CN104518205B - The preparation method and zinc load and battery of zinc load - Google Patents
The preparation method and zinc load and battery of zinc load Download PDFInfo
- Publication number
- CN104518205B CN104518205B CN201310452547.0A CN201310452547A CN104518205B CN 104518205 B CN104518205 B CN 104518205B CN 201310452547 A CN201310452547 A CN 201310452547A CN 104518205 B CN104518205 B CN 104518205B
- Authority
- CN
- China
- Prior art keywords
- zinc
- ion
- solution
- electrolyte
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 kind of preparation method of zinc load.The preparation method includes pre-processing metallic zinc, and pretreated metallic zinc then is made into negative pole；The pretreatment includes being modified metal zinc surface metallic zinc contact treatment fluid；The one kind of the treatment fluid in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.The zinc load obtained present invention also offers a kind of above-mentioned preparation method and the battery containing above-mentioned zinc load.The present invention is pre-processed by treatment fluid to metallic zinc, reduces the generation of zinc load side reaction, is effectively suppressed the generation of zinc load gas, so as to avoid battery swell, the security performance of battery is enhanced, while also effectively inhibiting cell performance decay.
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 above method is obtained.
The present invention relates to a kind of battery containing above-mentioned zinc load.
Background technology
Lead-acid battery, it, which goes out, has surpassed a century, possesses the battery technology of maturation, in occupation of automobile starting storage battery, electronic
The absolute market share in the energy storage such as bicycle, UPS field.Although lead-acid battery service life cycle is relatively low, energy density also phase
To relatively low, but possess that price is very cheap, cost performance very high advantage.Therefore, in the last few years, Ni-MH battery, lithium ion
Battery, sodium-sulphur battery etc., can not replace lead-acid battery in energy storage field.
Newly occur in that a kind of battery exchanged based on inner ion.The operation principle of the battery is that positive pole is based on the first gold medal
Belong to abjection-insertion reaction of ion, deposition of the negative pole based on zinc ion-dissolving reaction, electrolyte positive pole containing participation abjection-insertion
First metal ion of reaction and the zinc ion for participating in cathode deposition-dissolving reaction.The type battery theoretical energy density is
160Wh/Kg, it is contemplated that actual energy density is up to 50~80Wh/Kg.In summary, the type battery is promised to be very much replaces
For the energy-storage battery of future generation of lead-acid battery, with great commercial value.
But, in use for some time, inside battery can produce a large amount of gases to the current battery, easily cause battery hair
Drum, causes battery using there is potential safety hazard；Simultaneously because the generation of gas, also results in battery performance deterioration.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of negative pole, are obtained by the preparation method
Application of electrode in battery, it is to avoid produce a large amount of gases.
The invention provides a kind of preparation method of zinc load, the preparation method comprises the following steps, metallic zinc is entered
Row pretreatment, is then made zinc load by pretreated metallic zinc；The pretreatment includes making metallic zinc contact treatment fluid
Metal zinc surface is modified；The treatment fluid be selected from hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium from
One kind in sub- solution.
Present invention also offers a kind of preparation method of zinc load, the preparation method is pending including metallic zinc is made
Negative pole, then the pending negative pole is pre-processed, obtain zinc load；The pretreatment is included the pending negative pole
Contact treatment fluid is modified metal zinc surface；It is molten that the treatment fluid is selected from hydrogen peroxide solution, permanganate solution, ferric ion
One kind in liquid and quadrivalent cerium solion.
Preferably, the mass percentage concentration of the hydrogen peroxide solution is 1~30%.
Preferably, the time of contact of the treatment fluid and metallic zinc is 0.5~24h.
Preferably, the way of contact of the treatment fluid and metallic zinc is immersion.
Preferably, the permanganate solution is liquor potassic permanganate.
Preferably, the one kind of the ferric ion solution in ferric chloride solution, iron nitrate solution, ferrum sulfuricum oxydatum solutum
Or it is several.
Preferably, the quadrivalent cerium solion is ceric sulfate solution.
Present invention also offers the preparation method that a kind of zinc load, the zinc load pass through zinc load provided by the present invention
It is made.
Present invention also offers a kind of zinc load, the zinc load includes the metallic zinc that surface has passivating film, described blunt
Change in film and contain zinc oxide.
Present invention also offers a kind of battery, including positive pole, negative pole and electrolyte, the positive pole includes reversible taking off
Go out-be embedded in the positive active material of the first metal ion；The electrolyte, which includes at least one, can dissolve electrolyte and make institute
The solvent of electrolyte ionization is stated, the solvent is water or alcohol, and the pH value of the electrolyte is 3~7；The electrolyte include zinc from
In son and charge and discharge process the positive pole can it is reversible deviate from-the first metal ion for being embedded in；The negative pole is institute of the present invention
The zinc load of offer.
