CN109119635A - battery - Google Patents

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Publication number
CN109119635A
CN109119635A CN201810879257.7A CN201810879257A CN109119635A CN 109119635 A CN109119635 A CN 109119635A CN 201810879257 A CN201810879257 A CN 201810879257A CN 109119635 A CN109119635 A CN 109119635A
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China
Prior art keywords
ion
battery
metal
electrolyte
anode
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CN201810879257.7A
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CN109119635B (en
Inventor
刘洋
陈璞
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Positec Power Tools Suzhou Co Ltd
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Positec Power Tools Suzhou Co Ltd
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Priority to CN201810879257.7A priority Critical patent/CN109119635B/en
Priority to CN201310711703.0A priority patent/CN104733774A/en
Publication of CN109119635A publication Critical patent/CN109119635A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/028Positive electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention provides a kind of battery, including anode, cathode and electrolyte, anode include can it is reversible deviate from-be embedded in positive active material and the positive conductive agent of the first metal ion;Electrolyte includes the solvent that can be dissolved electrolyte and ionize electrolyte;Electrolyte includes the first metal ion and the second metal ion, and the second metal ion can be deposited as the second metal in cathodic reduction in charge and discharge process, and the oxidation dissolution that the second metal can be reversible is the second metal ion;Wherein, battery further includes the additive being added in anode, and additive is inorganic oxide, and the overpotential for oxygen evolution of inorganic oxide is not less than 2V.Battery provided by the invention can improve etching problem existing for conductive agent in anode, to further improve the self discharge problem of battery, improve the chemical property of battery.

Description

Battery
The application is entitled battery filed in applicant's on December 20th, 2013, and application No. is 201310711703.0 Chinese invention patent application divisional application.
Technical field
The invention belongs to field of batteries, and in particular to a kind of battery based on inner ion exchange.
Background technique
Lead-acid battery has surpassed a century out, possesses mature battery technology, in occupation of automobile starting storage battery, electronic The absolute market share of the energy storage fields such as bicycle, UPS.Although lead-acid battery service life cycle is lower, energy density also phase To lower, but it is very cheap to possess price, the very high advantage of cost performance.Therefore, in recent years, nickel-metal hydride battery, lithium ion Battery, sodium-sulphur battery etc. can not replace lead-acid battery in energy storage field.
Newly there is a kind of battery based on inner ion exchange.The working principle of the battery is that anode is based on the first gold medal Belong to abjection-insertion reaction of ion, deposition of the cathode based on the second metal ion-dissolution reaction, it is de- that electrolyte contains participation anode The second metal ion of the first metal ion of out-insertion reaction and participation cathode deposition-dissolution reaction.The reason of the type battery It is 160Wh/Kg by energy density, it is contemplated that actual energy density is up to 50~80Wh/Kg.In conclusion the type battery is very The next-generation energy-storage battery of substitution lead-acid battery is promised to be, there is great commercial value.
But such self-discharge of battery problem is more serious at present, will lead to battery performance and deteriorates rapidly, limitation The practical application of such battery, it would therefore be highly desirable to find a kind of new ion exchange battery, the self discharge that can improve battery is asked Topic.
Summary of the invention
The object of the present invention is to provide a kind of ion exchange batteries, can improve the corruption of ion exchange anode conductive agent Erosion problem, to further improve the self discharge problem of battery.
A kind of battery, including anode, cathode and electrolyte, the anode include can it is reversible deviate from-be embedded in the first metal The positive active material of ion and positive conductive agent;The electrolyte includes that can dissolve electrolyte and ionize the electrolyte Solvent;The electrolyte includes the first metal ion and the second metal ion, and second metal ion is in charge and discharge process In can be deposited as the second metal in the cathodic reduction, the oxidation dissolution that second metal can be reversible be the second metal from Son;Wherein, the battery further includes the additive being added in the anode, and the additive is inorganic oxide, the nothing The overpotential for oxygen evolution of machine oxide is not less than 2V.
Preferably, the inorganic oxide is TiO2、Bi2O3、SnO2、SrO、Al2O3、PbO2、CeO2At least one of.
Preferably, on the basis of the mass percentage of the anode, the mass percentage of the inorganic oxide is not Higher than 10%.
Preferably, the pH value of the electrolyte is 3~7.
Preferably, the solvent is water or alcohol.
