CN104518205A - Preparation method for zinc anode, zinc anode and battery - Google Patents
Preparation method for zinc anode, zinc anode and battery Download PDFInfo
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- CN104518205A CN104518205A CN201310452547.0A CN201310452547A CN104518205A CN 104518205 A CN104518205 A CN 104518205A CN 201310452547 A CN201310452547 A CN 201310452547A CN 104518205 A CN104518205 A CN 104518205A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
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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
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method for a zinc anode. The preparation method comprises: pretreating a metal zinc, and preparing the anode from the pretreated metal zinc, wherein pretreatment comprises contacting the metal zinc with a processing liquid for modifying the metal zinc surface, and the processing liquid is one of a hydrogen peroxide solution, a permanganate solution, a trivalent ferric ion solution and a tetravalent cerium ion solution. The invention also provides the zinc anode obtained by employing the above preparation method and a battery containing the above zinc anode. By using the processing liquid for pretreating the metal zinc, the side reaction of the zinc anode is reduced, generation of a zinc anode gas is effectively inhibited, and thus cell inflation is avoided, the safety performance of the cell is improved, and cell performance attenuation is effectively inhibited.
Description
Technical field
The present invention relates to a kind of preparation method of zinc load.
The present invention relates to the zinc load that a kind of said method obtains.
The present invention relates to a kind of battery containing above-mentioned zinc load.
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 zinc ion, and electrolyte deviates from containing participating in positive pole-the first metal ion of insertion reaction and participate in the zinc ion of cathode deposition-solubilizing reaction.The type battery theoretical energy density 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.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of preparation method of negative pole, and the application of electrode obtained by this preparation method, in battery, is avoided producing a large amount of gas.
The invention provides a kind of preparation method of zinc load, described preparation method comprises the following steps, and carries out preliminary treatment to metallic zinc, then pretreated metallic zinc is made zinc load; Described preliminary treatment comprises makes metallic zinc surface modification by metallic zinc contact pairs liquid; Described treatment fluid is selected from the one in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
Present invention also offers a kind of preparation method of zinc load, described preparation method comprises metallic zinc is made pending negative pole, then described pending negative pole is carried out preliminary treatment, obtains zinc load; Described preliminary treatment comprises makes metallic zinc surface modification by described pending cathode contact treatment fluid; Described treatment fluid is selected from the one in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
Preferably, the mass percentage concentration of described hydrogen peroxide solution is 1 ~ 30%.
Preferably, the time of contact of described treatment fluid and metallic zinc is 0.5 ~ 24h.
Preferably, the way of contact of described treatment fluid and metallic zinc is for soak.
Preferably, described permanganate solution is liquor potassic permanganate.
Preferably, described ferric ion solution is selected from one or more in ferric chloride solution, iron nitrate solution, ferrum sulfuricum oxydatum solutum.
Preferably, described quadrivalent cerium solion is ceric sulfate solution.
Present invention also offers a kind of zinc load, described zinc load is obtained by the preparation method of zinc load provided by the present invention.
Present invention also offers a kind of zinc load, described zinc load comprises the metallic zinc of surface with passivating film, containing zinc oxide in described passivating film.
Present invention also offers 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 at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes, and described solvent is water or alcohol, and the pH value of described electrolyte is 3 ~ 7; Described electrolyte comprises in zinc ion and charge and discharge process at the first metal ion that described positive pole can reversiblely be deviate from-embed; Described negative pole is zinc load provided by the present invention.
Preferably, described electrolyte comprises one or more in sulfate ion, chloride ion, acetate ion, nitrate ion and alkyl sulfonate ion.
Preferably, described alkylsulfonate radical ion is methanesulfonate ions.
Preferably, described battery also comprises the barrier film between positive pole and negative pole.
Preferably, described first metal ion is selected from lithium ion or sodium ion.
Preferably, described positive active material is selected from LiMn
2o
4, LiFePO
4and LiCoO
2in one or more.
Compared with prior art, zinc load preparation method of the present invention comprises, through treatment fluid, preliminary treatment is carried out to metallic zinc, make the surface modification of metallic zinc, reduce the generation of zinc load side reaction, effectively can suppress the generation of zinc load gas, thus avoid battery swell, enhance the security performance of battery, also effectively inhibit cell performance decay simultaneously.
