.Along with the carrying out of discharge and recharge, zinc ion deposits at negative pole-dissolves, and lithium ion embeds at positive pole-deviates from.
Under a preferred implementation, electrolyte comprises bromide ion, and along with the carrying out of discharge and recharge, zinc ion deposits at negative pole-dissolves, and bromide ion is at positive pole generation oxidation-reduction reaction.
The second metal ion included in electrolyte is the metal ion that overpotential of hydrogen evolution is higher than the overpotential of hydrogen evolution of zinc, the second metal ion be selected from tin ion, indium ion, bismuth ion one or several.Second metal ion derives from the inorganic additive added in electrolyte, inorganic additive be selected from tin compound, indium compound, bismuth compound one or several.These inorganic additives join in electrolyte, produce metal ion, and because overpotential of hydrogen evolution is higher, hydrogen is separated out in negative terminal surface difficulty, is of value to the generation suppressing gas.Preferably, the metal ion in electrolyte of the present invention is divalent tin ion.Preferably, provide the inorganic additive of divalent tin ion to be selected from tin compound, tin compound be selected from the oxide of tin, acetate, carbonate, sulfate, nitrate one or several.Under a preferred implementation, tin compound is stannous sulfate.
Inorganic additive adds the method for electrolyte, according to the different situations of electrolyte or barrier film, can select different feed postition.Feed postition includes but not limited to directly add in electrolyte, or is added on barrier film with hanging drop.More preferably, inorganic additive is directly joined in electrolyte, then electrolyte is dripped on barrier film.
Quaternary ammonium alkyl radical ion in electrolyte of the present invention, ionizes generation in the electrolytic solution by alkyl quaternary ammonium salts compounds.Alkyl quaternary ammonium salts compounds is a kind of organic cation surfactant, and itself has certain inhibitory action to the corrosion of zinc load and liberation of hydrogen.Alkyl quaternary ammonium salts compounds includes but not limited to aliphatic quaternary ammonium salt compounds.Preferably, alkyl quaternary ammonium salts compounds is halide salt.More preferably, alkyl quaternary ammonium salts compounds is alkyl bromination ammonium.Particularly preferably, alkyl quaternary ammonium salts compounds is the one in softex kw (CTAB), DTAB, Cetyltrimethylammonium bromide or TBAB.
Alkyl quaternary ammonium salts compounds and the high metallic compound of overpotential of hydrogen evolution all have certain liberation of hydrogen inhibition separately, respective advantage can be played because both synergies are used in combination, make up the deficiency of the other side, thus the inhibition drastically increasing their combinations presses down hydrogen effect.Preferably, CTAB and tin compound used in combination, better inhibition can be produced.
In a preferred embodiment, tin ion content accounts for 0.01% ~ 5% of electrolyte total weight.
In a preferred embodiment, in electrolyte, the concentration range of CTAB is 0.0001 ~ 0.5mol/L.
Cetyltrimethylammonium ion and tin ion all have certain suppression liberation of hydrogen effect separately, due to cooperative effect together when using, can strengthen and suppress liberation of hydrogen effect.
In a preferred embodiment, APES (Op-10) is also comprised in electrolyte.
Op-10 is a kind of non-ionic surface active agent of pH=6 ~ 7, has the function of froth breaking.It joins after in the electrolyte containing CTAB and tin compound, not only can well reduce the foam in electrolyte, can also produce act synergistically with CTAB and tin compound, strengthens the function of the suppression negative pole liberation of hydrogen of electrolyte further.
Preferably, the alkyl of Op-10 is nonyl, octyl group or dodecyl, and more preferably, the alkyl of Op-10 is nonyl.
In a preferred embodiment, the concentration of Op-10 is 10 ~ 40ppm.
In order to make battery performance more optimize, electrolyte ph scope of the present invention preferably 3 ~ 7.The scope of pH can be adjusted by buffer.The pH of electrolyte is too high, may affect the concentration of zinc ion in electrolyte, and the pH of electrolyte is too low, then can aggravate the corrosion of electrode material.And the pH scope of electrolyte is remained on 3 ~ 7, both effectively can ensure the concentration of metal ion in electrolyte, can also electrode corrosion be avoided.Simultaneously within the scope of the pH of 3 ~ 7, be also applicable to very much the existence of cationic surfactant.
Present invention further teaches a kind of battery, comprise positive pole, negative pole and above-mentioned electrolyte.Positive pole comprises the positive active material for positive pole discharge and recharge, and electrolyte is electrolyte provided by the invention.