Preferably, the anion in the electrolyte include sulfate ion, chloride ion, acetate ion, formate from It is one or more of in son, phosphate anion or alkyl sulfonate ion.
Preferably, first metal ion is selected from lithium ion or sodium ion.
Preferably, second metal ion is manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin Ion or lead ion.
Preferably, the positive active material is selected from LiMn2O4、LiFePO4Or LiCoO2Middle one or more.
Preferably, the positive conductive agent be conducting polymer, conductive oxide, activated carbon, graphene, carbon black, graphite, One or more of carbon fiber, metallic fiber, metal powder and sheet metal.
The present invention is added to the inorganic oxide that overpotential for oxygen evolution is not less than 2V by the anode in battery, is able to suppress oxygen Gas improves the etching problem of anode conductive agent in the precipitation of anode, to further improve the self discharge problem of battery, together When also improve the chemical property and security performance of battery.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is 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 used to explain The present invention is not intended to limit the present invention.
The present invention provides a kind of battery, including anode, cathode and electrolyte, anode include can it is reversible deviate from-be embedded in the The positive active material of one metal ion and positive conductive agent;Electrolyte includes that can dissolve electrolyte and ionize electrolyte Solvent;Electrolyte includes the first metal ion and the second metal ion, and the second metal ion can be negative in charge and discharge process Pole reduction is deposited as the second metal, and the oxidation dissolution that the second metal can be reversible is the second metal ion;Wherein, battery further includes The additive being added in anode, additive are inorganic oxide, and the overpotential for oxygen evolution of inorganic oxide is not less than 2V.
The charge-discharge principle of battery of the present invention are as follows: when charging, positive active material deviates from the first metal ion, while adjoint Positive active material is oxidized, and ejected electron;Electronics reaches battery cathode, while the second gold medal in electrolyte via external circuit Category ion obtains electronics on cathode and is reduced, and is deposited on cathode.When electric discharge, the second metal on cathode is deposited on by oxygen Change, loses electronics and be changed into the second metal ion and enter in electrolyte;Electronics reaches anode through external circuit, and positive active material connects It is reduced by electronics, while in the first metal ion insertion positive active material.
The anode of battery includes positive active material, and positive active material participates in anode reaction, and can it is reversible deviate from- It is embedded in the first metal ion.
Preferably, the first metal ion is selected from lithium ion or sodium ion.
Positive active material, which can be, meets general 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.Preferably, positive active material contains LiMn2O4.It is furthermore preferred that positive-active Substance contains the LiMn through overdoping or coating modification2O4
Positive active material, which can be, meets general 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.
Positive active material, which can also be, meets general 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.
Preferably, positive active material is selected from LiMn2O4、LiFePO4Or LiCoO2Middle one or more.
In current battery industry, nearly all positive active material all can be through modifications such as overdoping, claddings.But it mixes 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 general formula of " LiMn2O4 ", and should be with general formula Li1+xMnyMzOkSubject to, it widely include the LiMn by various modifications2O4 Positive active material.Likewise, LiFePO4And LiCoO2Also it should be construed broadly to include by various doping, cladding etc. Modified, general formula corresponds with LixM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nPositive active material.
When positive active material is the substance of the reversible abjection-insertion lithium ion of energy, it can preferably select such as LiMn2O4、 LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).In addition, anode of the invention When active material is the substance of the reversible abjection-insertion sodium ion of energy, NaVPO can be preferably selected4F etc..
Specifically, anode further includes the plus plate current-collecting body for loading positive active material, plus plate current-collecting body is only used as electronics to pass The carrier led and collected is not involved in electrochemical reaction, i.e., within the scope of battery operating voltage, what plus plate current-collecting body can be stable is deposited It is in electrolyte and side reaction does not occur substantially, to guarantees that battery has stable cycle performance.
The material of plus plate current-collecting body is selected from one of carbon-based material, metal or alloy.
Carbon-based material is selected from one of vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.Having In the embodiment of body, plus plate current-collecting body is graphite, such as the foil of commercialized graphite compacting, wherein weight ratio shared by graphite Range is 90-100%.
Metal includes one in Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or above-mentioned metal Jing Guo Passivation Treatment Kind.
Alloy includes stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt- Rh alloy or one of above-mentioned metal Jing Guo Passivation Treatment.
