CN104733785B - Battery - Google Patents
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- CN104733785B CN104733785B CN201310710879.4A CN201310710879A CN104733785B CN 104733785 B CN104733785 B CN 104733785B CN 201310710879 A CN201310710879 A CN 201310710879A CN 104733785 B CN104733785 B CN 104733785B
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- electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
Abstract
The invention discloses a kind of battery, including positive pole, negative pole and electrolyte.Positive pole includes the positive active material for being capable of reversible embedded first metal ion of abjection；The solvent that electrolyte includes dissolving electrolyte and ionizes electrolyte；Electrolyte includes the first metal ion and the second metal ion；The second metal ion is reduced to the second metal deposit in negative pole in charging process, and the second metal reversible oxidation is dissolved as the second metal ion in discharge process.Battery also includes the additive being added in electrolyte, and additive includes the one or more in tween, tertiary amine compound, heterocyclic quaternary ammonium salt and thioamides.The present invention effectively inhibits the generation of gas, so as to avoid battery swell, enhances the security performance of battery.
Description
Technical field
The invention belongs to field of batteries, and in particular to a kind of battery exchanged based on inner ion.
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 the second metal ion-dissolving reaction, electrolyte takes off containing positive pole is participated in
Go out-the first metal ion of insertion reaction and participate in the second metal ion of cathode deposition-dissolving 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 summary, the type battery is very
The energy-storage battery of future generation for substituting lead-acid battery is promised to be, 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 and deteriorates rapidly.
The content of the invention
The technical problems to be solved by the invention are that a large amount of gases can be produced when ion exchange battery is used.
The invention provides a kind of battery, including positive pole, negative pole and electrolyte, the positive pole include can it is reversible deviate from-
The positive active material of embedded first metal ion；The electrolyte includes dissolving electrolyte and makes the molten of the electrolyte ionization
Agent；The electrolyte includes the first metal ion and the second metal ion；The second metal ion described in charging process is reduced
Be the second metal deposit in the negative pole, and in discharge process the second metal reversible oxidation be dissolved as second metal from
Son；The battery also includes being added to additive in the electrolyte, and the additive includes tween, tertiary amine compound, miscellaneous
One or more in ring quaternary ammonium salt and thioamides；
The formula of the thioamides is as follows：
Wherein, R1、R2、R3、R4One kind in H, alkyl and phenyl, and R1、R2、R3、R4It is asynchronously H.
Preferably, the alkyl is methyl.
Preferably, the thioamides is selected from tetramethyl thiourea, N, N- dimethyl sulfoureas, N- methylthioureas and diphenyl sulphur
One or more in urea.
Preferably, in the electrolytic solution, the weight/mass percentage composition of the thioamides is 0.01%~5%.
Preferably, one or more of the tertiary amine compound in triacetamide, triethylamine and triethanolamine；It is described
Heterocyclic quaternary ammonium salt is selected from N- ethylpyridines hydrochloride, N- benzyl pyridines hydrochloride, N-2- ethoxys pyridine hydrochloride, N-2-
One or more in hydroxypropyl ylpyridine hydrochloride and pyridine radicals-N- propane sulfonic acid betaines.
Preferably, in the electrolytic solution, the weight/mass percentage composition of tertiary amine compound or the heterocyclic quaternary ammonium salt be 0.01%~
5%。
Preferably, the tween is selected from polysorbate40.
Preferably, in the electrolytic solution, the weight/mass percentage composition of the tween is 0.01%~0.1%.
Preferably, the additive also includes the oxygen-containing acid ion compound of boron.
Preferably, the electrolyte also includes sulfate ion, chlorion, acetate ion, nitrate ion and alkyl
One or more in sulfonate ion.
Preferably, the alkyl sulfonate ion is selected from tosylate ion.
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, sodium ion or magnesium ion.
Preferably, second metal is selected from manganese, iron, copper, zinc, chromium, nickel, tin or lead.
Preferably, the pH value of the electrolyte is 3~7.
Preferably, the solvent is water or alcohol.
