CN104733774A - Battery - Google Patents
Battery Download PDFInfo
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- CN104733774A CN104733774A CN201310711703.0A CN201310711703A CN104733774A CN 104733774 A CN104733774 A CN 104733774A CN 201310711703 A CN201310711703 A CN 201310711703A CN 104733774 A CN104733774 A CN 104733774A
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- Prior art keywords
- ion
- battery
- metal
- electrolyte
- positive
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/028—Positive 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention provides a battery comprising a cathode, an anode, and an electrolyte solution. According to the battery, the cathode comprises a cathode active material capable of realizing reversible deintercalation-intercalation into first metal ions, and a cathode conductive agent; the electrolyte solution comprises a solvent capable of dissolving and ionizing electrolytes; the electrolytes comprise the first metal ions and second metal ions; in charging and discharging processes, the second metal ions can be transformed into a second metal via reduction and be deposited on the anode, and the second metal can be reversibly transformed into the second metal ions via oxidation dissolving; the battery also comprises an additive which is added into the cathode; the additive is an inorganic oxide; and oxygen evolution over-potential of the inorganic oxide is 2V or higher. The battery is capable of avoiding corrosion caused by the conductive agent in the battery cathode, improving a problem of battery self-discharging further, and improving battery electrochemical performance.
Description
Technical field
The invention belongs to field of batteries, be specifically related to a kind of battery exchanged based on inner ion.
Background technology
Lead-acid battery, its appearance is super century-old, has ripe battery technology, in occupation of the absolute market share in the energy storage fields such as automobile starting storage battery, electric bicycle, UPS.Although lead-acid battery service life cycle is lower, energy density is also relatively low, has price very cheap, the advantage that cost performance is very high.Therefore, in the last few years, Ni-MH battery, lithium ion battery, sodium-sulphur battery etc., all cannot replace lead-acid battery in energy storage field.
Newly there is a kind of battery exchanged based on inner ion.The operation principle of this battery is, positive pole deviates from-insertion reaction based on the first metal ion, negative pole is based on the deposition-solubilizing reaction of the second metal ion, and electrolyte deviates from containing participating in positive pole-the first metal ion of insertion reaction and participate in the second metal ion of cathode deposition-solubilizing reaction.The theoretical energy density of the type battery is 160Wh/Kg, estimates that actual energy density can reach 50 ~ 80Wh/Kg.In sum, the type battery promises to be the energy-storage battery of future generation of alternative lead-acid battery very much, has great commercial value.
But such self-discharge of battery problem is comparatively serious at present, battery performance can be caused to worsen rapidly, limit the practical application of such battery, therefore, urgently find a kind of new ion-exchange battery, can improve the self discharge problem of battery.
Summary of the invention
The object of this invention is to provide a kind of ion-exchange battery, the etching problem of ion-exchange anode conductive agent can be improved, thus improve the self discharge problem of battery further.
A kind of battery, comprise positive pole, negative pole and electrolyte, described positive pole comprises the positive active material and positive conductive agent that can reversiblely deviate from-embed the first metal ion; Described electrolyte comprises and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte comprises the first metal ion and the second metal ion, and described second metal ion can be deposited as the second metal at described cathodic reduction in charge and discharge process, and the oxidation dissolution that described second metal can be reversible is the second metal ion; Wherein, described battery also comprises the additive joined in described positive pole, and described additive is inorganic oxide, and the overpotential for oxygen evolution of described inorganic oxide is not less than 2V.
Preferably, described inorganic oxide is TiO
2, Bi
2o
3, SnO
2, SrO, Al
2o
3, PbO
2, CeO
2in at least one.
Preferably, with the mass percentage of described positive pole for benchmark, the mass percentage of described inorganic oxide is not higher than 10%.
Preferably, the pH value of described electrolyte is 3 ~ 7.
Preferably, described solvent is water or alcohol.
Preferably, the anion in described electrolyte comprises one or more in sulfate ion, chloride ion, acetate ion, formate ion, phosphate anion or alkyl sulfonate ion.
Preferably, described first metal ion is selected from lithium ion or sodium ion.
