CN105336993A - Electrolyte solution and battery - Google Patents
Electrolyte solution and battery Download PDFInfo
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- CN105336993A CN105336993A CN201410307591.7A CN201410307591A CN105336993A CN 105336993 A CN105336993 A CN 105336993A CN 201410307591 A CN201410307591 A CN 201410307591A CN 105336993 A CN105336993 A CN 105336993A
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 82
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- -1 alkyl sulfonate ion Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
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- 239000011701 zinc Substances 0.000 abstract description 13
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- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
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- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
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- 229910003086 Ti–Pt Inorganic materials 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte solution of an aqueous battery. The electrolyte solution comprises an electrolyte and an aqueous solution. The electrolyte solution comprises first metal ions and second metal ions, wherein the first metal ions can be reversibly intercalated and deintercalated in a positive electrode in the charging and discharging process; the second metal ions are reduced and deposited into a second metal in a negative electrode in the charging process, and the second metal is oxidized and dissolved into the second metal ions in the discharging process. The electrolyte solution also comprises a polyvinyl alcohol additive, and the electrolyte solution is aqueous. According to the electrolyte solution provided by the invention, the corrosion of zinc electrodes and the generation of dendritic crystals and hydrogen can be retarded, so that the cycle life of the battery is prolonged, and the electrochemical performance and safety performance of the battery are improved. The invention also provides a battery containing the electrolyte solution.
Description
Technical field
The invention belongs to electrochemical energy storage field, be specifically related to a kind of water system battery electrolyte and utilize the water system battery of this electrolyte.
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, flow battery etc., all cannot replace lead-acid battery in energy storage field.
There is a kind of novel aqoue seconary battery in recent years.The positive pole of this secondary cell can carry out reversible deviating from-insertion reaction based on the first metal ion, negative pole can carry out reversible reduction deposition-oxidation solubilizing reaction based on the second metal ion, and electrolyte contains and participates in positive pole and deviates from-the first metal ion of insertion reaction and participate in the second metal ion of cathode deposition-solubilizing reaction.The electrolyte of the type battery is the aqueous solution, there is not the potential safety hazard of organic electrolyte in similar lithium ion battery, and environmentally friendly, and cost is lower, and energy density is high.Therefore, the type battery promises to be the energy-storage battery of future generation of alternative lead-acid battery very much, has great using value.
Second metal ion of the type battery can be zinc ion, now negative pole is zinc electrode, but zinc electrode in aqueous discharge and recharge time usually with problems such as electrode deformation, dendrite, burn into liberations of hydrogen, make deterioration of cell properties, as short in cycle life, self discharge is comparatively serious, circulation volume decline is fast, battery lost efficacy very soon in actual use, can not practical requirement, and this is also the major reason that such battery does not obtain extensive use always.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of aqueous electrolyte, zinc electrode can be suppressed to corrode and liberation of hydrogen problem, improve the cycle life of water system battery, improve battery electrical property.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows: a kind of water system battery electrolyte, comprise electrolyte and the aqueous solution, described electrolyte comprises the first metal ion and the second metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described second metal ion is deposited as the second metal at cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion; Described electrolyte also comprises additives polyvinyl alcohol, and described electrolyte is liquid.
Preferably, described polyvinyl alcohol concentration is in the electrolytic solution not more than 0.5g/L.
Preferably, the pH value of described electrolyte is 3-5.
Preferably, described first metal ion is different from described second metal ion.
Preferably, described first metal ion comprises lithium ion, sodium ion or magnesium ion.
Preferably, described second metal ion comprises zinc ion.
Preferably, described electrolyte also comprises sulfate ion, chloride ion, acetate ion, nitrate ion, one or more in formate ion and alkyl sulfonate ion.
Present invention also offers a kind of water system battery, comprise positive pole, negative pole and electrolyte, described electrolyte is above-mentioned electrolyte.
Preferably, described positive pole comprises the positive electrode active material can reversiblely deviating from-embed the first metal ion.
The present invention slows down the burn into dendrite of zinc electrode and the generation of hydrogen by being added with organic compounds polyvinyl alcohol in the electrolytic solution, thus increases the cycle life of battery, improves chemical property and the security performance of battery.
Accompanying drawing explanation
Fig. 1 is the discharge capacity of battery and the graph of relation of cycle-index in embodiment 1 and comparative example 1.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
A kind of water system battery electrolyte, comprise electrolyte and the aqueous solution, described electrolyte comprises the first metal ion and the second metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described second metal ion is deposited as the second metal at cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion; Described electrolyte also comprises additives polyvinyl alcohol, and described electrolyte is liquid.