Preferably, the electrolyte includes sulfate ion, chlorion, acetate ion, nitrate ion and alkyl
One or more in sulfonate ion.
Preferably, the alkylsulfonate radical ion is methanesulfonate ions.
Preferably, the battery also includes the barrier film being located between positive pole and negative pole.
Preferably, first metal ion is selected from lithium ion or sodium ion.
Preferably, the positive active material is selected from LiMn2O4、LiFePO4And LiCoO2In one or more.
Compared with prior art, zinc load preparation method of the invention includes, and metallic zinc is located in advance by treatment fluid
Reason, is modified the surface of metallic zinc, reduces the generation of zinc load side reaction, can effectively suppress the generation of zinc load gas, from
And battery swell is avoided, the security performance of battery is enhanced, while also effectively inhibiting cell performance decay.
Brief description of the drawings
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 that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
A kind of preparation method of zinc load, the preparation method comprises the following steps, metallic zinc is pre-processed, then
Zinc load is made in pretreated metallic zinc；The pretreatment includes changing metal zinc surface metallic zinc contact treatment fluid
Property；The treatment fluid in hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion one
Kind.
Wherein, metallic zinc can be zinc powder, can also be zinc metal sheet.
, it is necessary to prerinse be carried out to metallic zinc, to remove metallic zinc table before being handled with treatment fluid metallic zinc
The grease in face.
Specifically, metallic zinc is washed with a large amount of clear water, or be immersed in degreaser, then rinsed with substantial amounts of clear water
Totally.
Metallic zinc is pre-processed using treatment fluid, to be modified to metal zinc surface, changes the surface of metallic zinc
Activity；Make it in battery charging and discharging circulation, the generation of negative pole side reaction can be suppressed, while having no effect in electrolyte
Zinc ion reduction is deposited as metallic zinc and reversible by negative pole electrochemical reaction of the metallic zinc oxidation dissolution for zinc ion.
Treatment fluid selects 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 soluble permanganate formation soluble in water.The permanganate of the present invention
Solution can selected from 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 are molten
One or more in liquid.Preferably, permanganate solution is liquor potassic permanganate.
Ferric ion solution refers to the aqueous solution containing ferric ion.The 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
One or more in ferric chloride solution, iron nitrate solution and ferrum sulfuricum oxydatum solutum.
Quadrivalent cerium solion refers to the aqueous solution containing tetravalence cerium ion.The 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 invention is sulfuric acid
High cerium solution.
The treatment fluid of the present invention, it is preferred to use hydrogen peroxide solution.Using hydrogen peroxide solution as treatment fluid, after it is handled
Product it is easily separated, and other impurity are not introduced, while the zinc load excellent performance being made.
In order to increase the effect of processing, the mass percentage concentration of hydrogen peroxide is preferably 1~30%, and more preferably 5~30%.
The purpose that the present invention is contacted is to make metallic zinc in the presence for the treatment of fluid, and surface reacts, so that its surface
It is modified.
Under a preferred embodiment, contact is preferably to soak, i.e., metallic zinc is immersed in treatment fluid.For example handle zinc
During powder, zinc powder is immersed in treatment fluid.In another example during processing zinc metal sheet, zinc metal sheet is immersed in treatment fluid, while to zinc metal sheet
It is two-sided to be handled.
It is preferable to carry out under method, is contacted as by zinc metal sheet single-contact treatment fluid another.
Wherein, zinc metal sheet single-contact treatment fluid can use diaphragm mode, be in particular：The one side of zinc metal sheet is enclosed into guarantor
Zinc metal sheet, is then totally immersed into treatment fluid and soaks by cuticula, one side with diaphragm in the presence of diaphragm not with processing
Liquid is contacted；After treating that immersion is finished, diaphragm is removed.
Zinc metal sheet single-contact can also be direct single-contact, be in particular：By zinc metal sheet one side upward, one down, court
Under one side contact the liquid level for the treatment of fluid, and one side upward is located on the liquid level for the treatment of fluid, is not contacted with treatment fluid.
Zinc metal sheet single-contact is preferably immersed treatment fluid by the present invention.One that zinc metal sheet is deposited-dissolved without zinc ion
Face（Equivalent to the one side as collector）Without pretreatment；Zinc metal sheet carries out the one side of zinc ion deposition-dissolving（Equivalent to work
For the one side of negative electrode active material）Pre-processed.Only the one side for participating in negative reaction is pre-processed, can preferably be pressed down
Gas processed is produced, while having no effect on the electric conductivity of negative pole.
According to different situations, stir to strengthen treatment effect in contact process；It can not certainly stir, i.e., directly stand
.
Preferably, the temperature of processing is 15~50 DEG C, more preferably room temperature.At this temperature, enhancing processing is not only improved
Speed and effect, can also avoid influence of the high temperature to hydrogen peroxide.