Compared with prior art, the present invention adds additive in the electrolytic solution, effectively inhibits the generation of gas, so that
Battery swell is avoided, the security performance of battery is enhanced.
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 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 dissolving electrolyte and makes the solvent of the electrolyte ionization；The electrolysis
Matter includes the first metal ion and the second metal ion；The second metal ion described in charging process is reduced to the second metal and sunk
In the negative pole, and in discharge process, the second metal reversible oxidation is dissolved as second metal ion to product；The battery is also
Including the additive being added in the electrolyte, the additive includes tween, tertiary amine compound, heterocyclic quaternary ammonium salt and thio
One or more in acid amides；
The formula of the thioamides is as follows：
Wherein, R1、R2、R3、R4One kind in H, alkyl and phenyl, and R1、R2、R3、R4It is asynchronously H.
It is highly preferred that the alkyl is methyl.
The charge-discharge principle of battery of the present invention is：During charging, positive active material deviates from the first metal ion, while adjoint
Positive active material is oxidized, and ejected electron；Electronics reaches GND via external circuit, while the second gold medal in electrolyte
Category ion obtains electronics on negative pole and is reduced, and is deposited on negative pole.During electric discharge, the second metal on negative pole is deposited on by oxygen
Change, lose electronics and be changed into the second metal ion into electrolyte；Electronics reaches positive pole through external circuit, and positive active material connects
It is reduced by electronics, while in the first metal ion insertion positive active material.
Tween is added in the electrolytic solution, the generation of gas is effectively inhibited, so as to avoid battery swell, enhances battery
Security performance.
Tween（English：tween）Known to those skilled in the art, its main component is polyoxyethylene sorbitan
Alcohol fatty acid ester（Also abbreviation polysorbate）, it is the condensation product of Span and oxirane.
Preferably, tween is selected from Tween-40.
Preferably, in the electrolytic solution, the weight/mass percentage composition of tween is 0.01%~0.1%.
Tertiary amine compound and heterocyclic quaternary ammonium salt are added in the electrolytic solution, can not only effectively suppress the generation of gas, so as to keep away
Exempt from battery swell, enhance the security performance of battery；While the cycle performance of battery can also be improved.
Tertiary amine compound in the present invention, refers to containing while the compound for the N atoms being connected with three C atoms.
Preferably, one or more of the tertiary amine compound in triacetamide, triethylamine and triethanolamine.
Preferably, heterocyclic quaternary ammonium salt is selected from N- ethylpyridines hydrochloride, N- benzyl pyridines hydrochloride, N-2- ethoxys
One or more in pyridine hydrochloride, N-2- hydroxypropyls ylpyridine hydrochloride and pyridine radicals-N- propane sulfonic acid betaines.
Preferably, in the electrolytic solution, the weight/mass percentage composition of tertiary amine compound or heterocyclic quaternary ammonium salt is 0.01%~5%；More
Preferably 0.1%~0.5%.
Thioamides is added in the electrolytic solution, the generation of gas is effectively inhibited, so as to avoid battery swell, is enhanced
The security performance of battery；And thioamides can also greatly improve the cycle performance of battery simultaneously.
It is particularly preferred that thioamides is selected from tetramethyl thiourea, N, N- dimethyl sulfoureas, N- methylthioureas and phenylthiourea
In one or more.
Wherein, R in tetramethyl thiourea, i.e. formula1、R2、R3、R4Thioamides when being methyl；N, N- dimethyl disulfide
R in urea, i.e. formula1With R3It is methyl, and R2With R4Thioamides when being H；R in N- methylthioureas, i.e. formula1、R2、
R3、R4One of be methyl, remaining be H when thioamides；R in rhenocure CA, i.e. formula1With R3It is phenyl, and R2With
R4Thioamides when being H.
Preferably, in the electrolytic solution, the weight/mass percentage composition of thioamides is 0.01%~5%；More preferably 0.1%~
0.5%。
In order to further lift the performance of battery, additive can also include the oxygen-containing acid ion compound of boron.