Stainless steel includes stainless (steel) wire, stainless steel foil, and the model of stainless steel includes but are not limited to stainless steel 304 or not Become rusty one of steel 316 or Stainless steel 316 L.
Preferably, processing is passivated to plus plate current-collecting body, main purpose be to form the surface of plus plate current-collecting body The oxidation film of one layer of passivation, so that stable collection and conduction electronics can be played the role of in battery charge and discharge process, without Cell reaction can be participated in, guarantees that battery performance is stablized.Plus plate current-collecting body deactivating process for the treatment of includes chemical passivation processing or electrification Learn Passivation Treatment.
Chemical passivation processing includes so that plus plate current-collecting body surface is formed passivating film by oxidizing plus plate current-collecting body. The principle that oxidant selects 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 or ceric sulfate (Ce (SO4)2)。
Electrochemical passivation processing includes electrochemical oxidation being carried out to plus plate current-collecting body 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 made to form passivating film.
More preferred, anode further includes the composite current collector for loading positive active material, and composite current collector includes anode Collector and it is coated on plus plate current-collecting body upper conductive film.
The selection of conductive film must satisfy can be stabilized in aqueous electrolyte, insoluble in electrolyte, do not occur it is molten Swollen, high voltage cannot be oxidized, be easily processed into fine and close, waterproof and conductive film.On the one hand, conductive film is to anode collection Body can play a protective role, and avoid corrosion of the aqueous electrolyte to plus plate current-collecting body.On the other hand, positive plate is advantageously reduced Contact internal resistance between plus plate current-collecting body, improves the energy of battery.
Preferably, conductive film with a thickness of 10 μm~2mm, conductive film can not only effectively play protection plus plate current-collecting body Effect, and advantageously reduce the contact internal resistance between positive active material and plus plate current-collecting body, improve the energy of battery.
Plus plate current-collecting body has the first face and the second face that are oppositely arranged, it is preferred that the first face of plus plate current-collecting body and the Two faces are coated with conductive film.
Conductive film includes the polymer as necessary component, and the weight proportion that polymer accounts for conductive film is 50~95%, excellent Choosing, polymer is selected from thermoplastic polymer.In order to keep conductive film conductive, there are two types of feasible forms: (1) polymer is Conducting polymer;(2) other than polymer, conductive film also includes conductive filler.
Conducting polymer choice requirement be with conductive capability but electrochemicaUy inert, i.e., will not be as charge transfer medium Ionic conduction.Specifically, conducting polymer include but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, Polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and its any mixture.Conducting polymer inherently has It is conductive, it is also possible to be doped or be modified to conducting polymer to further increase its conductive capability.From electric conductivity It is considered with the use of stablizing in battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Likewise, the choice requirement of conductive filler is that surface area is small, be difficult to aoxidize, crystallinity is high, conductive but electric Chemical inertness, i.e., will not be as the ionic conduction of charge transfer medium.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler Mass percent range in the conductive film is 5~50%.The average grain diameter of conductive filler is not particularly limited, usual range In 100nm~100 μm.
When in conductive film including conductive filler, the polymer in conductive film, which preferably comprises, to be played the role of in conjunction with conductive filler Non-conductive polymer, non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, non- Conducting polymer is thermoplastic polymer.
Specifically, thermoplastic polymer includes but are not limited to polyolefin such as polyethylene, polypropylene, polybutene, polychlorostyrene second Alkene, polystyrene, polyamide, polycarbonate, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, polyether sulfone, butylbenzene rubber One of glue or Kynoar are a variety of.Wherein, preferably polyolefin, polyamide and Kynoar.These polymer It is easy to melt by heat, therefore is easy to be combined with each other with plus plate current-collecting body.In addition, these polymer have big electrochemical window Mouthful, to make just extremely stable and save weight for battery output density.Preferably, conductive film by hot pressing is compound, vacuumize or The mode of spraying is integrated on plus plate current-collecting body.
In a particular embodiment, when preparation anode, other than positive active material, anode often can be also added all Conductive agent and positive electrode binder promote the performance of anode.
Positive conductive agent be selected from conducting polymer, conductive oxide, conductivity ceramics, activated carbon, graphene, carbon black, graphite, One of carbon fiber, metallic fiber, metal powder and sheet metal are a variety of.