Preferably, 0.5~24h of time of processing, preferably 24h.It can so ensure that zinc fully reacts with hydrogen peroxide, in gold
Belong to the good passivating film of the Surface Creation of zinc.
After contact, metallic zinc is separated, rinsed well, and is dried.
After pre-processing, the metallic zinc by pretreatment is fabricated to negative pole.
According to the difference of final zinc load morphosis, negative pole is made using required method.For example will be pretreated
Zinc metal sheet carries out cutting and is fabricated to negative pole；In another example pretreated zinc powder is mixed with binding agent, it is supported on negative current collector
Negative pole is made.
The present invention also provides a kind of preparation method of zinc load, and the preparation method includes the metallic zinc pending bear is made
Pole, then the pending negative pole is pre-processed, obtain zinc load；
The pretreatment includes being modified metal zinc surface the pending cathode contact treatment fluid；The treatment fluid choosing
One kind from hydrogen peroxide solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
The preparation method of this method and foregoing zinc load, unlike, sequence of steps is not in preparation method for pretreatment
Rather than metallic zinc together, namely the object of this method pretreatment is the pending negative pole that is made of metallic zinc,.Other parts are with before
The preparation method for the zinc load stated is essentially identical, is specifically referred to the preparation method of foregoing zinc load, will not be repeated here！
Present invention also offers the zinc load that a kind of above method is obtained.
The zinc load of the present invention, it includes containing zinc oxide in the metallic zinc that surface has passivating film, the passivating film.When
Metallic zinc is after pretreatment, and the surface of metallic zinc can generate one layer of passivating film containing zinc oxide.The passivating film can be effective
Suppress the generation of gas in battery, but it is heavy to have no effect on the reduction of the oxidation dissolution and zinc ion of the metallic zinc of normal negative pole
Product.
When in ion exchange battery electrochemical reaction occurs for zinc load, zinc in zinc load can oxidation dissolution be zinc from
Zinc ion energy reversible reduction in son, electrolyte is zinc and is deposited on negative pole.
The difference acted in the battery according to negative pole, can have two kinds of different forms：
In the first preferred embodiment, negative pole includes negative current collector, and pretreated metallic zinc is supported on negative pole collection
On fluid.Metallic zinc is present in negative pole as negative electrode active material, the load that negative current collector only conducts and collected as electronics
Body, is not involved in electrochemical reaction.
The material of negative current collector is selected from W metal, Cu, Ag, Pb, Mn, Sn, Fe, Al or the above-mentioned gold Jing Guo Passivation Treatment
At least one of category, either elemental silicon or carbon-based material；Wherein, carbon-based material includes graphite material, such as commercialized
The paper tinsel of graphite compacting, the part by weight scope wherein shared by graphite is 90~100%.The material of negative current collector is also selected from
Stainless steel or the stainless steel of passivated processing.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, likewise, stainless
The model of steel can be the stainless steel of 300 series, such as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.In addition, negative
Pole collector is also selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, so as to reduce the generation of negative pole side reaction.Plating/
Coating is selected from least one of the simple substance containing C, Sn, In, Ag, Pb, Co, alloy, or oxide.The thickness model of plating/coating
Enclose for 1~1000nm.For example：Tin, lead or silver are plated on the negative current collector surface of copper foil or graphite foil.
When using zinc metal sheet as negative electrode active material, the zinc metal sheet by pretreatment is formed compound with negative current collector
Layer.
When using zinc powder as negative electrode active material, slurry is made in the zinc powder by pretreatment, then slurry is applied
Overlay on and negative pole is made on negative current collector.
In a particular embodiment, when preparing negative pole, in addition to negative electrode active material zinc powder, according to actual conditions,
The performance of negative pole is lifted always according to needing to add cathode conductive agent and negative electrode binder.
Preferably, zinc powder accounts for the 80~95% of negative pole gross weight, and negative electrode binder accounts for the 5~20% of negative pole gross weight.
In the second preferred embodiment, directly using pretreated zinc metal sheet as negative pole, zinc metal sheet is both as negative pole collection
Fluid, while being also negative electrode active material.
A kind of battery, including positive pole, negative pole and electrolyte, the positive pole include can it is reversible deviate from-be embedded in the first metal
The positive active material of ion；The electrolyte includes at least one to dissolve electrolyte and making the molten of electrolyte ionization
Agent, the solvent is water or alcohol, and the pH value of the electrolyte is 3~7；The electrolyte is included in zinc ion and charge and discharge process
The positive pole can it is reversible deviate from-the first metal ion for being embedded in；The negative pole is negative pole provided by the present invention.