Electrolyte comprises electrolyte and solvent.Wherein, in electrolyte, 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.In the present invention, solvent is preferably the aqueous solution.
The first metal ion included in electrolyte reversiblely can be deviate from-embeds at positive pole in charge and discharge process.Namely, when battery charges, the first metal ion is deviate from from positive active material, enters electrolyte; When battery discharge, the first metal ion in electrolyte embeds in positive active material.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion.Preferred, the first metal ion is lithium ion.
Preferably, electrolyte also comprises the second metal ion, and the second metal ion is deposited as the second metal at cathodic reduction in charging process, and in discharge process, the second burning is dissolved as the second metal ion.Preferably, the second metal ion is zinc ion.
Preferably, the first metal ion is different from the second metal ion.Under a preferred implementation, electrolyte comprises lithium ion and zinc ion.In charge and discharge process, lithium ion embeds at positive pole-deviates from, and zinc ion deposits at negative pole-dissolves.
Organic additive polyvinyl alcohol is also included in electrolyte.Preferably, after adding additives polyvinyl alcohol, electrolyte is liquid.Polyvinyl alcohol is a kind of high molecular weight water soluble polymer, in battery electrode makes, is commonly used for binding agent, is also usually used in addition preparing polymer dielectric, plays gelatification.In the present invention, a small amount of polyvinyl alcohol is added in liquid electrolyte, when not changing electrolyte form, namely electrolyte still keeps liquid after adding polyvinyl alcohol, polyvinyl alcohol is preferentially adsorbed on the surface of zinc load collector, zinc ion in electrolyte is deposited thereon, can crystal grain thinning, produce uniform zinc sedimentary deposit, improve the deposition morphology of zinc, the growth of dendrite inhibition, also play mechanical isolation effect simultaneously, slow down zinc load corrosion in the electrolytic solution, decrease the generation of hydrogen, thus improve battery cycle life.Preferably, described polyvinyl alcohol concentration is in the electrolytic solution not more than 0.5g/L.
Additive adds the mode in electrolyte, (adds solvent together with electrolyte) when can be electrolyte dissolution; Or before electrolyte dissolution also or after electrolyte dissolution, additive is joined in solvent.
Anion in electrolyte can be anyly substantially do not affect both positive and negative polarity reaction and the anion that dissolves in a solvent of electrolyte.Can be such as sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate anion, formate ion, 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.
In order to make battery performance more optimize, the pH value range of electrolyte is 3 ~ 5.The scope of pH can be adjusted by buffer.The pH of electrolyte is too high, may affect the concentration of zinc ion in electrolyte, and the pH of electrolyte is too low, then can aggravate the corrosion of electrode material.And the pH scope of electrolyte is remained on 3 ~ 5, both effectively can ensure the concentration of metal ion in electrolyte, can also electrode corrosion be avoided.Simultaneously within the scope of the pH of 3 ~ 5, be also applicable to very much the existence of organic additive polyvinyl alcohol.
Present invention also offers a kind of water system battery, comprise positive pole, negative pole and electrolyte, positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Electrolyte is above-mentioned electrolyte.
Positive pole 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, sodium ion or magnesium ion.Preferred, the first metal ion is lithium ion.
Preferably, positive active material has spinel structure, layer structure or olivine structural.
Positive active material can be meet general formula Li
1+xmn
ym
zo
kcan the reversible compound deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn
2o
4.Preferred, positive active material contains the LiMn through overdoping or coating modification
2o
4.
Positive active material can be meet general formula Li
1+xm
ym '
zm "
co
2+ncan the reversible compound deviating from-embed the layer structure of lithium ion, wherein,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material contains LiCoO
2.
Positive active material can also be meet general formula Li
xm
1-ym '
y(XO
4)
ncan the reversible compound deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO
4.
In current battery industry, nearly all positive active material all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn
2o
4can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li
1+xmn
ym
zo
kbe as the criterion, comprise the LiMn through various modification widely
2o
4positive active material.Same, LiFePO
4and LiCoO
2also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively
xm
1-ym '
y(XO
4)
nand Li
1+xm
ym '
zm "
co
2+npositive active material.
Positive active material is, when reversiblely can deviate from-embed the material of lithium ion, preferably can select as LiMn
2o
4, LiFePO
4, LiCoO
2, LiM
xpO
4, LiM
xsiO
ycompounds such as (wherein M are a kind of variable valency metal).