The oxygen-containing acid ion compound of the boron of the present invention, refers to contain boron atom in compound and oxygen atom ligand is formed
Acid ion.The compound of such as radical ion containing ortho-boric acid, the compound of the radical ion containing metaboric acid, containing many borate ions
Compound, the compound containing perboric acid ion.
Preferably, one or more of the oxygen-containing acid ion compound of boron in boric acid, borate and perborate.
Wherein, boric acid includes but is not limited to ortho-boric acid, metaboric acid or many boric acid.
Borate includes but is not limited to ortho-borate, metaborate or multi-borate.Preferably, borate is selected from boric acid
Sodium, kodalk, magnesium metaborate, the one or more of calcium metaborate or barium metaborate.
Perborate includes but is not limited to sodium perborate, perboric acid lithium, perboric acid rubidium, potassium perborate, excessively perboric acid caesium, boron
Sour calcium or perboric acid barium.
It is highly preferred that additive is selected from boric acid and borate.Boric acid and borate can combine to form soda acid cushioning liquid,
Can more preferable stable cell electrolyte pH value, improve the stability of battery.
In the electrolytic solution, on the basis of the gross weight of electrolyte, the quality percentage of the oxygen-containing acid ion compound of boron contains
Amount is preferably 0.01%~2%.
Additive is dispersed in the electrolytic solution.
The mode that additive is added in electrolyte, when can be electrolyte dissolution（Solvent is added together with electrolyte）；
Or before electrolyte dissolution also or after electrolyte dissolution, additive is added in solvent.
Wherein, the purpose of solvent is dissolving electrolyte in electrolyte, and electrolyte is ionized in a solvent, finally in electrolysis
The cation and anion that can move freely are generated in liquid.
Solvent includes but is not limited to water and alcohol, and alcohol includes but is not limited to methanol or ethanol.
Wherein, the first metal ion in electrolyte, in charge and discharge process positive pole can it is reversible deviate from-be embedded in.I.e.
In battery discharge, in the first metal ion insertion positive active material in electrolyte；When battery charges, the first metal from
Son is deviate from from positive active material, into electrolyte.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion, more preferably lithium ion.
Wherein, the second metal ion in electrolyte, the second metal ion is heavy in the cathodic reduction in charging process
Product is the second metal, and second metal oxidation dissolution in discharge process is the second metal ion；I.e. in charge and discharge process
It can be reduced in negative pole and be deposited as the second metal and the dissolving of the second metal energy reversible oxidation.
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. electrolyte cationic are lithium ion 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, phosphoric acid
Radical ion and its mixing etc..
Under a preferred embodiment, anion includes sulfate ion, chlorion, acetate ion and nitre in electrolyte
It is one or more of in acid ion.
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.
In order that battery performance more optimizes, the pH value range of electrolyte is preferably 3~7.
The pH value range of electrolyte is 3~7, and the concentration of the second metal ion in electrolyte so can be both effectively ensured,
So as to ensure the capacity and multiplying power discharging property of battery, the problem of proton is embedded in altogether can also be avoided.
Below to the positive pole of the present invention, it is described in detail and illustrates.
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.
Specifically, positive active material has spinel structure, layer structure or olivine structural.
Specifically, positive active material can it is reversible deviate from-be embedded in lithium ion, sodium ion or magnesium 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, Ni.It is preferred that, positive active material contains LiMn2O4.It is furthermore preferred that positive pole is lived
Property 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 can meet formula LixM1-yM′y(XO4)nCan it is reversible deviate from-be embedded in the olive of lithium ion
The compound of olive stone structure, 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 lithium ion abjection-inlaid scheme, such as LiMn can be selected2O4、LiFePO4、
LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).
In addition, can deviate from-be embedded in the compound N aVPO of sodium ion4F, can deviate from-be embedded in the compound Mg M of magnesium ionxOy
(wherein M is a kind of metal, 0.5<x<3,2<y<6) and with similar functions, it can deviate from-be embedded in the change of the first metal ion
Compound can serve as the positive active material of battery of the present invention.