In a preferred embodiment, the positive active material of battery is can the reversible material deviating from-embed metal ion.Positive active material can the reversible metal ion deviate from-embed be lithium ion.During negative pole charging, positive active material deviates from lithium ion, and the zinc ion simultaneously in electrolyte obtains electronics and is reduced to zinc metal and is deposited on negative pole on negative pole.During electric discharge, the zinc metal be deposited on negative pole is oxidized, loses electronics and changes zinc ion into and enter in electrolyte; Lithium ion in electrolyte is embedded in positive active material again.
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.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 also 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 is, when reversiblely can deviate from-embed the material of lithium ion, preferably 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, positive active material is, when reversiblely can deviate from-embed the material of sodium ion, preferably can select NaVPO 4f etc.Positive pole, also comprises the plus plate current-collecting body of load positive active material, and the material of plus plate current-collecting body is selected from the one in carbon-based material, metal or alloy.
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, there is not side reaction in being present in electrolyte that plus plate current-collecting body can be stable substantially, thus ensure that battery has stable cycle performance.
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 mixture and the derivative of a kind of or above-mentioned polymer in polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, poly-divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates.More preferably, positive electrode binder is selected from polytetrafluoroethylene (PTFE), Kynoar (PVDF) or butadiene-styrene rubber (SBR).
The negative pole of battery, it is the first metal that the material of electrochemical reaction occurs, and the first metal can be the first metal ion and the first metal ion energy reversible reduction is deposited as the first metal by oxidation dissolution.Preferably, negative pole also comprises cathode additive agent, and cathode additive agent comprises tin compound, and tin compound adds the mode of negative pole, may be slightly different according to negative pole different situations.Adding Way can be selected from physical method or chemical method, and physical method includes but not limited to suspension method, Vacuum Deposition, magnetron sputtering; Chemical method comprises electrochemistry plating etc.More preferably, tin compound is one or several in the oxide of tin, acetate, carbonate, sulfate, nitrate.The addition of tin compound accounts for 0.01% ~ 10% of negative pole total weight.
In a preferred embodiment, negative pole comprises negative current collector, and negative current collector is only as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.Now, negative current collector is the carrier for negative pole discharge and recharge.Under this execution mode, tin compound adds the mode of negative pole, includes but not limited to, tin compound is added dispersant and makes dispersion liquid, by dispersion on negative current collector, finally removes dispersant.
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, the such as paper tinsel of 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 a preferred embodiment, negative pole, except negative current collector, also comprises the negative electrode active material of load on negative current collector.Now, negative electrode active material is the carrier for negative pole discharge and recharge.Negative electrode active material is zinc.
In a preferred embodiment, directly adopt zinc metal sheet as negative pole, zinc metal sheet, both as negative current collector, is also negative electrode active material simultaneously.Now, zinc metal sheet be for negative pole discharge and recharge carrier.
In a preferred embodiment, battery is a kind of flow battery.Preferably, the positive active material of battery is vanadium ion electrolyte or bromide ion electrolyte.In a preferred embodiment, positive active material is bromide ion electrolyte; During charging, the oxidized generation bromine of the bromide ion in electrolyte simple substance, and lose electronics; Electronics arrives battery cathode via external circuit, and the zinc ion simultaneously in electrolyte obtains electronics and is reduced to zinc metal and is deposited on negative pole on negative pole; During electric discharge, the zinc metal be deposited on negative pole is oxidized, loses electronics and changes zinc ion into and enter in electrolyte; Electronics arrives positive pole through external circuit, and the bromine simple substance of positive pole accepts electronics and is reduced generation bromide ion, and bromide ion enters electrolyte.
Certainly in order to make battery performance more excellent, in negative pole and electrolyte, add tin compound simultaneously.
Preferably, tin compound is selected from one or several in the oxide of tin, acetate, carbonate, sulfate, nitrate.
The using dosage of tin compound in negative pole is preferably as follows: when being used alone stannous sulfate, and stannous sulfate accounts for 0.01 ~ 10% of negative pole total weight.When being used alone nitric acid Asia tin, the sub-tin of nitric acid accounts for 0.01 ~ 10% of negative pole total weight.The mixture of stannous sulfate and the sub-tin of nitric acid can certainly be used.
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 of the present invention 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.