Preferably, described second metal ion is manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
Preferably, described positive active material is selected from LiMn
2o
4, LiFePO
4or LiCoO
2in one or more.
Preferably, described positive conductive agent is one or more in conducting polymer, conductive oxide, activated carbon, Graphene, carbon black, graphite, carbon fiber, metallic fiber, metal dust and sheet metal.
The present invention is by with the addition of at the positive pole of battery the inorganic oxide that overpotential for oxygen evolution is not less than 2V, oxygen can be suppressed in the precipitation of positive pole, improve the etching problem of anode conductive agent, thus improve the self discharge problem of battery further, also improve chemical property and the security performance of battery simultaneously.
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.
The invention provides a kind of battery, comprise positive pole, negative pole and electrolyte, positive pole comprises the positive active material and positive conductive agent that can reversiblely deviate from-embed the first metal ion; Electrolyte comprises can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte comprises the first metal ion and the second metal ion, and the second metal ion can be deposited as the second metal at 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 also comprises the additive joined in positive pole, and additive is 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 is: during charging, and positive active material deviates from the first metal ion, simultaneously oxidized with positive active material, and ejected electron; Electronics arrives battery cathode via external circuit, and the second metal ion simultaneously in electrolyte obtains electronics and is reduced on negative pole, and is deposited on negative pole.During electric discharge, the second metal be deposited on negative pole is oxidized, loses electronics and changes the second metal ion into and enter in electrolyte; Electronics arrives positive pole through external circuit, and positive active material accepts electronics and is reduced, and the first metal ion embeds in positive active material simultaneously.
The positive pole of battery comprises positive active material, and positive active material participates in positive pole reaction, and reversiblely can deviate from-embed the first metal ion.
Preferably, the first metal ion is selected from lithium ion or sodium ion.
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.
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 is selected from LiMn
2o
4, LiFePO
4or LiCoO
2in one or more.
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.
Concrete, positive pole also comprises the plus plate current-collecting body of load positive active material, plus plate current-collecting body is only as the carrier of electrical conductivity and collection, do not participate in electrochemical reaction, namely within the scope of battery operating voltage, plus plate current-collecting body can be stable be present in electrolyte and substantially side reaction do not occur, thus ensure that battery has stable cycle performance.
The material of plus plate current-collecting body is selected from the one in carbon-based material, metal or alloy.
Carbon-based material is selected from the one in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In a particular embodiment, plus plate current-collecting body is graphite, and as the paper tinsel that business-like graphite is suppressed, the part by weight scope wherein shared by graphite is 90-100%.
Metal comprises Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.
Alloy comprises stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned metal of Passivation Treatment.
Stainless steel comprises stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Preferably, carry out Passivation Treatment to plus plate current-collecting body, its main purpose is, make the surface of plus plate current-collecting body form the oxide-film of one deck passivation, thus in battery charge and discharge process, stable collection and the effect of conduction electron can be played, and cell reaction can not be participated in, ensure that battery performance is stablized.Plus plate current-collecting body deactivating process for the treatment of comprises chemical passivation process or electrochemical passivation process.
Chemical passivation process comprises by oxidizing plus plate current-collecting body, makes anode collection surface form passivating film.The principle that oxidant is selected is that oxidant can make anode collection surface form one deck passivating film and can not dissolve plus plate current-collecting body.Oxidant is selected from but is not limited only to red fuming nitric acid (RFNA) or ceric sulfate (Ce (SO
4)
2).
Electrochemical passivation process comprises and aligns pole collector and carry out electrochemical oxidation or carry out discharge and recharge process to the battery containing plus plate current-collecting body, makes anode collection surface form passivating film.
Be more preferably, positive pole also comprises the composite current collector of load positive active material, and composite current collector comprises plus plate current-collecting body and is coated on plus plate current-collecting body upper conductive film.
The selection of conducting film must to meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, do not occur swelling, high voltage can not oxidized, be easy to be processed into densification, the waterproof and film of conduction.On the one hand, conducting film can play a protective role to plus plate current-collecting body, avoids aqueous electrolyte to the corrosion of plus plate current-collecting body.On the other hand, be conducive to reducing the contact internal resistance between positive plate and plus plate current-collecting body, improve the energy of battery.