Specifically, positive pole also includes the plus plate current-collecting body of load positive active material, plus plate current-collecting body is only passed as electronics
The carrier led and collected, is not involved in electrochemical reaction, i.e., in the range of battery operating voltage, and what plus plate current-collecting body can be stablized deposits
It is in electrolyte and does not occur side reaction substantially, so as to ensures that battery has stable cycle performance.
The one kind of the material of plus plate current-collecting body in carbon-based material, metal or alloy.
The one kind of carbon-based material in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In tool
In the embodiment of body, plus plate current-collecting body is graphite, the paper tinsel that such as commercialized graphite is suppressed, the wherein part by weight shared by graphite
Scope is 90-100%.
One in above-mentioned metal of the metal including Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or Jing Guo Passivation Treatment
Kind.
Alloy includes stainless steel, carbon steel, Al alloys, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-
One kind in Rh alloys or 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
The one kind become rusty in steel 316 or Stainless steel 316 L.
Preferably, processing is passivated to plus plate current-collecting body, its main purpose is that the surface for making plus plate current-collecting body is formed
The oxide-film of one layer of passivation, so that in battery charge and discharge process, collection and the conduction electronics of stabilization can be played a part of, without
Cell reaction can be participated in, it is ensured that battery performance is stable.Plus plate current-collecting body deactivating process for the treatment of includes chemical passivation and handled or electrification
Learn Passivation Treatment.
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 or ceric sulfate (Ce (SO4)2)。
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.
More preferred, positive pole also includes the composite current collector of load positive active material, and composite current collector includes positive pole
Collector and it is coated on plus plate current-collecting body upper conductive film.
The selection of conducting film must is fulfilled in aqueous electrolyte being stabilized, insoluble in electrolyte, do not occur it is molten
Swollen, high voltage can not be oxidized, be easily processed into fine and close, waterproof and conductive film.On the one hand, conducting film is to anode collection
Body can play a protective role, it is to 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.
It is preferred that, the thickness of conducting film is 10 μm of -2mm, and conducting 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 conducting film.
Conducting film includes the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50-95%, preferably
, polymer is selected from thermoplastic polymer.In order that conducting film can be conductive, there are two kinds of feasible forms：(1) polymer is to lead
Electric polymer；(2) in addition to polymer, conducting film also includes conductive filler.
Conducting polymer choice requirement is that with conductive capability but electrochemicaUy inert, i.e., will not be used 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 to conducting polymer or modified further to improve its conductive capability.From electric conductivity
Considered with stable use in battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Likewise, the choice requirement of conductive filler for surface area is small, be difficult to aoxidize, crystallinity is high, conductive but electricity
Chemical inertness, i.e., will not as charge transfer medium ionic conduction.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler
Mass percent scope in the conductive film is 5-50%.The average grain diameter of conductive filler is not particularly limited, and usual scope exists
100nm to 100 μm.
When including conductive filler in conducting film, the polymer in conducting film, which is preferably comprised, to be played with reference to conductive filler effect
Non-conductive polymer, non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.It is preferred that, it is 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, makrolon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, polyether sulfone, butylbenzene rubber
One or more in glue or Kynoar.Wherein, preferably polyolefin, polyamide and Kynoar.These polymer
Melt, therefore be easily combined with each other with plus plate current-collecting body easily by heat.In addition, these polymer have big electrochemical window
Mouthful, so that positive stabilizer pole and saving weight for battery output density.
It is preferred that, conducting film is attached on plus plate current-collecting body by way of hot pressing is combined, vacuumizes or sprayed.
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）.
Below to the negative pole of the present invention, it is described in detail and illustrates.
The negative pole of battery, occur electrochemical reaction material 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.
Preferably, the second metal is manganese, iron, copper, zinc, chromium, nickel, tin or lead.
Negative pole, according to its structure and the difference of effect, can be following three kinds of different forms：
In the first preferred embodiment, negative pole only includes negative current collector, and negative current collector is only passed as electronics
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 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.