Accompanying drawing explanation
Fig. 1 is the cycle performance figure of the battery of embodiment 6.
Fig. 2 is the cycle performance figure of the battery of embodiment 9.
Fig. 3 is the cycle performance figure of the battery of comparative example 2.
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 preparation method for zinc load, described preparation method comprises the following steps, and carries out preliminary treatment to metallic zinc, then pretreated metallic zinc is made zinc load; Described preliminary treatment comprises makes metallic zinc surface modification by metallic zinc contact pairs liquid; Described treatment fluid is selected from the one in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
Wherein, metallic zinc can be zinc powder, can also be zinc metal sheet.
Before processing metallic zinc treatment fluid, need to carry out prerinse to metallic zinc, to remove the grease on metallic zinc surface.
Particularly, a large amount of clear water of metallic zinc is washed, or is immersed in degreaser, then rinse well with a large amount of clear water.
Adopt treatment fluid to carry out preliminary treatment to metallic zinc, with to metallic zinc modifying surface, change the surface activity of metallic zinc; Make it in battery charging and discharging circulation, the generation of negative pole side reaction can be suppressed, do not affect simultaneously the zinc ion reduction in electrolyte is deposited as metallic zinc and reversible be the negative electricity chemical reaction of zinc ion by metallic zinc oxidation dissolution.
Treatment fluid is selected one and is selected from hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
Wherein, permanganate solution refers to the solution of solubility permanganate formation soluble in water.Permanganate solution of the present invention can be selected from one or more in high manganese lithium solution, sodium permanganate solution, liquor potassic permanganate, ammonium permanganate solution, acerdol solution, barium permanganate solution, zinc permanganate solution, magnesium permanganate solution, permanganic acid mercury solution, cadmium permanganate solution and permanganic acid rubidium solution.Preferably, permanganate solution is liquor potassic permanganate.
Ferric ion solution refers to the aqueous solution containing ferric ion.Ferric ion solution of the present invention can be selected from ferric chloride solution, ferric bromide, iron nitrate solution, ferrum sulfuricum oxydatum solutum, thiocyanation ferrous solution etc.Preferably, ferric ion solution is selected from one or more in ferric chloride solution, iron nitrate solution and ferrum sulfuricum oxydatum solutum.
Quadrivalent cerium solion refers to the aqueous solution containing quadrivalent cerium ion.Quadrivalent cerium solion of the present invention can be selected from ceric sulfate solution, Cericammoniumsulfate solution, ceric ammonium nitrate solution etc.Preferably, quadrivalent cerium solion of the present invention is ceric sulfate solution.
Treatment fluid of the present invention, preferably adopts hydrogen peroxide solution.Adopt hydrogen peroxide solution as treatment fluid, the product after its process is easily separated, and does not introduce other impurity, the zinc load excellent performance simultaneously made.
In order to increase the effect of process, the mass percentage concentration of hydrogen peroxide is preferably 1 ~ 30%, is more preferably 5 ~ 30%.
The object of the present invention's contact is that make metallic zinc under the effect for the treatment of fluid, surface reacts, thus makes its surface modification.
Under a preferred implementation, contact is preferably soaks, and is immersed in treatment fluid by metallic zinc.Such as, when processing zinc powder, zinc powder is immersed in treatment fluid.When such as processing again zinc metal sheet, zinc metal sheet is immersed in treatment fluid, the two-sided of zinc metal sheet is processed simultaneously.
Under another preferred implementation method, contact as by zinc metal sheet single-contact treatment fluid.
Wherein, zinc metal sheet single-contact treatment fluid can adopt diaphragm mode, is in particular: the one side of zinc metal sheet is enclosed diaphragm, and then all immersed in treatment fluid by zinc metal sheet and soak, the one side with diaphragm does not contact with treatment fluid under the effect of diaphragm; After treating that immersion is complete, remove diaphragm.
Zinc metal sheet single-contact can also be direct single-contact, is in particular: faced up by zinc metal sheet one, one to face down, the liquid level of a contact pairs liquid down, and one side is upward positioned on the liquid level for the treatment of fluid, does not contact with treatment fluid.