Preferably, the thickness of conducting film is 10 μm ~ 2mm, and conducting film effectively can not only play the effect of protection plus plate current-collecting body, and is conducive to reducing the contact internal resistance between positive active material and plus plate current-collecting body, improves the energy of battery.
Plus plate current-collecting body has the first surface and second that are oppositely arranged, and preferably, the first surface of plus plate current-collecting body and second are all coated with conducting film.
Conducting film comprises the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50 ~ 95%, and preferably, polymer is selected from thermoplastic polymer.In order to enable conducting film conduct electricity, there is the form that two kinds feasible: (1) polymer is conducting polymer; (2) except polymer, conducting film also comprises conductive filler.
Conducting polymer choice requirement, namely can not as the ionic conduction of charge transfer medium for having conductive capability but electrochemicaUy inert.Concrete, conducting polymer includes but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and any mixture thereof.Conducting polymer inherently has conductivity, but can also adulterate to conducting polymer or modification to improve its conductive capability further.Consider from the stable use electric conductivity and battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler be surface area little, be difficult to oxidation, degree of crystallinity high, there is conductivity but electrochemicaUy inert, namely can not as the ionic conduction of charge transfer medium.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler mass percent scope is in the conductive film 5 ~ 50%.The average grain diameter of conductive filler is not particularly limited, and usual scope is in 100nm ~ 100 μm.
When comprising conductive filler in conducting film, the polymer in conducting film preferably comprises the non-conductive polymer played in conjunction with conductive filler effect, and non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.
Concrete, thermoplastic polymer includes but are not limited to polyolefin as polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, polyolefin, polyamide and Kynoar is preferably.These polymer are easily melted by heat, and therefore easy and plus plate current-collecting body is combined with each other.In addition, these polymer have large potential window, thus make positive stabilizer pole be also battery output density saving in weight.Preferably, conducting film is attached on plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.
In a particular embodiment, when preparing positive pole, except positive active material, all often also can add positive conductive agent and positive electrode binder to promote the performance of positive pole.
Positive conductive agent be selected from conducting polymer, conductive oxide, conductivity ceramics, 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).
In a particular embodiment, when preparing battery, also add inorganic oxide in positive pole, the overpotential for oxygen evolution of inorganic oxide is not less than 2V.Preferred embodiment, the inorganic oxide that positive pole adds is TiO
2, Bi
2o
3, SnO
2, SrO, Al
2o
3, PbO
2, CeO
2in at least one.With the mass percentage of positive pole for benchmark, add the mass percentage of inorganic oxide not higher than 10%.The inorganic oxide mode of adding in positive pole can be and directly inorganic oxide and positive electrode active materials and positive conductive agent, positive pole bonding agent is mixed together and prepares anode sizing agent.By adding at positive pole the inorganic oxide that overpotential for oxygen evolution is not less than 2V, the problem that positive conductive agent is corroded in battery charge and discharge process can be improved, thus the self discharge problem of the type ion-exchange battery can be improved.
The negative pole of battery, it is the second metal that the material of electrochemical reaction occurs, and the second metal can be the second metal ion and the second metal ion energy reversible reduction is deposited as the second metal by oxidation dissolution.Preferred embodiment, the second metal ion is manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
The negative pole of battery, according to the difference of structure and effect, can be following three kinds of different forms:
In the first preferred embodiment, negative pole only comprises negative current collector, and negative current collector is only as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.
Material selected from metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al of negative current collector or at least one in the above-mentioned metal of Passivation Treatment, or elemental silicon, or carbon-based material; Wherein, carbon-based material comprises graphite material, and the paper tinsel of such as business-like graphite compacting, the part by weight scope wherein shared by graphite is 90 ~ 100%.The material of negative current collector can also be selected from stainless steel or the stainless steel through Passivation Treatment.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, same, and stainless model can be the stainless steel of 300 series, as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.In addition, negative current collector can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, alloy, or at least one in oxide.The thickness range of plating/coating is 1 ~ 1000nm.Such as: tin on the negative current collector plated surface of Copper Foil or graphite foil, plumbous or silver-colored.