In addition, the compound N aVPO of sodium ion can be deviate from-embed
4f, can deviate from-embed the compound Mg M of magnesium ion
xo
y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive active material of battery of the present invention, therefore, the present invention is not limited to lithium ion battery.
In a particular embodiment, when preparing positive electrode, except positive active material, usually also can add positive conductive agent and positive electrode binder to promote the performance of positive pole.In positive electrode, use the object of conductive agent to be reduce the resistance of overall positive pole, strengthen the conductive path between positive electrode particle simultaneously.Positive conductive agent is selected from one or more in conducting polymer, activated carbon, Graphene, carbon black, graphite, carbon fiber.Binding agent is conducive to positive active material and conductive agent are bonded together uniformly, thus is processed to form positive pole.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.Preferred, positive electrode binder is selected from polytetrafluoroethylene (PTFE), Kynoar (PVDF) or butadiene-styrene rubber (SBR).
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.
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 the conducting film on plus plate current-collecting body.
Conducting film 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 requirement 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.
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.
Reversible reduction deposition-oxidation solubilizing reaction can be there is in the negative pole of battery.During charging, positive active material deviates from the first metal ion, there is the second metal ion in electrolyte, and the second metal ion can be reduced to the second metal in negative side, and is deposited on negative pole.During electric discharge, the second metal be deposited on negative pole is reoxidized into the second metal ion and enters in electrolyte, and the first metal ion embeds in positive active material simultaneously.Preferably, the second metal ion is zinc ion.Now, the negative material of battery, according to the difference of structure and effect, can be divided into again 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 metal of load on negative current collector.
Preferably, negative electrode active material is metallic zinc.
Wherein, negative current collector with reference to the first preferred implementation, can not repeat them here.
Negative electrode active material is with sheet or Powdered existence.
When adopting the negative electrode active material of sheet, sheet metal and negative current collector form composite bed.
When adopting pulverous negative electrode active material, metal dust being made slurry, then slurry is coated on negative current collector and makes negative pole.In concrete execution mode, when preparing negative pole, except negative electrode active material 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 sheet metal as negative pole, sheet metal, both as negative current collector, is also negative electrode active material simultaneously.
In order to provide better security performance, preferably between positive pole and negative pole, be also provided with barrier film 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.
Below by embodiment, the present invention is further described.
Embodiment 1
By by mass ratio 86:7:7, LiMn2O4 LMO, conductive agent acetylene black, binding agent PVDF are mixed in NMP, form uniform anode sizing agent.Be coated in by anode sizing agent on plus plate current-collecting body (PE) and form active material layer, coating layer thickness is 150 μm, is carried out compressing tablet subsequently, and compacting rate is 15%, is cut into the disk that diameter is 12mm size, makes positive plate.Negative pole adopts thickness to be that the zinc metal sheet of 0.2mm is as negative current collector.Barrier film is AGM fibreglass diaphragm.Barrier film is suitable with positive pole with negative pole size.
Take a certain amount of zinc sulfate, lithium sulfate is dissolved in deionized water, then adds PVAC polyvinylalcohol wherein, stir, be configured to that zinc sulfate concentration is 1mol/L, lithium sulfate concentration is 2mol/L, polyvinyl alcohol concentration is the electrolyte of 0.5g/L.
Positive plate, negative plate and membrane layer stacked group are dressed up battery core, loads in housing, then inject electrolyte, sealing, is assembled into battery.
Comparative example 1
Be do not add PVAC polyvinylalcohol in electrolyte with embodiment 1 difference, other parts, with embodiment 1, are assembled into battery.
Electrochemical property test
Carry out chemical property detection to the battery of embodiment 1 and comparative example 1 respectively, carry out constant current cycle discharge and recharge at normal temperatures with 4C multiplying power, voltage range is 1.4-2.1V.Fig. 1 is the discharge capacity of battery and the graph of relation of cycle-index in embodiment 1 and comparative example 1.
The discharge capacity first of the battery as can be seen from the figure in embodiment 1 is slightly lower than the discharge capacity first of the battery in comparative example 1, circulate after about 160 times, battery capacity in embodiment 1 has exceeded the battery capacity in comparative example 1, circulate 300 times, the battery capacity conservation rate in embodiment 1 improves about 9% than the battery capacity conservation rate in comparative example 1.After showing to add PVAC polyvinylalcohol in electrolyte, the capacity attenuation of battery is slack-off, capability retention increase, cycle life be improved significantly.