In the second preferred embodiment, negative pole is except negative current collector, in addition to is supported on negative on negative current collector
Pole active material.Negative electrode active material is the second metal.
Wherein, negative current collector may be referred to the first preferred embodiment, will not be repeated here！
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 formation composite bed.
When using the second metal dust as negative electrode active material, slurry is made in the second metal dust, then will slurry
Material, which is coated on negative current collector, is made negative pole.
In a particular embodiment, when preparing negative pole, in addition to the metal dust of negative electrode active material second, according to reality
Border situation, the performance of negative pole is lifted always according to needing to add cathode conductive agent and negative electrode binder.
In the 3rd preferred embodiment, directly using the second sheet metal as negative pole, the second sheet metal is both as negative pole
Collector, while being also negative electrode active material.
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 short circuit that the both positive and negative polarity that other unexpected factors that barrier film can avoid are caused is connected and caused.
Barrier film does not have particular/special requirement, as long as allow electrolyte by and electronic isolation barrier film.Organic system lithium from
The various barrier films that sub- 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, the second metal ion is limited in electrolyte liquid, such barrier film energy
The mutual pollution of both positive and negative polarity electrolyte is prevented, may be selected to be more suitable for the electrolyte of negative or positive electrode, but do not influence ionic charge
Transmission.For example with anion-exchange membrane or hydrogen ion exchange membrane as barrier film, in anode electrolyte the first metal from
Son, so can not enter electrolyte liquid, can not can only be limited in anode electrolyte by barrier film；In electrolyte liquid
Second metal ion, so can not enter anode electrolyte, can not can only be limited in electrolyte liquid by barrier film.But
It is that anion or hydrogen ion can be passed freely through in electrolyte, therefore has no effect on electrolyte intermediate ion charge transfer.
When electrolyte is divided into anode electrolyte and electrolyte liquid, preferable additives only add electrolyte liquid, so that
Influence of the additive to positive pole can be avoided.
Battery of the present invention, due to the addition of additive in electrolyte, effectively inhibits the generation of gas, so as to avoid electricity
Pond swell, and battery performance deteriorate, and enhance the security performance of battery.
Below in conjunction with specific embodiment, the present invention will be further elaborated and explanation.
Embodiment 1.1
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC according to mass ratio 90:5:2.5:2.5 mix in water
Close, form uniform anode sizing agent.Anode sizing agent is coated in plus plate current-collecting body（50 μm of stainless steel plate）Upper formation active matter
Matter layer, is then carried out tabletting, is cut into 6cm × 6cm sizes, positive plate is made.
Negative pole is used as using thick 50 μm zinc paper tinsel.Barrier film is AGM fibreglass diaphragms.Barrier film and negative pole size and positive pole phase
When.
Weigh the methanesulfonic acid lithium of certain mass, methanesulfonic acid zinc to be dissolved in deionized water, then add N- methylthioureas, be made
The electrolyte that 2mol/L methanesulfonic acids lithium, 3mol/L methanesulfonic acids zinc, the content of N- methylthioureas are 0.5wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, is sealed, assembling
Into battery.Obtained battery, is denoted as A1.
Embodiment 1.2
With embodiment 1.1 except that, replace N- methylthioureas with tetramethyl thiourea, other parts be the same as Example 1.1,
Battery is obtained, A2 is denoted as.
Embodiment 1.3
With embodiment 1.1 except that, 0.5wt% N- methylthioureas are replaced with 0.01wt% rhenocure CA, its
His part be the same as Example 1.1, obtains battery, is denoted as A3.
Embodiment 1.4
With embodiment 1.1 except that, weigh the methanesulfonic acid lithium of certain mass, methanesulfonic acid zinc and be dissolved in deionized water,
Then N- methylthioureas and boric acid are added, 2mol/L methanesulfonic acids lithium, 3mol/L methanesulfonic acids zinc, the content of N- methylthioureas, which is made, is
The electrolyte that 0.5wt%, the content of boric acid are 1wt%.