In the second preferred implementation, negative pole, except negative current collector, also comprises the negative electrode active material of load on negative current collector.Negative electrode active material is the second metal, and the second metal comprises its simple substance.Preferably, negative electrode active material is Zn, Ni, Fe, Cr, Cu, Mn, Sn or Pb.
Wherein, negative current collector with reference to the first preferred implementation, can not repeat them here.
Second metal is with sheet or Powdered existence.
When employing second sheet metal is as negative electrode active material, the second sheet metal and negative current collector form composite bed.
In concrete execution mode, when preparing negative pole, except negative electrode active material second metal dust, according to actual conditions, also interpolation cathode conductive agent and negative electrode binder promote the performance of negative pole as required.
In the 3rd preferred implementation, directly adopt the second sheet metal as negative pole, the second sheet metal, both as negative current collector, is also negative electrode active material simultaneously.
In the electrolyte of battery, the object of solvent dissolves electrolyte, and electrolyte is ionized in a solvent, finally generates the cation that can move freely and anion in the electrolytic solution.
Solvent is preferably water and/or alcohol.Wherein alcohol includes but not limited to methyl alcohol or ethanol.
Electrolyte comprises the first metal ion and the second metal ion, and wherein, the first metal ion in electrolyte, reversiblely can deviate from-embed at positive pole in charge and discharge process.Namely, when battery discharge, the first metal ion in electrolyte embeds in positive active material; When battery charges, the first metal ion is deviate from from positive active material, enters electrolyte.
Preferably, the first metal ion is selected from lithium ion or sodium ion, is more preferably lithium ion.
The second metal ion in electrolyte, can reduce at negative pole and be deposited as the second metal and the second metal energy reversible oxidation dissolving in charge and discharge process.Namely, when battery charges, the second reducing metal ions in electrolyte becomes the second metal, is deposited on negative pole; When battery discharge, the second metal oxygen changes into the second metal ion and dissolves from negative pole, enters electrolyte.
Preferably, the second metal ion is selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion; Be more preferably zinc ion.
Under a preferred embodiment, the first metal ion of the present invention is selected from lithium ion, and the second metal ion is selected from zinc ion simultaneously, and namely electrolyte cationic is lithium ion and zinc ion.
Anion in electrolyte can be any anion substantially not affecting both positive and negative polarity reaction and electrolyte dissolving in a solvent.Can be such as sulfate ion, chloride ion, acetate ion, formate ion, phosphate anion, alkyl sulfonate ion and mixing thereof etc.
The concentration of each ion in electrolyte, can carry out change allotment according to different situations such as the applications of different electrolyte, solvent and battery.
Preferably, in the electrolytic solution, the concentration of the first metal ion is 0.1 ~ 10mol/L.
Preferably, in the electrolytic solution, the concentration of the second metal ion is 0.5 ~ 15mol/L.
Preferably, in the electrolytic solution, the concentration of anion is 0.5 ~ 12mol/L.
Preferably, the pH value range of electrolyte is 3 ~ 7.So both effectively can ensure the concentration of the second metal ion in electrolyte, thus ensure capacity and the multiplying power discharging property of battery, proton can also be avoided to be total to the generation of imbedding problem.
Battery can not contain barrier film.Certainly, in order to provide better security performance, preferably between positive pole and negative pole, also barrier film is provided with in the electrolytic solution.The short circuit that the both positive and negative polarity that barrier film can avoid other unexpected factors to cause is connected and causes.
Barrier film does not have particular/special requirement, as long as allow electrolyte to pass through and the barrier film of electronic isolation.The various barrier films that organic system lithium ion battery adopts, all go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.