Positive electrode binder can be selected from polyethylene oxide, polypropylene oxide, and polyacrylonitrile, polyester, gathers polyimides Ether, fluorinated polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, in 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), gathers Vinylidene (PVDF) or butadiene-styrene rubber (SBR).
In a particular embodiment, when preparing battery, inorganic oxide, the analysis oxygen of inorganic oxide are also added in anode Overpotential is not less than 2V.In preferred embodiment, inorganic oxide added by anode is TiO2、Bi2O3、SnO2、SrO、 Al2O3、PbO2、CeO2At least one of.On the basis of the mass percentage of anode, the quality of added inorganic oxide Percentage composition is not higher than 10%.Inorganic oxide is added to the mode in anode can be for directly by inorganic oxide and positive-active Material and positive conductive agent, positive bonding agent are mixed together and prepare anode sizing agent.By adding overpotential for oxygen evolution not in anode Inorganic oxide lower than 2V can improve the problem of positive conductive agent is corroded in battery charge and discharge process, so as to Improve the self discharge problem of the type ion exchange battery.
The cathode of battery, occur electrochemical reaction substance be the second metal, the second metal can oxidation dissolution be second Metal ion and the second metal ion energy reversible reduction is deposited as the second metal.In preferred embodiment, the second metal ion For manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
The cathode of battery can be following three kinds of different forms according to structure and the difference of effect:
In the first preferred embodiment, cathode only includes negative current collector, and negative current collector is only used as electronics to pass The carrier led and collected, 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 belong to perhaps elemental silicon or carbon-based material;Wherein, carbon-based material includes graphite material, such as commercialized The foil of graphite compacting, wherein weight ratio range 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 plating/coating metal high containing hydrogen-evolution overpotential, to reduce the generation of cathode side reaction.Plating/ Coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, at least one of alloy or oxide.Plating/coating thickness model It encloses for 1~1000nm.Such as: tin, lead or silver are plated on the negative current collector surface of copper foil or graphite foil.
In the second preferred embodiment, cathode further includes being supported on bearing on negative current collector in addition to negative current collector Pole active material.Negative electrode active material is the second metal, and the second metal includes its simple substance.Preferably, negative electrode active material Zn, Ni, Fe, Cr, Cu, Mn, Sn or Pb.
Wherein, negative current collector can refer to the first preferred embodiment, and details are not described herein.
Second metal is with sheet or powdered presence.
When using the second sheet metal as negative electrode active material, the second sheet metal and negative current collector form composite layer.
In specific embodiment, when preparing cathode, other than the second metal powder of negative electrode active material, according to reality Situation promotes the performance of cathode also according to needing to add cathode conductive agent and negative electrode binder.
In third preferred embodiment, the second sheet metal is directlyed adopt as cathode, the second sheet metal is both used as cathode Collector, while being also negative electrode active material.
In the electrolyte of battery, the purpose of solvent is dissolution electrolyte, and ionizes electrolyte in a solvent, finally in electricity The cation and anion that can move freely are generated in solution liquid.
Solvent is preferably water and/or alcohol.Wherein alcohol includes but is not limited to methanol or ethyl alcohol.
Electrolyte includes the first metal ion and the second metal ion, wherein the first metal ion in electrolyte is filling In discharge process anode can it is reversible deviate from-be embedded in.I.e. in battery discharge, the first metal ion insertion in electrolyte is just In the active material of pole;In battery charging, the 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.
The second metal ion in electrolyte can restore in cathode in charge and discharge process and be deposited as the second metal and The dissolution of two metal energy reversible oxidations.I.e. when battery charges, the second metal ion in electrolyte is reduced into the second metal, deposits On cathode;In battery discharge, the second metal is oxidized to the second metal ion and dissolves from cathode, into electrolyte.
Preferably, the second metal ion be selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin from Son or lead ion;More preferably zinc ion.
Under a preferred embodiment, the first metal ion of the invention is selected from lithium ion, while the second metal ion is selected from Zinc ion, i.e., cation is lithium ion and zinc ion in electrolyte.
Anion in electrolyte can be and any have substantially no effect on positive and negative anodes reaction and electrolyte in a solvent molten The anion of solution.Such as it can be sulfate ion, chloride ion, acetate ion, formate ion, phosphate anion, alkyl Sulfonate ion and its mixing etc..
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 0.1~10mol/L.