The charge-discharge principle of battery is：Deviate from the first metal ion during charging, in positive active material, while with positive pole
Active material is oxidized, and ejected electron；Electronics reaches GND via external circuit, while the zinc ion in electrolyte is negative
Electronics is obtained on extremely to be reduced, and is deposited on negative pole.During electric discharge, the zinc being deposited on negative pole is oxidized, and loses electronics transformation
Enter for zinc ion in electrolyte；Electronics reaches positive pole through external circuit, and positive active material receives electronics and is reduced, while first
In metal ion insertion positive active material.
Wherein, positive active material in positive pole participates in positive pole reaction, and can it is reversible deviate from-be embedded in the first metal from
Son.
It is preferred that, positive active material can it is reversible deviate from-be embedded in lithium ion or sodium ion.
Positive active material can meet formula Li1+xMnyMzOkCan it is reversible deviate from-be embedded in the spinelle of lithium ion
The compound of structure, wherein, -1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M be selected from Na, Li, Co, Mg, Ti,
At least one of Cr, V, Zn, Zr, Si, Al.It is preferred that, positive active material contains LiMn2O4.It is furthermore preferred that positive-active
Material contains the LiMn through overdoping or coating modification2O4。
Positive active material can meet formula Li1+xMyM′zM″cO2+nCan it is reversible deviate from-be embedded in the layer of lithium ion
The compound of shape structure, wherein, -1<X≤0.5,0≤y≤1,0≤z≤1,0≤c≤1, -0.2≤n≤0.2, M, M ', M " points
Not Xuan Zi Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al at least one of.It is preferred that, positive active material contains
LiCoO2。
Positive active material, which can also be, meets formula LixM1-yM′y(XO4)nCan it is reversible deviate from-be embedded in lithium ion
The compound of olivine structural, wherein, 0<X≤2,0≤y≤0.6,1≤n≤1.5, M be selected from Fe, Mn, V or Co, M ' be selected from Mg,
At least one of Ti, Cr, V or Al, X is selected from least one of S, P or Si.It is preferred that, positive active material contains
LiFePO4。
In current battery industry, nearly all positive active material all can be through modifications such as overdoping, claddings.But mix
Miscellaneous, the means such as coating modification cause the chemical general formula of material to express complicated, such as LiMn2O4Can not represent makes extensively at present
The formula of " LiMn2O4 ", and should be with formula Li1+xMnyMzOkIt is defined, widely including the LiMn Jing Guo various modifications2O4
Positive active material.Likewise, LiFePO4And LiCoO2Also it should be construed broadly to include by various doping, cladding etc.
Modified, formula corresponds with LixM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nPositive active material.
When positive active material is the material of the reversible abjection-insertion lithium ion of energy, such as LiMn can be preferably selected2O4、
LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).In addition, the positive pole of the present invention
When active material is the material of the reversible abjection-insertion sodium ion of energy, NaVPO can be preferably selected4F etc..
Positive pole, includes the plus plate current-collecting body of load positive active material, the material of plus plate current-collecting body be selected from carbon-based material,
One kind in metal or alloy.
The carrier that plus plate current-collecting body only conducts and collected as electronics, is not involved in electrochemical reaction, i.e., work electric in battery
In the range of pressure, what plus plate current-collecting body can be stablized is present in electrolyte and does not occur side reaction substantially, so as to ensure that battery has
There is stable cycle performance.
Preferably, processing is passivated to plus plate current-collecting body, main purpose is that the surface for making plus plate current-collecting body forms one layer
The oxide-film of passivation, so that in battery charge and discharge process, collection and the conduction electronics of stabilization can be played a part of, without joining
With cell reaction, it is ensured that battery performance is stable.Plus plate current-collecting body deactivating process for the treatment of includes chemical passivation processing or electrochemistry is blunt
Change is handled.
Chemical passivation processing includes, by oxidizing plus plate current-collecting body, making plus plate current-collecting body surface form passivating film.
The principle of oxidant selection can make plus plate current-collecting body surface form one layer of passivating film without dissolving plus plate current-collecting body for oxidant.
Oxidant is selected from but is not limited only to concentrated nitric acid.
Specifically, chemical passivation process step is：Plus plate current-collecting body is inserted in oxidizing agent solution, maintenance 0.5~1 is small
When, plus plate current-collecting body surface is formed passivating film, finally take out plus plate current-collecting body and clean and dry.
Electrochemical passivation processing includes carrying out plus plate current-collecting body electrochemical oxidation or to the battery containing plus plate current-collecting body
Charge and discharge electric treatment is carried out, plus plate current-collecting body surface is formed passivating film.
Under a preferred embodiment, electrochemical oxidation directly is carried out to plus plate current-collecting body, i.e., is used in plus plate current-collecting body
Battery assembling advance row pre-passivating.Specifically, using plus plate current-collecting body as working electrode, selection is suitable to electrode and reference electricity
Pole constitutes three-electrode system, and plus plate current-collecting body is aoxidized；Application voltage is 2.1~2.4V.Plus plate current-collecting body can be gold
Category, such as metallic aluminium；Plus plate current-collecting body can also be alloy, such as stainless steel or aluminium alloy.It is of course also possible to use with anode collection
Body is two electrode systems of working electrode, and plus plate current-collecting body is aoxidized, and application voltage is 2.1~2.4V.