Under a preferred implementation, barrier film is barrier film electrolyte being divided into anode electrolyte and electrolyte liquid.Be limited in anode electrolyte by the first metal ion, the second metal ion is limited in electrolyte liquid, and such barrier film can stop the mutual pollution of both positive and negative polarity electrolyte, can select the electrolyte being more applicable to negative or positive electrode, but not affect ionic charge transmission.Such as adopt anion-exchange membrane or hydrogen ion exchange membrane as barrier film, be arranged in anode electrolyte first metal ion not by barrier film, so electrolyte liquid can not be entered, can only be limited in anode electrolyte; Be arranged in electrolyte liquid second metal ion by barrier film, so can not anode electrolyte be entered, can only to be limited in electrolyte liquid.But anion or hydrogen ion can freely pass through in electrolyte, therefore do not affect electrolyte intermediate ion charge transfer.
Battery of the present invention, the inorganic oxide that overpotential for oxygen evolution is not less than 2V is added in positive pole, the generation of anode gas in charge and discharge process can be suppressed, improve the etching problem of anode conductive agent, thus improve the self discharge problem of battery further, also improve the security performance of battery simultaneously, and add the serviceability of battery.
Below by embodiment, the present invention is further described.
Embodiment 1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, adds the Bi of LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC gross mass 5%
2o
3, be mixed to form 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.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
Take the zinc sulfate of certain mass, lithium sulfate, be added to the water dissolving, be configured to that zinc sulfate concentration is 2mol/L, lithium sulfate concentration is the electrolyte of 1mol/L.
Electrolyte is added drop-wise to the side of barrier film, then positive pole, barrier film, negative electrode layer stacked group are dressed up battery core, the side that barrier film drips is arranged towards negative pole; Then load in housing, be assembled into battery.The battery obtained, is denoted as S1.
Embodiment 2
Be with the difference of embodiment 1: LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, add the TiO of LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC gross mass 5%
2, be mixed to form uniform anode sizing agent.
The battery obtained, is denoted as S2.
Embodiment 3
Be with the difference of embodiment 1: LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, add the SnO of LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC gross mass 5%
2, be mixed to form uniform anode sizing agent.
The battery obtained, is denoted as S3.
Embodiment 4
Be with the difference of embodiment 1: LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, add the Al of LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC gross mass 5%
2o
3, be mixed to form uniform anode sizing agent.
The battery obtained, is denoted as S4.
Embodiment 5
Be with the difference of embodiment 2: institute adds TiO
2amount be 1%.
The battery obtained, is denoted as S5.
Embodiment 6
Be with the difference of embodiment 2: institute adds TiO
2amount be 10%.
The battery obtained, is denoted as S6.
Comparative example 1
LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC are mixed according to mass ratio 90:5:2.5:2.5 in water, forms uniform anode sizing agent.Anode sizing agent is coated on plus plate current-collecting body (stainless steel cloths of 50 μm) and forms active material layer, carried out compressing tablet subsequently, be cut into 6 × 6cm size, make positive plate.Positive plate thickness is 0.4mm, and positive active material surface density is 750g/m
2.
Adopt the zinc paper tinsel of thick 50 μm as negative pole.Barrier film is 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, negative pole and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.The battery obtained, is denoted as D1.
Self-discharge performance is tested
First battery is placed one day at 60 DEG C, again at ambient temperature with the charge/discharge capacity of 0.2C multiplying power at 1.4V ~ 2.1V voltage range build-in test S1 ~ S4 and D1 battery, by battery capacity with do not compare in the battery capacity of lower placement, obtain the capability retention that battery is placed after a day at 60 DEG C, as shown in table 1.
Table 1
| Battery sequence number | S1 | S2 | S3 | S4 | D1 |
| Capability retention (%) | 91.9 | 92.6 | 93.7 | 92.3 | 90 |
As can be seen from Table 1, the battery of S1-S4, is higher than the capability retention of D1 battery at 60 DEG C of capability retentions placed after a day, the inorganic oxide being not less than 2V at positive pole interpolation overpotential for oxygen evolution is described, improve the self discharge problem of battery, improve the chemical property of battery simultaneously.
Although inventor has done more detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, to those skilled in the art, above-described embodiment to be modified and/or flexible or adopt equivalent replacement scheme to be obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.