Preferably, in the electrolytic solution, the concentration of the second metal ion is 0.5~15mol/L.
Preferably, in the electrolytic solution, the concentration of anion is 0.5~12mol/L.
Preferably, the pH value range of electrolyte is 3~7.The second metal ion in electrolyte can both be effectively ensured in this way Concentration proton can also be avoided to be total to the generation of imbedding problem to guarantee the capacity and multiplying power discharging property of battery.
Battery can be free of diaphragm.Certainly, in order to provide better security performance, preferably in the electrolytic solution be located at anode with Diaphragm is additionally provided between cathode.Diaphragm can to avoid positive and negative anodes caused by other unexpected factors be connected and caused by short circuit.
Diaphragm does not have particular/special requirement, as long as permission electrolyte passes through and the diaphragm of electronic isolation.Organic system lithium from The various diaphragms that sub- battery uses, can be adapted for the present invention.Diaphragm can also be the other materials such as micropore ceramics partition.
Under a preferred embodiment, diaphragm is the diaphragm that electrolyte is divided into anode electrolyte and electrolyte liquid. The first metal ion is limited in anode electrolyte, the second metal ion is limited in electrolyte liquid, such diaphragm energy The mutual pollution for preventing positive and negative anodes electrolyte, may be selected to be more suitable the electrolyte of positive or negative pole, but not influence ionic charge Transmitting.For example, by using anion-exchange membrane or hydrogen ion exchange membrane as diaphragm, be located in anode electrolyte the first metal from Son, so not can enter electrolyte liquid, cannot can only be limited in anode electrolyte by diaphragm;In electrolyte liquid Second metal ion, so can not enter anode electrolyte, can not can only be limited in electrolyte liquid by diaphragm.But It is that anion or hydrogen ion can pass freely through in electrolyte, therefore have no effect on electrolyte intermediate ion charge transfer.
The inorganic oxide that overpotential for oxygen evolution is not less than 2V is added battery of the invention in anode, is able to suppress charge and discharge The generation of anode gas in electric process improves the etching problem of anode conductive agent, to further improve battery Self discharge problem, while the security performance of battery is also improved, and increase the service performance of battery.
Below by embodiment, the present invention is further described.
Embodiment 1
LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC are mixed in water according to mass ratio 90:5:2.5:2.5 Close, be added LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC gross mass 5% Bi2O3, it is mixed to form uniform anode Slurry.Anode sizing agent is coated in be coated on plus plate current-collecting body (50 μm of stainless steel cloths) two sides of conductive film and forms activity Material layer is then carried out tabletting, is cut into 8 × 10cm size, anode is made.Positive plate is with a thickness of 0.4mm, positive-active Substance surface density is 750g/m2
Using thick 50 μm of zinc foil as cathode.Diaphragm is AGM fibreglass diaphragm.Diaphragm and cathode size and positive phase When.
Zinc sulfate, the lithium sulfate for weighing certain mass, are added to the water dissolution, and being configured to sulfuric acid zinc concentration is 2mol/L, sulphur Sour lithium concentration is the electrolyte of 1mol/L.
Electrolyte is added drop-wise to the side of diaphragm, then anode, diaphragm, negative electrode layer stacked group are dressed up into battery core, what diaphragm was added dropwise Side is arranged towards cathode;It is then charged into shell, is assembled into battery.Obtained battery, is denoted as S1.
Embodiment 2
Difference from example 1 is that: by LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC according to quality It is mixed in water than 90:5:2.5:2.5, LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC gross mass 5% is added TiO2, it is mixed to form uniform anode sizing agent.
Obtained battery, is denoted as S2.
Embodiment 3
Difference from example 1 is that: by LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC according to quality It is mixed in water than 90:5:2.5:2.5, LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC gross mass 5% is added SnO2, it is mixed to form uniform anode sizing agent.
Obtained battery, is denoted as S3.
Embodiment 4
Difference from example 1 is that: by LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC according to quality It is mixed in water than 90:5:2.5:2.5, LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC gross mass 5% is added Al2O3, it is mixed to form uniform anode sizing agent.
Obtained battery, is denoted as S4.
Embodiment 5
With embodiment 2 the difference is that: TiO be added2Amount be 1%.
Obtained battery, is denoted as S5.
Embodiment 6
With embodiment 2 the difference is that: TiO be added2Amount be 10%.
Obtained battery, is denoted as S6.