Under a preferred embodiment, discharge and recharge can also be carried out to the battery containing plus plate current-collecting body and be aligned so as to reach
The purpose that pole collector is passivated, voltage is charged to 2.1~2.4V during charging, and voltage is put to 1.35~1.45V during electric discharge,
Discharge and recharge number of times is not less than 1.
In a particular embodiment,, may according to actual conditions in addition to positive active material when preparing positive pole
Addition positive conductive agent and positive electrode binder is also needed to lift the performance of positive pole.
Positive conductive agent is selected from conducting polymer, activated carbon, graphene, carbon black, graphite, carbon fiber, metallic fiber, metal
One or more in powder and sheet metal.
Positive electrode binder can be selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, poly-
In ether, fluorinated polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates
The mixture and derivative of a kind of or above-mentioned polymer.It is highly preferred that positive electrode binder is selected from polytetrafluoroethylene (PTFE) (PTFE), gathered
Vinylidene (PVDF) or butadiene-styrene rubber（SBR）.
Solvent dissolves electrolyte in electrolyte, and ionizes electrolyte, finally generates what be can move freely in the electrolytic solution
Cation and anion.
Solvent is water or alcohol；Wherein alcohol includes but is not limited to methanol or ethanol.
Wherein, the first metal ion in electrolyte, in battery charge and discharge process, can positive pole it is reversible abjection-it is embedding
Enter.I.e. in battery discharge, in the first metal ion insertion positive active material in electrolyte；When battery charges, first
Metal ion is deviate from from positive active material, into electrolyte.
Preferably, the first metal ion is selected from lithium ion or sodium ion, more preferably lithium ion.
Zinc ion in electrolyte, can be in the reversible deposition-dissolving of negative pole in battery charge and discharge process.I.e. in battery
During charging, the zinc ion in electrolyte is reduced into metallic zinc, is deposited on negative pole；In battery discharge, metallic zinc is oxidized to zinc
Ion, dissolving enters electrolyte from negative pole.
Under a preferred embodiment, the first metal ion of the invention be lithium ion, i.e. electrolyte cationic be lithium from
Son and zinc ion.
Anion in electrolyte, can any have substantially no effect on both positive and negative polarity reaction and electrolyte in a solvent molten
The anion of solution.For example can be sulfate ion, chlorion, nitrate ion, acetate ion, formate ion and
One or more in phosphate anion.
Under a preferred embodiment, anion includes sulfate ion, chlorion, acetate ion and nitre in electrolyte
One or more in acid ion.
Under another preferred embodiment, anion includes alkyl sulfonate ion in electrolyte.
Electrolyte containing alkyl sulfonate ion, has the advantage that：
First, alkyl sulfonate ion can effectively improve the dissolving of the first metal ion and zinc ion in the electrolytic solution
Degree；Second, alkyl sulfonate ion can further suppress the generation of gas；3rd, alkyl sulfonate ion can also be effective
Reduce the self-discharge rate of battery.4th, with respect to other anion salts, the electrolyte of alkyl sulfonate ion does not freeze at -20 DEG C,
It can make battery that there is more preferable cryogenic property.
It is further preferred that the anion in electrolyte is containing only the alkane that alkyl sulfonate ion, i.e. electrolyte are the first metal
Base sulfonate and alkyl sulfonic acid zinc.
It is particularly preferred that electrolyte is Lithium perchlorate and alkyl sulfonic acid zinc.
Alkyl sulfonate ion includes but is not limited to aliphatic sulfonic radical ion, and is not limited to carry on aliphatic group
Functional group or substituent.Preferably conform to below general formula：
R-SO3 -Or Y-R '-SO3 -
In above-mentioned formula, Y refers to substituent, such as-F ,-OH.
In above-mentioned formula, R can be branched or nonbranched fat-based；Can be the fat-based of 1~12 carbon atom,
The fat-based of preferably 1~6 carbon atom, particularly preferred methyl, ethyl and n-propyl.
In above-mentioned formula, R ' can be branched or nonbranched fat-based；Can be the fat of 2~12 carbon atoms
Base, the fat-based of preferably 2~6 carbon atoms, fat-based more preferably unbranched, containing 2~6 carbon atoms, wherein replacing
Base and sulfonic group are not attached on same carbon atom.
It is particularly preferred that alkyl sulfonate ion is methanesulfonate ions.
Using methanesulfonate ions, the dissolving of the first metal ion and zinc ion in electrolyte can be further enhanced
Degree, and its cost is relatively low.
The concentration of each ion in electrolyte, can be according to differences such as the application fields of different electrolyte, solvent and battery
Situation and be changed allotment.