Zinc metal sheet single-contact is preferably immersed treatment fluid by the present invention.The one side (being equivalent to the one side as collector) of not carrying out zinc ion deposition-dissolving by zinc metal sheet does not carry out preliminary treatment; The one side (being equivalent to the one side as negative electrode active material) that zinc metal sheet carries out zinc ion deposition-dissolving carries out preliminary treatment.Only preliminary treatment is carried out to the one side participating in negative reaction, can better suppress gas to produce, do not affect the conductivity of negative pole simultaneously.
According to different situations, stir in contact process to strengthen treatment effect; Can not certainly stir, namely directly leave standstill.
Preferably, the temperature of process is 15 ~ 50 DEG C, is more preferably room temperature.At this temperature, be both conducive to strengthening processing speed and effect, high temperature can also be avoided dioxygen water mitigation.
Preferably, the time 0.5 ~ 24h of process, preferred 24h.Can ensure that zinc and hydrogen peroxide fully react like this, at the passivating film that the Surface Creation of metallic zinc is good.
After contact, metallic zinc is separated, rinses well, and dry.
After pre-processing, negative pole will be made into through pretreated metallic zinc.
According to the difference of final zinc load morphosis, the method needed for employing makes negative pole.Such as pretreated zinc metal sheet is carried out cutting and be made into negative pole; Such as mixed with binding agent by pretreated zinc powder again, load makes negative pole on negative current collector.
The present invention also provides a kind of preparation method of zinc load, and described preparation method comprises metallic zinc is made pending negative pole, then described pending negative pole is carried out preliminary treatment, obtains zinc load;
Described preliminary treatment comprises makes metallic zinc surface modification by described pending cathode contact treatment fluid; Described treatment fluid is selected from the one in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
The preparation method of the method and aforesaid zinc load, unlike, preliminary treatment sequence of steps in preparation method is different, and also namely the pretreated object of the method is the pending negative pole that metallic zinc is made, instead of metallic zinc.Other parts are substantially identical with the preparation method of aforesaid zinc load, specifically with reference to the preparation method of aforesaid zinc load, can not repeat them here!
Present invention also offers the zinc load that a kind of said method obtains.
Zinc load of the present invention, it comprises the metallic zinc of surface with passivating film, containing zinc oxide in described passivating film.When metallic zinc is after preliminary treatment, the surface of metallic zinc can generate the passivating film that one deck contains zinc oxide.This passivating film effectively can suppress the generation of gas in battery, but does not affect the oxidation dissolution of the metallic zinc of normal negative pole and the reduction deposition of zinc ion.
When zinc load, in ion-exchange battery, electrochemical reaction occurs, the zinc in zinc load can oxidation dissolution be zinc ion, and the zinc ion energy reversible reduction in electrolyte is zinc and is deposited on negative pole.
According to the difference that negative pole acts in the battery, two kinds of different forms can be had:
In the first preferred embodiment, negative pole comprises negative current collector, and pretreated metallic zinc load is on negative current collector.Metallic zinc is present in negative pole as negative electrode active material, and negative current collector 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 on the negative current collector plated surface of Copper Foil or graphite foil, plumbous or silver-colored.
When adopting zinc metal sheet as negative electrode active material, composite bed will be formed through pretreated zinc metal sheet and negative current collector.
When adopting zinc powder as negative electrode active material, slurry will be made through pretreated zinc powder, and then slurry being coated on negative current collector and making negative pole.
In a particular embodiment, when preparing negative pole, except negative electrode active material zinc powder, according to actual conditions, also interpolation cathode conductive agent and negative electrode binder promote the performance of negative pole as required.
Preferably, zinc powder accounts for 80 ~ 95% of negative pole total weight, and negative electrode binder accounts for 5 ~ 20% of negative pole total weight.
In the second preferred implementation, directly adopt pretreated zinc metal sheet as negative pole, zinc metal sheet, both as negative current collector, is also negative electrode active material simultaneously.
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 at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes, and described solvent is water or alcohol, and the pH value of described electrolyte is 3 ~ 7; Described electrolyte comprises in zinc ion and charge and discharge process at the first metal ion that described positive pole can reversiblely be deviate from-embed; Described negative pole is negative pole provided by the present invention.
The charge-discharge principle of battery is: during charging, deviates from the first metal ion in positive active material, simultaneously oxidized with positive active material, and ejected electron; Electronics arrives battery cathode via external circuit, and the zinc ion simultaneously in electrolyte obtains electronics and is reduced on negative pole, and is deposited on negative pole.During electric discharge, the zinc 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 positive active material accepts electronics and is reduced, and the first metal ion embeds in positive active material simultaneously.