Other parts be the same as Example 1.1, obtains battery, is denoted as A4.
Embodiment 2.1
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC according to mass ratio 90:5:2.5:2.5 mix in water
Close, form uniform anode sizing agent.Anode sizing agent is coated in plus plate current-collecting body（50 μm of stainless steel plate）Upper formation active matter
Matter layer, is then carried out tabletting, is cut into 6cm × 6cm sizes, positive plate is made.
Negative pole is used as using thick 50 μm zinc paper tinsel.Barrier film is AGM fibreglass diaphragms.Barrier film and negative pole size and positive pole phase
When.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, then adds triacetamide, be configured to sulfuric acid
Zinc concentration is that 2mol/L, sulfuric acid lithium concentration are the electrolyte that 1mol/L, the content of triacetamide are 0.5wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, is sealed, assembling
Into battery.Obtained battery, is denoted as B1.
Embodiment 2.2
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC according to mass ratio 90:5:2.5:2.5 mix in water
Close, form uniform anode sizing agent.Anode sizing agent is coated in plus plate current-collecting body（50 μm of stainless steel plate）Upper formation active matter
Matter layer, is then carried out tabletting, is cut into 6cm × 6cm sizes, positive plate is made.
Negative pole is used as using thick 50 μm zinc paper tinsel.Barrier film is AGM fibreglass diaphragms.Barrier film and negative pole size and positive pole phase
When.
Weigh the methanesulfonic acid lithium of certain mass, methanesulfonic acid zinc to be dissolved in deionized water, then add triacetamide, be made
The electrolyte that 2mol/L methanesulfonic acids lithium, 3mol/L methanesulfonic acids zinc, the content of triacetamide are 0.5wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, is sealed, assembling
Into battery.Obtained battery, is denoted as B2.
Embodiment 2.3
With embodiment 2.2 except that, triacetamide is replaced with triethylamine, other parts be the same as Example 2.2 obtains electricity
Pond, is denoted as B3.
Embodiment 3.1
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC according to mass ratio 90:5:2.5:2.5 mix in water
Close, form uniform anode sizing agent.Anode sizing agent is coated in plus plate current-collecting body（50 μm of stainless steel plate）Upper formation active matter
Matter layer, is then carried out tabletting, is cut into 6cm × 6cm sizes, positive plate is made.
Negative pole is used as using thick 50 μm zinc paper tinsel.Barrier film is AGM fibreglass diaphragms.Barrier film and negative pole size and positive pole phase
When.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, then adds polysorbate40, be configured to zinc sulfate
Concentration is that 2mol/L, sulfuric acid lithium concentration are the electrolyte that 1mol/L, the content of polysorbate40 are 0.1wt%.
Positive pole, negative pole and membrane layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, is sealed, assembling
Into battery.Obtained battery, is denoted as C1.
Comparative example 1
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC according to mass ratio 90:5:2.5:2.5 mix in water
Close, form uniform anode sizing agent.Anode sizing agent is coated in plus plate current-collecting body（50 μm of stainless steel plate）Upper formation active matter
Matter layer, is then carried out tabletting, is cut into 6cm × 6cm sizes, positive plate is made.
Negative pole is used as using thick 50 μm zinc paper tinsel.Barrier film is AGM fibreglass diaphragms.Barrier film and negative pole size and positive pole phase
When.
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, negative pole and membrane layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, is sealed, assembling
Into battery.Obtained battery, is denoted as AC1.
Comparative example 2
By LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC according to mass ratio 90:5:2.5:2.5 mix in water
Close, form uniform anode sizing agent.Anode sizing agent is coated in plus plate current-collecting body（50 μm of stainless steel plate）Upper formation active matter
Matter layer, is then carried out tabletting, is cut into 6cm × 6cm sizes, positive plate is made.
Negative pole is used as using thick 50 μm zinc paper tinsel.Barrier film is AGM fibreglass diaphragms.Barrier film and negative pole size and positive pole phase
When.