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 influence Zn in electrolyte2+Concentration；Electrolyte pH is too low, then electrode material occurs
The problems such as proton is embedded in altogether in material corrosion and charge and discharge process., so both can be effective and the pH value range of electrolyte is 3~7
Ensure Zn in electrolyte2+Concentration, so as to ensure the capacity and multiplying power discharging property of battery, can also avoid electrode corrosion and
The problem of proton is embedded in altogether.
Battery can be free of barrier film.Certainly, in order to provide more preferable security performance, preferably in the electrolytic solution be located at positive pole with
Barrier film is additionally provided between negative pole.The both positive and negative polarity short circuit that other unexpected factors that barrier film can avoid are caused.
As long as barrier film allows ionic conduction and electronic isolation.The various barrier films that organic series lithium ion battery is used,
Go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.
Under a preferred embodiment, barrier film is the barrier film that electrolyte is divided into anode electrolyte and electrolyte liquid.
The first metal ion is limited in anode electrolyte, Zn2+It is limited in electrolyte liquid, such barrier film can prevent both positive and negative polarity
The mutual pollution of electrolyte, may be selected to be more suitable for the electrolyte of negative or positive electrode, but do not influence ionic charge to transmit.For example adopt
With anion-exchange membrane or hydrogen ion exchange membrane as barrier film, the first metal ion can not pass through in anode electrolyte
Barrier film, so can not enter electrolyte liquid, can only be limited in anode electrolyte；The Zn in electrolyte liquid2+Can not
By barrier film, so anode electrolyte can not be entered, it can only be limited in electrolyte liquid.But in electrolyte anion or
Hydrogen ion can be passed freely through, therefore have no effect on electrolyte intermediate ion charge transfer.
The present invention is pre-processed by treatment fluid to metallic zinc, is modified the surface of metallic zinc, is reduced zinc load pair
The generation of reaction, can effectively suppress the generation of zinc load gas, so as to avoid battery swell, enhance the security of battery
Can, while also effectively inhibiting cell performance decay.
Below in conjunction with specific embodiment, the present invention will be further elaborated and explanation.
Embodiment 1
By 20g zinc powders, 50ml5wt% hydrogen peroxide solution is added, 24h is soaked at room temperature, is then filtered by vacuum, is used in combination
Distilled water flushing is several times.Dried at 60 DEG C to constant weight.
Zinc powder and binding agent PVDF will be obtained（Kynoar）It is 90 in mass ratio:After 10 ratio mixing, it is coated on
On stainless steel plate, dry and be densified to 100 μm, negative pole is made.It is denoted as A1.
Embodiment 2
By 10 × 10cm zinc metal sheet, 50ml5wt% hydrogen peroxide solution is added, 24h is soaked at room temperature, then vacuum is taken out
Filter, and with distilled water flushing several times.Dried at 60 DEG C to constant weight.Zinc metal sheet is cut into suitably sized negative pole, is denoted as
A2。
Embodiment 3
By 20g zinc powders, 50ml30wt% hydrogen peroxide solution is added, 12h is soaked at room temperature, is then filtered by vacuum, is used in combination
Distilled water flushing is several times.Dried at 60 DEG C to constant weight.
Zinc powder and binding agent SBR will be obtained（Butadiene-styrene rubber）It is 90 in mass ratio:After 10 ratio mixing, it is coated on not
Become rusty on steel plate, dry and be densified to 100 μm, negative pole is made.It is denoted as A3.
Embodiment 4
By 20g zinc powders, 50ml5wt% liquor potassic permanganate is added, 24h is soaked at room temperature, is then filtered by vacuum, and
With distilled water flushing several times.Dried at 60 DEG C to constant weight.
Zinc powder and binding agent PTFE will be obtained（Polytetrafluoroethylene (PTFE)）It is 90 in mass ratio:After 10 ratio mixing, it is coated on
On stainless steel plate, dry and be densified to 100 μm, negative pole is made.It is denoted as A4.
Embodiment 5-8
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose CMC according to mass ratio 90:5:
2.5:2.5 mix in water, form uniform anode sizing agent.Anode sizing agent is coated in the plus plate current-collecting body for being coated with conducting film
（50 μm of stainless steel cloth）Active material layer is formed on two sides, tabletting is then carried out, 8 × 10cm sizes are cut into, made
Into positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m2。
Barrier film is AGM fibreglass diaphragms, and barrier film and negative pole size are suitable with positive pole.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, sulfuric acid zinc concentration is configured to for 2mol/L, sulphur
Sour lithium concentration is 1mol/L electrolyte.
Positive pole, barrier film are assembled into battery core with negative pole A1~A4 stackings respectively, loads in housing, is then injected into electrolyte,
Sealing, is assembled into battery.Obtained battery, is denoted as B1~B4 respectively.