The all specialties used in the present invention and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Below in conjunction with embodiment, further illustrate content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.In the present invention, if not refer in particular to, all percentage is unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is conventional.
embodiment 1
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add CTAB and stannous sulfate simultaneously, be configured to the zinc sulfate of 2mol/L, the lithium sulfate of 1mol/L, the CTAB of 0.001mol/L, stannous sulfate content is the electrolyte of 0.1wt%, be denoted as A1.
embodiment 2
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add CTAB, stannous sulfate and Op-10 simultaneously, be configured to the zinc sulfate of 2mol/L, the electrolyte of the lithium sulfate of 1mol/L, the CTAB of 0.001mol/L, stannous sulfate content to be 0.1wt%, Op-10 content be 20ppm, be denoted as A2.
embodiment 3
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add CTAB, stannous sulfate and Op-10 simultaneously, be configured to the zinc sulfate of 2mol/L, the electrolyte of the lithium sulfate of 1mol/L, the CTAB of 0.001mol/L, stannous sulfate content to be 0.1wt%, Op-10 content be 40ppm, be denoted as A3.
comparative example 1
Take zinc sulfate, lithium sulfate is dissolved in deionized water, be configured to the electrolyte of the zinc sulfate of 2mol/L, the lithium sulfate of 1mol/L, be denoted as AC1.
comparative example 2
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add indium sulfate simultaneously, be configured to the zinc sulfate of 2mol/L, the lithium sulfate of 1mol/L, indium sulfate content is the electrolyte of 0.1wt%, be denoted as AC2.
comparative example 3
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add stannous sulfate simultaneously, be configured to the zinc sulfate of 2mol/L, the lithium sulfate of 1mol/L, stannous sulfate content is the electrolyte of 0.1wt%, be denoted as AC3.
comparative example 4
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add stannous sulfate and indium sulfate simultaneously, the content being configured to the zinc sulfate of 2mol/L, the lithium sulfate of 1mol/L, stannous sulfate and indium sulfate is the electrolyte of 0.1wt%, is denoted as AC4.
comparative example 5
Take zinc sulfate, lithium sulfate is dissolved in deionized water, add CTAB simultaneously, be configured to the electrolyte of the zinc sulfate of 2mol/L, the lithium sulfate of 1mol/L, the CTAB of 0.001mol/L, be denoted as AC5.
The preparation of battery
LiMn2O4 LMO, conductive agent graphite, binding agent butadiene-styrene rubber (SBR) and CMC (CMC) are mixed in water according to mass ratio 90:5:2.5:2.5, form uniform anode sizing agent, plus plate current-collecting body (50 μm of stainless steel cloths) two sides slurry being coated in coated with conductive film forms active material layer, carried out compressing tablet subsequently, be cut into 8 × 10cm (test gas content) or 6 × 6cm (for other performances of test battery) size, make positive plate, positive plate thickness is 0.4mm, and positive active material surface density is 750g/m 2.Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is ultra-fine fibre glass (AGM) barrier film, and barrier film is suitable with positive pole with negative pole size.
embodiment 4-6
Be electrolyte with A1-A3, prepare battery as stated above, be denoted as B1-B3.
comparative example 6-10
Be electrolyte with AC1-AC5, prepare battery as stated above, be denoted as BC1-BC5.
performance test:
Gassing rate is tested
The operation of zinc powder gassing rate testing experiment is as follows: 10g zinc powder 1%wt bonding agent polytetrafluoroethylene (PTFE) is made into calamine cream, fill in 50ml injection needles cylinder, inject 30ml electrolyte, drain gas, syringe needle rubber seal is lived, and observes aerogenesis at putting into 60 DEG C.Gas production is using the length in shared syringe space as unit.
Respectively electrolyte A1, AC1, AC2, AC3, AC4, AC5 are tested as stated above, using the gas production of electrolyte AC1 as with reference to statistics, its gas production is set as 1, and adds up relative to blank value with first day gas production.The gassing rate result of other electrolyte as shown in Figure 1.
As seen from Figure 1, the gassing rate of A1, AC2, AC3, AC4, AC5 is respectively 0.23,0.44,0.52,0.40,0.88 of AC1 gassing rate.Inorganic additive stannous sulfate, indium sulfate and organic additive CTAB all have certain inhibitory action to the aerogenesis of zinc load.And the aerogenesis of the combined additive of stannous sulfate and CTAB to zinc load has better inhibition, illustrate and create synergy between the two.
Respectively electrolyte A1, A2, A3 are tested as stated above, testing producing tolerance.Its result is as shown in table 1.Electrolyte A1, A2, A3 be corresponding following table Op-10 concentration 0,20ppm, 40ppm respectively.