Wherein, the positive active material in positive pole participates in positive pole reaction, and reversiblely can deviate from-embed the first metal ion.
Preferably, lithium ion or sodium 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.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 of the present invention 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.
Preferably, carry out Passivation Treatment to plus plate current-collecting body, 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).
Concrete, chemical passivation treatment step is: inserted by plus plate current-collecting body in oxidizing agent solution, maintains 0.5 ~ 1 hour, makes anode collection surface form passivating film, finally takes out plus plate current-collecting body and cleans also dry.
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.
Under a preferred implementation, directly electrochemical oxidation is carried out to plus plate current-collecting body, be namely used for battery assembling advance row pre-passivating at plus plate current-collecting body.Concrete, using plus plate current-collecting body as work electrode, it is suitable for electrode and reference electrode composition three-electrode system to select, and is oxidized plus plate current-collecting body; Applying voltage is 2.1 ~ 2.4V.Plus plate current-collecting body can be metal, as metallic aluminium; Plus plate current-collecting body also can be alloy, as stainless steel or aluminium alloy.Certainly, also can adopt with plus plate current-collecting body is two electrode systems of work electrode, and be oxidized plus plate current-collecting body, applying voltage is 2.1 ~ 2.4V.
Under a preferred implementation, also can carry out discharge and recharge to the battery containing plus plate current-collecting body thus reach the object of plus plate current-collecting body being carried out to passivation, during charging, voltage is all charged to 2.1 ~ 2.4V, and during electric discharge, voltage is all put to 1.35 ~ 1.45V, and discharge and recharge number of times is not less than 1.
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).
Dissolution with solvents electrolyte in electrolyte, and electrolyte is ionized, finally generate the cation that can move freely and anion in the electrolytic solution.
Solvent is water or alcohol; Wherein alcohol includes but not limited to methyl alcohol or ethanol.
Wherein, the first metal ion in electrolyte, in battery charge and discharge process, can deviate from-embeds positive pole is reversible.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 or sodium ion, is more preferably lithium ion.
Zinc ion in electrolyte, in battery charge and discharge process, can in the reversible deposition-dissolving of negative pole.Namely when battery charges, the zinc ion in electrolyte is reduced into metallic zinc, is deposited on negative pole; When battery discharge, metallic zinc is oxidized to zinc ion, dissolves enter electrolyte from negative pole.
Under a preferred embodiment, the first metal ion of the present invention is lithium ion, 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 one or more in sulfate ion, chloride ion, nitrate ion, acetate ion, formate ion and phosphate anion.
Under a preferred implementation, in electrolyte, anion comprises one or more in sulfate ion, chloride ion, acetate ion and nitrate ion.
Under another preferred implementation, in electrolyte, anion comprises alkyl sulfonate ion.
Containing the electrolyte of alkyl sulfonate ion, there is following benefit:
The first, alkyl sulfonate ion effectively can improve the first metal ion and zinc ion solubility in the electrolytic solution; The second, alkyl sulfonate ion can suppress the generation of gas further; 3rd, alkyl sulfonate ion effectively can also reduce the self-discharge rate of battery.4th, other anion salts relatively, the electrolyte of alkyl sulfonate ion does not freeze at-20 DEG C, and battery can be made to have better cryogenic property.
More preferably, the anion in electrolyte is only containing alkyl sulfonate ion, and namely electrolyte is alkylsulfonate and the alkyl sulfonic acid zinc of the first metal.
Particularly preferably, electrolyte is Lithium perchlorate and alkyl sulfonic acid zinc.
Alkyl sulfonate ion includes but not limited to aliphatic sulfonic radical ion, and is not limited on aliphatic group with functional group or substituting group.Preferably meet following general formula:
R-SO
3 -or Y-R '-SO
3 -
In above-mentioned general formula, Y refers to substituting group, such as-F ,-OH etc.
In above-mentioned general formula, R can be branching or nonbranched fat-based; Can be the fat-based of 1 ~ 12 carbon atom, be preferably the fat-based of 1 ~ 6 carbon atom, particularly preferably methyl, ethyl and n-pro-pyl.