Claims (10)
1. a battery, comprises positive pole, negative pole and electrolyte, and described positive pole comprises the positive active material and positive conductive agent that can reversiblely deviate from-embed the first metal ion; Described electrolyte comprises and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte comprises the first metal ion and the second metal ion, and described second metal ion can be deposited as the second metal at described cathodic reduction in charge and discharge process, and the oxidation dissolution that described second metal can be reversible is the second metal ion; It is characterized in that: described battery also comprises the additive joined in described positive pole, described additive is inorganic oxide, and the overpotential for oxygen evolution of described inorganic oxide is not less than 2V.
2. battery as claimed in claim 1, is characterized in that: described inorganic oxide is TiO
2, Bi
2o
3, SnO
2, SrO, Al
2o
3, PbO
2, CeO
2in at least one.
3. battery as claimed in claim 1, it is characterized in that: with the mass percentage of described positive pole for benchmark, the mass percentage of described inorganic oxide is not higher than 10%.
4. battery as claimed in claim 1, is characterized in that: the pH value of described electrolyte is 3 ~ 7.
5. battery as claimed in claim 1, is characterized in that: described solvent is water or alcohol.
6. battery as claimed in claim 1, is characterized in that: the anion in described electrolyte comprises one or more in sulfate ion, chloride ion, acetate ion, formate ion, phosphate anion or alkyl sulfonate ion.
7. battery as claimed in claim 1, is characterized in that: described first metal ion is selected from lithium ion or sodium ion.
8. battery as claimed in claim 1, is characterized in that: described second metal ion is manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
9. battery as claimed in claim 1, is characterized in that: described positive active material is selected from LiMn
2o
4, LiFePO
4or LiCoO
2in one or more.
10. battery as claimed in claim 1, is characterized in that: described positive conductive agent is one or more in conducting polymer, conductive oxide, activated carbon, Graphene, carbon black, graphite, carbon fiber, metallic fiber, metal dust and sheet metal.
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| CN201810879257.7A CN109119635B (en) | 2013-12-20 | 2013-12-20 | Battery with a battery cell |
| CN201310711703.0A CN104733774A (en) | 2013-12-20 | 2013-12-20 | Battery |
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| CN201310711703.0A CN104733774A (en) | 2013-12-20 | 2013-12-20 | Battery |
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| CN201810879257.7A Division CN109119635B (en) | 2013-12-20 | 2013-12-20 | Battery with a battery cell |
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| CN104733774A true CN104733774A (en) | 2015-06-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016202276A1 (en) * | 2015-06-18 | 2016-12-22 | 苏州宝时得电动工具有限公司 | Anode material and battery |
| 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 |
| CN107302107A (en) * | 2016-04-15 | 2017-10-27 | 苏州宝时得电动工具有限公司 | electrolyte, battery and battery pack |
| CN110854387A (en) * | 2019-11-04 | 2020-02-28 | 宁德新能源科技有限公司 | Positive electrode, and electrochemical device and electronic device comprising same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274956A (en) * | 1999-05-25 | 2000-11-29 | 三星Sdi株式会社 | Positive active material composition of chargeable lithium cell and prepn. of plus plate using the composition thereof |
| CN1127163C (en) * | 1999-04-05 | 2003-11-05 | 深圳市比亚迪股份有限公司 | High-temperature Ni/H2 battery and its manufacture |
| CN1801510A (en) * | 2006-01-06 | 2006-07-12 | 福建南平南孚電池有限公司 | Cathode material for alkaline batteries |