Embodiment 9
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose CMC according to mass ratio 90:5:
2.5:2.5 mix in water, form uniform anode sizing agent.Anode sizing agent is coated in the plus plate current-collecting body for being coated with conducting film
（50 μm of stainless steel cloth）Active material layer is formed on two sides, tabletting is then carried out, 8 × 10cm sizes are cut into, made
Into positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m2。
Barrier film is AGM fibreglass diaphragms, and barrier film and negative pole size are suitable with positive pole.
Zine methqne-sulfonate, the pyrovinic acid lithium of certain mass are weighed, is added to the water dissolving, is configured to pyrovinic acid zinc concentration
The electrolyte for being 3mol/L for 2mol/L, pyrovinic acid lithium concentration.
Positive pole, barrier film and negative pole A2 stacking are assembled into battery core, loads in housing, is then injected into electrolyte, seal, assembling
Into battery.Obtained battery, is denoted as C2 respectively.
Comparative example 1
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose CMC according to mass ratio 90:5:
2.5:2.5 mix in water, form uniform anode sizing agent.Anode sizing agent is coated in the plus plate current-collecting body for being coated with conducting film
（50 μm of stainless steel cloth）Active material layer is formed on two sides, tabletting is then carried out, 8 × 10cm sizes are cut into, made
Into positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m2。
By clean zinc powder and binding agent PTFE（Polytetrafluoroethylene (PTFE)）It is 90 in mass ratio:After 10 ratio mixing, coating
In on stainless steel plate, dry and be densified to 100 μm, negative pole is made.
Barrier film is AGM fibreglass diaphragms, and the size of barrier film and negative pole is suitable with positive pole.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, sulfuric acid zinc concentration is configured to for 2mol/L, sulphur
Sour lithium concentration is 1mol/L electrolyte.
Positive pole, barrier film and negative electrode layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, seals, is assembled into
Battery.
Obtained battery, is denoted as BC1.
Comparative example 2
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and sodium carboxymethylcellulose CMC according to mass ratio 90:5:
2.5:2.5 mix in water, form uniform anode sizing agent.Anode sizing agent is coated in the plus plate current-collecting body for being coated with conducting film
（50 μm of stainless steel cloth）Active material layer is formed on two sides, tabletting is then carried out, 8 × 10cm sizes are cut into, made
Into positive pole.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m2。
Take clean zinc metal sheet to be cut into suitably sized, negative pole is made.
Barrier film is AGM fibreglass diaphragms, and the size of barrier film and negative pole is suitable with positive pole.
Zine methqne-sulfonate, the pyrovinic acid lithium of certain mass are weighed, is added to the water dissolving, is configured to pyrovinic acid zinc concentration
The electrolyte for being 3mol/L for 2mol/L, pyrovinic acid lithium concentration.
Positive pole, barrier film and negative electrode layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, seals, is assembled into
Battery.
Obtained battery, 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 produced by record battery.It the results are shown in Table 1.
Table 1 is the gas production that battery B1 and BC1 is stood at 50 DEG C
As it can be seen from table 1 battery B1 is with respect to battery BC1, gas production significantly reduces.The zinc load system of this explanation present invention
Preparation Method, can effectively suppress the generation of gas in battery.
Cycle performance of battery is tested：
Battery B2, C2 and BC2 are subjected to charge and discharge cycles test, test result is shown in Fig. 1-3.
Battery B2 and battery C2 are can be seen that by multiple circulation from Fig. 1, Fig. 2, and capacity attenuation is smaller.This explanation is originally
The battery that the zinc load preparation method of invention is obtained has excellent cycle performance.In addition, from Fig. 1 and Fig. 2 relatively from the point of view of, Fig. 2
Cyclic curve it is more straight, this explanation in the electrolyte containing tosylate ion, zinc is preferably deposited on negative pole, zinc
Negative pole is more stablized, and effectively reduces the corrosion and other side reactions of zinc load.
Relative battery C2 is can be seen that from Fig. 2 and Fig. 3, battery BC2 cyclic curve is substantially on a declining curve, and under
Reduction of speed rate is very fast.This illustrates the stability invention enhances zinc load, effectively suppresses the corrosion of zinc load, and then suppress electricity
Tankage is decayed, and can effectively keep battery capacity.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of zinc load, it is characterised in that：The preparation method comprises the following steps, and metallic zinc is carried out pre-
Processing, is then made zinc load by pretreated metallic zinc；
The pretreatment includes being modified metal zinc surface metallic zinc contact treatment fluid；It is water-soluble that the treatment fluid is selected from dioxygen
One kind in liquid, permanganate solution, ferric ion solution and quadrivalent cerium solion.