In above-mentioned general formula, R ' can be branching or nonbranched fat-based; Can be the fat-based of 2 ~ 12 carbon atoms, be preferably the fat-based of 2 ~ 6 carbon atoms, be more preferably non-branching, fat-based containing 2 ~ 6 carbon atoms, wherein substituting group and sulfonic group be connected on same carbon atom.
Particularly preferably, alkyl sulfonate ion is methanesulfonate ions.
Adopt methanesulfonate ions, the solubility of the first metal ion and zinc ion in electrolyte can be strengthened further, and its cost is lower.
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 1 ~ 7mol/L.
Preferably, in the electrolytic solution, the concentration of zinc ion is 1 ~ 4mol/L.
Preferably, in the electrolytic solution, the concentration of alkyl sulfonate ion is 0.5 ~ 12mol/L.
The pH value range of electrolyte is 3 ~ 7.
Electrolyte pH is too high, may affect Zn in electrolyte
2+concentration; Electrolyte pH is too low, then there will be the problems such as proton embeds altogether in electrode material corrosion and charge and discharge process.And the pH value range of electrolyte is 3 ~ 7, so both can effectively ensure Zn in electrolyte
2+concentration, thus ensure the capacity of battery and multiplying power discharging property, the problem that electrode corrosion and proton embed altogether can also be avoided.
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 both positive and negative polarity short circuit that barrier film can avoid other unexpected factors to cause.
As long as barrier film allows ionic conduction and 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, Zn
2+be limited in electrolyte liquid, 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 Zn
2+can not barrier film be passed through, so can not anode electrolyte be entered, can only 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.
The present invention carries out preliminary treatment by treatment fluid to metallic zinc, makes the surface modification of metallic zinc, reduces the generation of zinc load side reaction, effectively can suppress the generation of zinc load gas, thus avoid battery swell, enhance the security performance of battery, also effectively inhibit cell performance decay simultaneously.
Below in conjunction with specific embodiment, the present invention will be further elaborated and explanation.
Embodiment 1
By 20g zinc powder, add the hydrogen peroxide solution of 50ml5wt%, at room temperature soak 24h, then vacuum filtration, and use distilled water flushing several times.Constant weight is dried at 60 DEG C.
By obtain zinc powder, with binding agent PVDF(Kynoar) in mass ratio for after the ratio of 90:10 mix, be coated on corrosion resistant plate, drying is also densified to 100 μm, makes negative pole.Be denoted as A1.
Embodiment 2
By the zinc metal sheet of 10 × 10cm, add the hydrogen peroxide solution of 50ml5wt%, at room temperature soak 24h, then vacuum filtration, and use distilled water flushing several times.Constant weight is dried at 60 DEG C.Zinc metal sheet is cut into the negative pole of suitable size, is denoted as A2.
Embodiment 3
By 20g zinc powder, add the hydrogen peroxide solution of 50ml30wt%, at room temperature soak 12h, then vacuum filtration, and use distilled water flushing several times.Constant weight is dried at 60 DEG C.
By obtain zinc powder, with binding agent SBR(butadiene-styrene rubber) in mass ratio for after the ratio of 90:10 mix, be coated on corrosion resistant plate, drying is also densified to 100 μm, makes negative pole.Be denoted as A3.
Embodiment 4
By 20g zinc powder, add the liquor potassic permanganate of 50ml5wt%, at room temperature soak 24h, then vacuum filtration, and use distilled water flushing several times.Constant weight is dried at 60 DEG C.
By obtain zinc powder, with binding agent PTFE(polytetrafluoroethylene) in mass ratio for after the ratio of 90:10 mix, be coated on corrosion resistant plate, drying is also densified to 100 μm, makes negative pole.Be denoted as A4.
Embodiment 5-8
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose 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 in be coated with conducting film plus plate current-collecting body (stainless steel cloths of 50 μm) two sides on form active material layer, carried out compressing tablet subsequently, be cut into 8 × 10cm size, make positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m
2.
Barrier film is AGM fibreglass diaphragm, and 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, barrier film are assembled into battery core with negative pole A1 ~ A4 is stacked respectively, load in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as B1 ~ B4 respectively.