Methanesulfonic acid zinc, the methanesulfonic acid lithium of certain mass are weighed, is added to the water dissolving, being configured to methanesulfonic acid zinc concentration is
2mol/L, methanesulfonic acid lithium concentration are 3mol/L electrolyte.
Positive pole, negative pole and membrane layer stacked group are dressed up into battery core, loads in housing, is then injected into electrolyte, is sealed, assembling
Into battery.Obtained battery, is denoted as AC2.
Performance test：
Gas content is tested：
Weigh in 5g zinc powders, the electrolyte for being separately added into 20ml batteries A1, then seal, placed 4 days at 50 DEG C, record
Gas flow produced by daily.Test result is shown in Table 1.
The gas production that table 1 stands for zinc powder at 50 DEG C in A1 and AC2 electrolyte
As it can be seen from table 1 the relative gas production for AC2 of battery A1 is significantly reduced, this explanation additive methylthiourea
The side reaction between mesylate electrolyte and negative pole zinc powder can effectively be suppressed, so as to effectively suppress the aerogenesis of battery.
Weigh in 5g zinc powders, the electrolyte for being separately added into 20ml batteries B1, AC1, then seal, 10 are placed at 50 DEG C
My god, record the 1st, the gas flow produced by 3,5,10 day same day.Test result is shown in Table 2.
The gas production that table 2 stands for zinc powder at 50 DEG C in B1 and AC1 electrolyte
From table 2 it can be seen that the relative gas production for AC1 of battery B1 is significantly reduced, this explanation additive triacetamide
The side reaction between stannous sulphate electrolyte and negative pole zinc powder can effectively be suppressed, so as to effectively suppress the aerogenesis of battery.
Battery B2, AC2 is fully charged, then by negative pole zinc paper tinsel take out, after be separately added into new 20ml batteries B2, AC2's
In electrolyte, then seal, placed a couple of days at 50 DEG C, record gas flow produced daily.Test result is shown in Table 3.
The gas production that table 3 stands for zinc paper tinsel at 50 DEG C in B2 and AC2 electrolyte
From table 3 it can be seen that the relative gas production for AC2 of battery B2 is significantly reduced, this explanation additive triacetamide
The side reaction between mesylate electrolyte and negative pole zinc paper tinsel can effectively be suppressed, so as to effectively suppress the aerogenesis of battery.
Battery C1, AC1 is fully charged, then by negative pole zinc paper tinsel take out, after be separately added into new 20ml batteries C1, AC1's
In electrolyte, then seal, placed a couple of days at 50 DEG C, record gas flow produced daily.Test result is shown in Table 4.
The gas production that table 4 stands for zinc paper tinsel at 50 DEG C in C1 and AC1 electrolyte
From table 4, it can be seen that the relative gas production for AC1 of battery C1 is significantly reduced, this explanation additive tween can be with
Effectively suppress the side reaction between stannous sulphate electrolyte and negative pole zinc paper tinsel, so as to effectively suppress the aerogenesis of battery.
Cycle performance of battery is tested：
Charge and discharge cycles are carried out 20 times to battery A1-A3, B2-B3 and AC2, its cycle performance is tested, is as a result shown in table
5。
Table 5 is cycle performance of battery test result
From table 5, it can be seen that the capability retention after 20 times of battery A1-A4, B2-B3 has the lifting of first mate, this
Illustrate the additive of the present invention, the cycle performance of battery can be effectively improved.
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 (16)
1. a kind of battery, it is characterised in that the battery includes positive pole, negative pole and electrolyte, and the positive pole includes can be reversible
The positive active material of the metal ion of abjection-insertion first；The electrolyte includes dissolving electrolyte and makes the electrolyte electricity
From solvent；The electrolyte includes the first metal ion and the second metal ion；The second metal described in charging process from
Son is reduced to the second metal deposit in the negative pole, and the second metal reversible oxidation is dissolved as second gold medal in discharge process
Belong to ion；The battery also includes the additive being added in the electrolyte, and the additive includes tween, tertiary amine chemical combination
One or more in thing, heterocyclic quaternary ammonium salt and thioamides；
The formula of the thioamides is as follows：
Wherein, R1、R2、R3、R4It is selected from one kind in H, alkyl and phenyl, and R1、R2、R3、R4It is asynchronously H.