Comparative example 1
LiMn2O4 LMO, conductive agent graphite, binder SBR and CMC are mixed in water according to mass ratio 90:5:2.5:2.5 It closes, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (50 μm of stainless steel cloths) and forms activity Material layer is then carried out tabletting, is cut into 6 × 6cm size, positive plate is made.For positive plate with a thickness of 0.4mm, anode is living Property substance surface density be 750g/m2
Using thick 50 μm of zinc foil as cathode.Diaphragm is AGM fibreglass diaphragm, diaphragm and cathode size and positive phase When.
Zinc sulfate, the lithium sulfate for weighing certain mass, are added to the water dissolution, and being configured to sulfuric acid zinc concentration is 2mol/L, sulphur Sour lithium concentration is the electrolyte of 1mol/L.
Anode, cathode and membrane layer stacked group are dressed up into battery core, is packed into shell, is then injected into electrolyte, is sealed, assembling At battery.Obtained battery, is denoted as D1.
Self-discharge performance test
First battery is placed one day at 60 DEG C, then at room temperature with 0.2C multiplying power in 1.4V~2.1V voltage range It is interior test S1~S4 and D1 battery charge/discharge capacity, by battery capacity be not compared in the battery capacity of lower placement, The capacity retention ratio after battery is placed one day at 60 DEG C is obtained, as shown in table 1.
Table 1
Battery serial number S1 S2 S3 S4 D1
Capacity retention ratio (%) 91.9 92.6 93.7 92.3 90
From table 1 it follows that the battery of S1-S4, the capacity retention ratio after placing one day at 60 DEG C is higher than D1 electricity The capacity retention ratio in pond illustrates to be not less than the inorganic oxide of 2V in anode addition overpotential for oxygen evolution, improves putting certainly for battery Electric problem, while improving the chemical property of battery.
Although inventor has done more detailed elaboration to technical solution of the present invention and has enumerated, it should be understood that for For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious , cannot all be detached from the essence of spirit of that invention, the term occurred in the present invention be used for elaboration to technical solution of the present invention and Understand, can not be construed as limiting the invention.

Claims (10)

1. a kind of battery, including anode, cathode and electrolyte, the anode include can it is reversible deviate from-be embedded in the first metal from The positive active material of son and positive conductive agent;The electrolyte includes that can dissolve electrolyte and ionize the electrolyte Solvent;The electrolyte includes the first metal ion and the second metal ion, and second metal ion is in charge and discharge process Can be deposited as the second metal in the cathodic reduction, the oxidation dissolution that second metal can be reversible be the second metal from Son;It is characterized by: the battery further includes the additive being added in the anode, the additive is inorganic oxide, The overpotential for oxygen evolution of the inorganic oxide is not less than 2V, and the inorganic oxide is TiO2、Bi2O3、SnO2、SrO、Al2O3、 PbO2、CeO2At least one of.
2. battery as described in claim 1, it is characterised in that: on the basis of the mass percentage of the anode, the nothing The mass percentage of machine oxide is not higher than 10%.
3. battery as described in claim 1, it is characterised in that: the pH value of the electrolyte is 3~7.
4. battery as described in claim 1, it is characterised in that: the solvent is water or alcohol.
5. battery as described in claim 1, it is characterised in that: the anion in the electrolyte includes sulfate ion, chlorine It is one or more of in ion, acetate ion, formate ion, phosphate anion or alkyl sulfonate ion.
6. battery as described in claim 1, it is characterised in that: first metal ion is selected from lithium ion or sodium ion.
7. battery as described in claim 1, it is characterised in that: second metal ion be manganese ion, iron ion, copper from Son, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
8. battery as described in claim 1, it is characterised in that: the positive active material is selected from LiMn2O4、LiFePO4Or LiCoO2Middle one or more.
9. battery as described in claim 1, it is characterised in that: the positive conductive agent be conducting polymer, conductive oxide, One or more of activated carbon, graphene, carbon black, graphite, carbon fiber, metallic fiber, metal powder and sheet metal.
10. battery as described in claim 1, it is characterised in that: the positive electrode binder is selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride Alkene or butadiene-styrene rubber.
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CN106450434A (en) * 2016-12-06 2017-02-22 龙能科技(苏州)有限责任公司 High-voltage high-energy-density lithium ion battery
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