Embodiment 9
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose 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 in be coated with conducting film plus plate current-collecting body (stainless steel cloths of 50 μm) two sides on form active material layer, carried out compressing tablet subsequently, be cut into 8 × 10cm size, make positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m
2.
Barrier film is AGM fibreglass diaphragm, and barrier film is suitable with positive pole with negative pole size.
Take the zine methqne-sulfonate of certain mass, pyrovinic acid lithium, be added to the water dissolving, be configured to that pyrovinic acid zinc concentration is 2mol/L, pyrovinic acid lithium concentration is the electrolyte of 3mol/L.
By positive pole, barrier film and negative pole A2 is stacked is assembled into battery core, load in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as C2 respectively.
Comparative example 1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose 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 in be coated with conducting film plus plate current-collecting body (stainless steel cloths of 50 μm) two sides on form active material layer, carried out compressing tablet subsequently, be cut into 8 × 10cm size, make positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m
2.
By clean zinc powder, with binding agent PTFE(polytetrafluoroethylene) in mass ratio for after the ratio of 90:10 mix, be coated on corrosion resistant plate, drying is also densified to 100 μm, makes negative pole.
Barrier film is AGM fibreglass diaphragm, and size and the positive pole of barrier film and negative pole are suitable.
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, barrier film and negative electrode 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 BC1.
Comparative example 2
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose 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 in be coated with conducting film plus plate current-collecting body (stainless steel cloths of 50 μm) two sides on form active material layer, carried out compressing tablet subsequently, be cut into 8 × 10cm size, make positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m
2.
Get clean zinc metal sheet and be cut into suitable size, make negative pole.
Barrier film is AGM fibreglass diaphragm, and size and the positive pole of barrier film and negative pole are suitable.
Take the zine methqne-sulfonate of certain mass, pyrovinic acid lithium, be added to the water dissolving, be configured to that pyrovinic acid zinc concentration is 2mol/L, pyrovinic acid lithium concentration is the electrolyte of 3mol/L.
Positive pole, barrier film and negative electrode 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 BC2.
Performance test:
Gas content is tested:
Battery B1 and BC1 is placed a couple of days at 50 DEG C, the gas flow that record battery produces.The results are shown in Table 1.
Table 1 is the gas production that battery B1 and BC1 leaves standstill at 50 DEG C
As can be seen from Table 1, the relative battery BC1 of battery B1, gas production significantly reduces.This illustrates zinc load preparation method of the present invention, effectively can suppress the generation of gas in battery.
Cycle performance of battery is tested:
Battery B2, C2 and BC2 are carried out charge and discharge cycles test, and test result is shown in Fig. 1-3.
As can be seen from Fig. 1, Fig. 2, battery B2 and battery C2 is through repeatedly circulating, and capacity attenuation is all less.This battery illustrating that zinc load preparation method of the present invention obtains has excellent cycle performance.In addition, from Fig. 1 and Fig. 2 relatively, the cyclic curve of Fig. 2 is more straight, and this illustrates that zinc is deposited on negative pole preferably, and zinc load is more stable, effectively reduces corrosion and other side reactions of zinc load in the electrolyte containing tosylate ion.
As can be seen from Fig. 2 and Fig. 3, the cyclic curve of relative battery C2, battery BC2 is obviously on a declining curve, and fall off rate is very fast.Which illustrate the stability that invention enhances zinc load, effectively suppress the corrosion of zinc load, and then suppress battery capacity decay, effectively can keep battery capacity.
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 (11)
1. a preparation method for zinc load, is characterized in that: described preparation method comprises the following steps, and carries out preliminary treatment to metallic zinc, then pretreated metallic zinc is made zinc load;
Described preliminary treatment comprises makes metallic zinc surface modification by metallic zinc contact pairs liquid; Described treatment fluid is selected from the one in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
2. a preparation method for zinc load, is characterized in that: described preparation method comprises metallic zinc is made pending negative pole, then described pending negative pole is carried out preliminary treatment, obtains zinc load;
Described preliminary treatment comprises makes metallic zinc surface modification by described pending cathode contact treatment fluid; Described treatment fluid is selected from the one in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
3. the preparation method of zinc load according to claim 1 and 2, is characterized in that: the mass percentage concentration of described hydrogen peroxide solution is 1 ~ 30%.