2. battery according to claim 1, it is characterised in that：The alkyl is methyl.
3. battery according to claim 1, it is characterised in that：The thioamides is selected from tetramethyl thiourea, N, N- diformazans
One or more in base thiocarbamide, N- methylthioureas and rhenocure CA.
4. battery according to claim 1, it is characterised in that：In the electrolytic solution, the quality percentage of the thioamides contains
Measure as 0.01%~5%.
5. battery according to claim 1, it is characterised in that：The tertiary amine compound be selected from triacetamide, triethylamine and
One or more in triethanolamine；The heterocyclic quaternary ammonium salt be selected from N- ethylpyridines hydrochloride, N- benzyl pyridines hydrochloride,
One kind in N-2- ethoxys pyridine hydrochloride, N-2- hydroxypropyls ylpyridine hydrochloride and pyridine radicals-N- propane sulfonic acid betaines
Or it is several.
6. battery according to claim 1, it is characterised in that：In the electrolytic solution, the tertiary amine compound or heterocyclic quaternary ammonium
The weight/mass percentage composition of salt is 0.01%~5%.
7. battery according to claim 1, it is characterised in that：The tween is selected from polysorbate40.
8. battery according to claim 1, it is characterised in that：In the electrolytic solution, the weight/mass percentage composition of the tween is
0.01%~0.1%.
9. battery according to claim 1, it is characterised in that：The additive also includes the oxygen-containing acid ion chemical combination of boron
Thing.
10. battery according to claim 1, it is characterised in that：The electrolyte also include sulfate ion, chlorion,
One or more in acetate ion, nitrate ion and alkyl sulfonate ion.
11. battery according to claim 10, it is characterised in that：The alkyl sulfonate ion be selected from methanesulfonate from
Son.
12. battery according to claim 1, it is characterised in that：The battery also includes being located between positive pole and negative pole
Barrier film.
13. battery according to claim 1, it is characterised in that：First metal ion be selected from lithium ion, sodium ion or
Magnesium ion.
14. battery according to claim 1, it is characterised in that：Second metal be selected from manganese, iron, copper, zinc, chromium, nickel,
Tin or lead.
15. battery according to claim 1, it is characterised in that：The pH value of the electrolyte is 3~7.
16. battery according to claim 1, it is characterised in that：The solvent is water or alcohol.
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| WO2019183224A1 (en) * | 2018-03-20 | 2019-09-26 | University Of Maryland, College Park | Electrolytes for rechargeable zn-metal battery |
| CN112909239B (en) | 2018-11-06 | 2023-03-24 | Sk新能源株式会社 | Positive electrode active material for lithium secondary battery and method for manufacturing same |
| CN110148787B (en) * | 2019-06-17 | 2022-08-26 | 中南大学 | Electrolyte for improving capacity of lithium-sulfur battery and lithium-sulfur battery |
| CN111525145B (en) * | 2019-07-26 | 2022-05-13 | 眉山茵地乐科技有限公司 | Electrolyte, battery and battery pack |
| CN112582673A (en) * | 2019-09-29 | 2021-03-30 | 比亚迪股份有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN110911750B (en) * | 2019-12-03 | 2022-06-24 | 珠海市赛纬电子材料股份有限公司 | High-voltage lithium ion battery electrolyte, additive and preparation method of additive |
| CN117747952A (en) * | 2021-11-15 | 2024-03-22 | 宁德时代新能源科技股份有限公司 | Lithium ion battery, battery module, battery pack and electricity utilization device |
| WO2023154748A1 (en) * | 2022-02-09 | 2023-08-17 | Rafie Ayda | Dual-role electrolyte additive for simultaneous polysulfide shuttle inhibition and redox mediation in sulfur batteries |
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