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 (9)
1. a water system battery electrolyte, comprises electrolyte and the aqueous solution, and described electrolyte comprises the first metal ion and the second metal ion, and described first metal ion reversiblely can be deviate from-embed at positive pole in charge and discharge process; Described second metal ion is deposited as the second metal at cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion; It is characterized in that: described electrolyte also comprises additives polyvinyl alcohol, described electrolyte is liquid.
2. electrolyte according to claim 1, is characterized in that: described polyvinyl alcohol concentration is in the electrolytic solution not more than 0.5g/L.
3. electrolyte according to claim 1, is characterized in that: the pH value range of described electrolyte is 3-5.
4. electrolyte according to claim 1, is characterized in that: described first metal ion is different from described second metal ion.
5. electrolyte according to claim 1, is characterized in that: described first metal ion comprises lithium ion, sodium ion or magnesium ion.
6. electrolyte according to claim 1, is characterized in that: described second metal ion comprises zinc ion.
7. electrolyte according to claim 1, is characterized in that: described electrolyte also comprises sulfate ion, chloride ion, acetate ion, nitrate ion, one or more in formate ion and alkyl sulfonate ion.
8. a water system battery, comprises positive pole, negative pole and electrolyte, it is characterized in that: described electrolyte is the electrolyte described in claim 1-7 any one.
9. battery according to claim 8, is characterized in that: described positive pole comprises the positive electrode active material can reversiblely deviating from-embed the first metal ion.
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| CN105826520A (en) * | 2016-03-28 | 2016-08-03 | 中国科学院青岛生物能源与过程研究所 | Water system high-voltage mixed ion secondary battery based on zinc-lithium ferric manganese phosphate |
| CN107256986A (en) * | 2017-07-27 | 2017-10-17 | 中国科学院宁波材料技术与工程研究所 | A kind of aqueous electrolyte and Water based metal ion battery |
| CN108631007A (en) * | 2017-03-17 | 2018-10-09 | 株式会社东芝 | Secondary cell, battery pack and vehicle |
| CN108832164A (en) * | 2018-05-28 | 2018-11-16 | 华中科技大学 | A kind of lead liquid flow battery electrolyte containing compound additive |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Use of metal dendrite inhibitory additive, electrolyte and battery containing the additive |
| CN111211360A (en) * | 2018-11-22 | 2020-05-29 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof |
| CN111525145A (en) * | 2019-07-26 | 2020-08-11 | 瑞新材料科技(香港)有限公司 | Electrolyte, battery and battery pack |
| CN111653834A (en) * | 2020-06-05 | 2020-09-11 | 恩力能源科技(安徽)有限公司 | Aqueous electrolyte, aqueous metal ion battery, and method for producing same |
| CN114914557A (en) * | 2022-05-20 | 2022-08-16 | 中国科学技术大学 | Water-based lithium ion secondary battery |
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| CN105826520A (en) * | 2016-03-28 | 2016-08-03 | 中国科学院青岛生物能源与过程研究所 | Water system high-voltage mixed ion secondary battery based on zinc-lithium ferric manganese phosphate |
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| CN108832164A (en) * | 2018-05-28 | 2018-11-16 | 华中科技大学 | A kind of lead liquid flow battery electrolyte containing compound additive |
| CN111211360A (en) * | 2018-11-22 | 2020-05-29 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof |
| CN111211360B (en) * | 2018-11-22 | 2021-07-06 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion colloidal electrolyte and preparation method thereof |
| CN111525145A (en) * | 2019-07-26 | 2020-08-11 | 瑞新材料科技(香港)有限公司 | Electrolyte, battery and battery pack |
| CN111525145B (en) * | 2019-07-26 | 2022-05-13 | 眉山茵地乐科技有限公司 | Electrolyte, battery and battery pack |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Use of metal dendrite inhibitory additive, electrolyte and battery containing the additive |
| CN111653834A (en) * | 2020-06-05 | 2020-09-11 | 恩力能源科技(安徽)有限公司 | Aqueous electrolyte, aqueous metal ion battery, and method for producing same |
| WO2023104999A1 (en) * | 2021-12-08 | 2023-06-15 | Atotech Deutschland GmbH & Co. KG | Aqueous stripping composition for electrolytically removing a metal deposit from a substrate |
| CN114914557A (en) * | 2022-05-20 | 2022-08-16 | 中国科学技术大学 | Water-based lithium ion secondary battery |
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