4. the preparation method of zinc load according to claim 1 and 2, is characterized in that: the time of contact of described treatment fluid and metallic zinc is 0.5 ~ 24h.
5. the preparation method of zinc load according to claim 1 and 2, is characterized in that: described permanganate solution is liquor potassic permanganate; Described ferric ion solution is selected from one or more in ferric chloride solution, iron nitrate solution and-ferrum sulfuricum oxydatum solutum; Described quadrivalent cerium solion is ceric sulfate solution.
6. a zinc load, is characterized in that: described zinc load is obtained by the method that one of claim 1 ~ 8 is described.
7. a zinc load, is characterized in that: described zinc load comprises the metallic zinc of surface with passivating film, containing zinc oxide in described passivating film.
8. a battery, comprises 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 at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes, and described solvent is water or alcohol, and the pH value of described electrolyte is 3 ~ 7; Described electrolyte comprises in zinc ion and charge and discharge process at the first metal ion that described positive pole can reversiblely be deviate from-embed; It is characterized in that, described negative pole is the zinc load described in claim 6 or 7.
9. battery according to claim 8, is characterized in that: described electrolyte comprises one or more in sulfate ion, chloride ion, acetate ion, nitrate ion and alkyl sulfonate ion.
10. battery according to claim 9, is characterized in that: alkylsulfonate radical ion is methanesulfonate ions.
11. batteries according to claim 8, is characterized in that: described first metal ion is selected from lithium ion or sodium ion.
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| CN107910195A (en) * | 2017-10-26 | 2018-04-13 | 刘小林 | A kind of hybrid super capacitor |
| CN110323413A (en) * | 2019-06-28 | 2019-10-11 | 佛山科学技术学院 | A kind of cathode base band and preparation method thereof and high-capacity secondary battery |
| CN110474017A (en) * | 2019-08-29 | 2019-11-19 | 瑞海泊有限公司 | The preparation method and applications of mangaic acid zinc electrode |
| CN111430819A (en) * | 2020-03-31 | 2020-07-17 | 恩力能源科技(安徽)有限公司 | Water-based ion battery and preparation method thereof |
| CN111933912A (en) * | 2020-08-14 | 2020-11-13 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
| CN113410452A (en) * | 2021-06-17 | 2021-09-17 | 中国科学技术大学 | Modified zinc cathode and preparation method and application thereof |
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| CN107910195A (en) * | 2017-10-26 | 2018-04-13 | 刘小林 | A kind of hybrid super capacitor |
| CN110323413A (en) * | 2019-06-28 | 2019-10-11 | 佛山科学技术学院 | A kind of cathode base band and preparation method thereof and high-capacity secondary battery |
| CN110474017A (en) * | 2019-08-29 | 2019-11-19 | 瑞海泊有限公司 | The preparation method and applications of mangaic acid zinc electrode |
| CN111430819A (en) * | 2020-03-31 | 2020-07-17 | 恩力能源科技(安徽)有限公司 | Water-based ion battery and preparation method thereof |
| CN111430819B (en) * | 2020-03-31 | 2022-11-08 | 北京恩力动力科技有限公司 | Water-based ion battery and preparation method thereof |
| CN111933912B (en) * | 2020-08-14 | 2021-10-08 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN111933912A (en) * | 2020-08-14 | 2020-11-13 | 华中科技大学 | Zinc cathode with zinc ion conductivity interface modification layer, battery and preparation method |
| CN113363410B (en) * | 2021-05-27 | 2022-04-12 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
| CN113363410A (en) * | 2021-05-27 | 2021-09-07 | 哈尔滨工业大学 | Preparation method and application of in-situ fast-growth multifunctional zinc cathode protective layer |
| CN113410452A (en) * | 2021-06-17 | 2021-09-17 | 中国科学技术大学 | Modified zinc cathode and preparation method and application thereof |
| CN113782842A (en) * | 2021-08-25 | 2021-12-10 | 华中科技大学 | Aqueous zinc ion battery electrolyte and battery |
| CN115117360A (en) * | 2022-08-31 | 2022-09-27 | 山东华太新能源电池有限公司 | Mercury-free active negative electrode material and preparation method thereof |
| CN115117360B (en) * | 2022-08-31 | 2022-11-11 | 山东华太新能源电池有限公司 | Mercury-free active negative electrode material and preparation method thereof |
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