| EP2048728A1 (en) * | 2006-07-27 | 2009-04-15 | Lexel Battery (Shenzhen) Co., Ltd. | A high-temperature composite additives for the nickel hydrogen rechargeable battery |
| CN103427119A (en) * | 2012-04-17 | 2013-12-04 | 苏州宝时得电动工具有限公司 | Battery with a battery cell |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU211445B (en) * | 1991-04-05 | 1995-11-28 | Battery Technologies Inc | Manganese dioxide cathode with improved supercharge characteristics for rechargeable alcaline manganese dioxide cells |
| JP4540025B2 (en) * | 1998-12-07 | 2010-09-08 | コーニング インコーポレイテッド | Production of ultra-low thermal expansion cordierite structures |
| US6838205B2 (en) * | 2001-10-10 | 2005-01-04 | Lynntech, Inc. | Bifunctional catalytic electrode |
| JP4661059B2 (en) * | 2004-02-23 | 2011-03-30 | パナソニック株式会社 | Alkaline storage battery and manufacturing method thereof |
| CN1917270A (en) * | 2006-09-01 | 2007-02-21 | 天津力神电池股份有限公司 | Method for increasing safe performance of square lithium ion secondary battery |
| CN101651208B (en) * | 2008-12-17 | 2011-12-28 | 成都和能科技有限公司 | Low self-discharge ferrous electrode material |
| CN102043004B (en) * | 2009-10-14 | 2013-10-30 | 同济大学 | Preparation method of PbO2 electrode with high oxygen evolution potential and long service life |
| WO2011065538A1 (en) * | 2009-11-30 | 2011-06-03 | 三洋電機株式会社 | Non-aqueous electrolyte rechargeable battery |
| CN105375039B (en) * | 2010-08-31 | 2018-06-22 | 中国科学院上海硅酸盐研究所 | A kind of air electrode for lithium air battery and preparation method thereof |
| CN102760868A (en) * | 2012-07-25 | 2012-10-31 | 哈尔滨工业大学 | Superbattery polar plate containing vacuum puffed grapheme, preparation method thereof and lead acid superbattery assembled thereby |
| CN102760867B (en) * | 2012-07-25 | 2014-09-10 | 哈尔滨工业大学 | Superbattery polar plate containing grapheme-based hydrogel, preparation method thereof and lead acid superbattery assembled thereby |
| CN103137945B (en) * | 2013-02-27 | 2015-09-16 | 浙江吉能电池科技有限公司 | The preparation method of electrodes of lithium-ion batteries and surface processing device |
| CN103253743A (en) * | 2013-04-28 | 2013-08-21 | 南京大学 | Preparation method and application of Fe-doped PTFE-PbO2/TiO2-NTs/Ti electrode |
| CN103247785B (en) * | 2013-05-23 | 2018-01-16 | 江苏欧力特能源科技有限公司 | A kind of lead-acid battery electrode group and preparation method thereof |
-
2013
- 2013-12-20 CN CN201810879257.7A patent/CN109119635B/en active Active
- 2013-12-20 CN CN201310711703.0A patent/CN104733774A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127163C (en) * | 1999-04-05 | 2003-11-05 | 深圳市比亚迪股份有限公司 | High-temperature Ni/H2 battery and its manufacture |
| CN1274956A (en) * | 1999-05-25 | 2000-11-29 | 三星Sdi株式会社 | Positive active material composition of chargeable lithium cell and prepn. of plus plate using the composition thereof |
| CN1801510A (en) * | 2006-01-06 | 2006-07-12 | 福建南平南孚電池有限公司 | Cathode material for alkaline batteries |
| EP2048728A1 (en) * | 2006-07-27 | 2009-04-15 | Lexel Battery (Shenzhen) Co., Ltd. | A high-temperature composite additives for the nickel hydrogen rechargeable battery |
| CN103427119A (en) * | 2012-04-17 | 2013-12-04 | 苏州宝时得电动工具有限公司 | Battery with a battery cell |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016202276A1 (en) * | 2015-06-18 | 2016-12-22 | 苏州宝时得电动工具有限公司 | Anode material and battery |
| CN107302107A (en) * | 2016-04-15 | 2017-10-27 | 苏州宝时得电动工具有限公司 | electrolyte, battery and battery pack |
| 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 |
| CN110854387A (en) * | 2019-11-04 | 2020-02-28 | 宁德新能源科技有限公司 | Positive electrode, and electrochemical device and electronic device comprising same |
| CN110854387B (en) * | 2019-11-04 | 2021-03-05 | 宁德新能源科技有限公司 | Positive electrode, and electrochemical device and electronic device comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109119635B (en) | 2021-10-15 |
| CN109119635A (en) | 2019-01-01 |
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