The impact of variable concentrations Op-10 on gassing rate is added in table 1 electrolyte
Can seeing from table 1, adding the Op-10 of 20ppm relative to only having 0.1%wt stannous sulfate and 10 -3the electrolyte of mol/LCTAB has better suppression liberation of hydrogen effect.And this solution of shake 50ml, can find bubble little (diameter is about 1-3mm), and quantity is few; And only have 0.1%wt stannous sulfate and 10 -3after the electrolyte shake of mol/LCTAB, bubble large (diameter is about 0-1cm), quantity is many.So, add Op-10 and there is froth breaking and the effect suppressing zinc liberation of hydrogen.
battery testing
Carry out battery performance detection to battery B1, B2, BC1, BC3 respectively, be first charged to 2.1V with constant current 0.2C under normal temperature, then constant voltage is charged to cut-off current 60mA, then constant current 0.2C is discharged to 1.4V, cycle charge-discharge like this.
The relation comparison diagram of battery capacity and cycle-index as shown in Figure 2.As seen from Figure 2, the initial capacity that electrolyte contains the B1 battery of CTAB and tin ion is 301mAh/g, the initial capacity that electrolyte contains the B2 battery of CTAB, stannous sulfate and Op-10 is 282mAh/g, the initial capacity that electrolyte does not contain the BC1 battery of additive is 240mAh/g, and the initial capacity that electrolyte contains the BC3 battery of stannous sulfate is 286mAh/g.Wherein, the discharge capacity of B1, B2 battery and cycle performance are better than BC1, BC3 battery.Composition graphs 1, Fig. 2 and table 1, electrolyte is when not doping, and capacity is lower, and gassing rate is larger; Electrolyte is after adding stannous sulfate, though there is the reduction of gassing rate, initial capacity rises to some extent, and capacity attenuation is very fast, and cycle performance reduces; After electrolyte adds stannous sulfate and CTAB, initial capacity continues to rise, and cycle performance is better, and gassing rate significantly reduces; After electrolyte adds CTAB, stannous sulfate and Op-10, battery gassing rate reduces further, but initial capacity and cycle performance decline to some extent.
Above result shows, electrolyte adds CTAB and tin compound produces synergy, and effectively enhance the effect of its zinc-plated negative pole liberation of hydrogen, defoamer Op-10 not only has defoaming effect to electrolyte, also have the effect reducing further liberation of hydrogen, itself and CTAB and tin also have synergy.
The graph of a relation of Fig. 3 and Fig. 4 is BC3 and A1 battery respectively in discharge and recharge voltage and time, corresponding with Fig. 2.As can be seen from Fig. 3 and Fig. 4, electrolyte adds the battery that tin compound and electrolyte adds tin compound and CTAB and all has stable charging and discharging curve.
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 (10)

1. for an electrolyte for battery, it is characterized in that: described electrolyte comprises electrolyte and at least one can be dissolved electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte comprise in charge and discharge process negative pole can reduce be deposited as the first metal and first metal energy reversible oxidation dissolve the first metal ion; Described electrolyte also comprises in charge and discharge process the ion participating in positive pole redox reaction; Described electrolyte also comprises additive, and described additive comprises the second metal ion and quaternary ammonium alkyl radical ion; Described second metal ion be selected from tin ion, indium ion, bismuth ion one or several.
2. electrolyte according to claim 1, is characterized in that: described second metal ion content accounts for 0.01% ~ 5% of electrolyte total weight.
3. electrolyte according to claim 1, is characterized in that: the concentration of described quaternary ammonium alkyl radical ion is 0.0001 ~ 0.5mol/L.
4. electrolyte according to claim 1, is characterized in that: described first metal ion is zinc ion.
5. electrolyte according to claim 1, is characterized in that: described second metal ion is tin ion, and described quaternary ammonium alkyl radical ion is cetyltrimethylammonium ion.
6. electrolyte according to claim 1, is characterized in that: described additive also comprises polyoxyethylene type organic.
7. electrolyte according to claim 6, is characterized in that: described polyoxyethylene type organic is APES.
8. electrolyte according to claim 6, is characterized in that: the organic concentration of described polyoxyethylene is 10 ~ 40ppm.
9. electrolyte according to claim 1, is characterized in that: the pH value of described electrolyte is 3 ~ 7.
10. a battery, is characterized in that: described battery positive pole, negative pole and as arbitrary in claim 1-9 as described in electrolyte.
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