2. a kind of preparation method of zinc load, it is characterised in that：The preparation method includes the metallic zinc pending negative pole is made,
Then the pending negative pole is pre-processed, obtains zinc load；
The pretreatment includes being modified metal zinc surface the pending cathode contact treatment fluid；The treatment fluid is selected from double
One kind in the oxygen aqueous solution, permanganate solution, ferric ion solution and quadrivalent cerium solion.
3. the preparation method of zinc load according to claim 1 or 2, it is characterised in that：The quality of the hydrogen peroxide solution
Percentage concentration is 1~30%.
4. the preparation method of zinc load according to claim 1 or 2, it is characterised in that：The treatment fluid and metallic zinc
Time of contact is 0.5~24h.
5. the preparation method of zinc load according to claim 1 or 2, it is characterised in that：The permanganate solution is height
Potassium manganate solution；One kind in ferric chloride solution, iron nitrate solution and ferrum sulfuricum oxydatum solutum of the ferric ion solution or
It is several；The quadrivalent cerium solion is ceric sulfate solution.
6. a kind of zinc load, it is characterised in that：The zinc load is made by the method described in one of claim 1~2.
7. a kind of battery, including positive pole, negative pole and electrolyte, the positive pole include can it is reversible deviate from-be embedded in the first metal from
The positive active material of son；The electrolyte includes at least one to dissolve electrolyte and making the molten of electrolyte ionization
Agent, the solvent is water or alcohol, and the pH value of the electrolyte is 3~7；The electrolyte is included in zinc ion and charge and discharge process
The positive pole can it is reversible deviate from-the first metal ion for being embedded in；Characterized in that, the negative pole is described in claim 6
Zinc load.
8. battery according to claim 7, it is characterised in that：The electrolyte includes sulfate ion, chlorion, vinegar
One or more in acid ion, nitrate ion and alkyl sulfonate ion.
9. battery according to claim 8, it is characterised in that：Alkylsulfonate radical ion is methanesulfonate ions.
10. battery according to claim 7, it is characterised in that：First metal ion is selected from lithium ion or sodium ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452547.0A CN104518205B (en) | 2013-09-27 | 2013-09-27 | The preparation method and zinc load and battery of zinc load |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452547.0A CN104518205B (en) | 2013-09-27 | 2013-09-27 | The preparation method and zinc load and battery of zinc load |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104518205A CN104518205A (en) | 2015-04-15 |
| CN104518205B true CN104518205B (en) | 2017-09-12 |
Family
ID=52793178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310452547.0A Active CN104518205B (en) | 2013-09-27 | 2013-09-27 | The preparation method and zinc load and battery of zinc load |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104518205B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107910195B (en) * | 2017-10-26 | 2020-07-28 | 刘小林 | 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 |
| CN110474017B (en) * | 2019-08-29 | 2022-02-11 | 瑞海泊有限公司 | Preparation method and application of zinc manganate electrode |
| 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030113630A1 (en) * | 2001-12-06 | 2003-06-19 | Kainthla Ramesh C. | Anodic zinc electrode for use in an alkaline based electrochemical cell |
| WO2011079482A1 (en) * | 2009-12-29 | 2011-07-07 | 万向电动汽车有限公司 | Battery |
| CN103107373B (en) * | 2011-11-14 | 2015-09-09 | 苏州宝时得电动工具有限公司 | Battery |
-
2013
- 2013-09-27 CN CN201310452547.0A patent/CN104518205B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104518205A (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104518205B (en) | The preparation method and zinc load and battery of zinc load | |
| KR101758967B1 (en) | Battery | |
| CN102903973B (en) | Battery | |
| CN102903924B (en) | Battery | |
| WO2017020860A1 (en) | Battery, battery set and uninterruptable power source | |
| CN103107373B (en) | Battery | |
| CN106058168A (en) | Prelithiated positive electrode material for lithium ion secondary battery | |
| CN104733785B (en) | Battery | |
| CN107403968A (en) | Aqoue seconary battery | |
| CN101859887A (en) | Transition metal phosphate-clad composite lithium ion battery anode material | |
| CN103094583B (en) | The processing method of battery and battery afflux liquid | |
| CN104882637B (en) | Electrolyte and electrochemical energy storage device | |
| CN106450509A (en) | Electrolyte and battery | |
| CN104766971B (en) | Positive electrode, the water system battery containing positive electrode | |
| CN107256946A (en) | Battery | |
| CN106328950A (en) | Positive electrode material and battery | |
| CN105742637A (en) | Positive material and battery containing same | |
| CN113690397B (en) | Zinc cathode pole piece and preparation method and application thereof | |
| CN104733787B (en) | Battery | |
| CN104282952B (en) | Electrolyte and battery | |
| CN109119635B (en) | Battery with a battery cell | |
| CN104282910A (en) | Battery | |
| CN108963241A (en) | battery, battery pack and uninterruptible power supply | |
| CN104681846A (en) | Battery and electrolytic solution thereof | |
| CN113140808B (en) | Water-based battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |