CN106207242A - Aqueous electrolyte and battery - Google Patents
Aqueous electrolyte and battery Download PDFInfo
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- CN106207242A CN106207242A CN201510217568.3A CN201510217568A CN106207242A CN 106207242 A CN106207242 A CN 106207242A CN 201510217568 A CN201510217568 A CN 201510217568A CN 106207242 A CN106207242 A CN 106207242A
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a kind of aqueous electrolyte, described electrolyte includes the first metal ion, and described first metal ion is deposited as the first metal at cathodic reduction in charging process, and described first metal reversible oxidation in discharge process is dissolved as the first metal ion；Described electrolyte also includes the compound of additive cyano-containing.The aqueous electrolyte that the present invention provides can slow down burn into dendrite and the generation of hydrogen of zinc electrode, thus increases the cycle life of battery, improves chemical property and the security performance of battery.The present invention also provides for a kind of water system battery comprising described electrolyte.
Description
Technical field
The invention belongs to electrochemical energy storage field, be specifically related to a kind of aqueous electrolyte and utilization
The water system battery of this electrolyte.
Background technology
Lead-acid battery, it goes out super century-old, has the battery technology of maturation, in occupation of vapour
Car starts the absolute market share in the energy storage fields such as storage battery, electric bicycle, UPS.Plumbic acid electricity
Although pond service life cycle is relatively low, energy density is relatively low, but has price very
Cheap, that cost performance is the highest advantage.Therefore, in the last few years, Ni-MH battery, lithium-ion electric
Pond, sodium-sulphur battery, flow battery etc., all cannot replace lead-acid battery in energy storage field.
A kind of novel aqoue seconary battery occurred in recent years.The negative pole of this secondary cell can base
Carrying out reversible reduction deposition-oxidation in the first metal ion and dissolve reaction, positive pole can be based on
Second metal ion carries out reversible abjection-insertion reaction, electrolyte contain participation cathode deposition-
Dissolve the first metal ion of reaction and participate in the second metal ion of positive pole abjection-insertion reaction.
The electrolyte of the type battery is aqueous solution, there is not organic electrolyte in similar lithium ion battery
Potential safety hazard, and environmentally friendly, cost is relatively low, and energy density is high.Therefore, the type
Battery promises to be the energy-storage battery of future generation substituting lead-acid battery very much, greatly should have
By value.
First metal ion of the type battery can be zinc ion, and now negative pole is zinc electrode,
But during zinc electrode discharge and recharge in aqueous, it is frequently accompanied by electrode deformation, dendrite, burn into analysis
The problems such as hydrogen, make deterioration of cell properties, as short in cycle life, self discharge is more serious, circulation hold
Amount decline is fast, and battery is quickly invalidated in actual use, can not meet actual demand, this
Also it is that such battery does not obtains wide variety of major reason always.
Such as, the type battery be used as ups power time, float life be one critically important
Technical specification.The direct acting factor of float life is floating current: floating current is the biggest, electricity
The side reactions such as the electrode corrosion in pond, liberation of hydrogen are the most serious, cause float life the lowest；Floating current
The least, side reaction is the fewest, and float life is the highest.But, in reality is tested, floating charging
The stream key factor that always restriction the type battery is applied in ups power field.
Summary of the invention
The technical problem to be solved is to provide a kind of aqueous electrolyte, it is possible to suppression is negative
The corrosion of pole and dendrite, thus improve battery performance.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is as follows: a kind of water system
Electrolyte, described electrolyte includes that the first metal ion, described first metal ion were charging
Journey is deposited as the first metal, described first metal reversible oxygen in discharge process at cathodic reduction
Change and be dissolved as the first metal ion；Described electrolyte also includes the compound of cyano-containing.
Preferably, the compound of described cyano-containing is acrylonitrile, and described acrylonitrile is in described electrolysis
Volume fraction in liquid is in the range of 1%-5%.
Preferably, the compound of described cyano-containing is acetonitrile, and described acetonitrile is in described electrolyte
Volume fraction in the range of 4-6%.
Preferably, the compound of described cyano-containing is cyanamide, and described cyanamide is in described electrolyte
Mass fraction in the range of 0.1%-1%.
Preferably, the compound of described cyano-containing is potassium rhodanate, and described potassium rhodanate is described
Mass fraction in electrolyte is in the range of 0.05%-0.1%.
Preferably, described first metal ion include zinc ion, iron ion, manganese ion, chromium from
One in son, copper ion and nickel ion.
Preferably, described electrolyte also includes that the second metal ion, described second metal ion exist
Charge and discharge process reversible can be deviate from-embed at positive pole.
Preferably, described second metal ion includes in lithium ion, sodium ion and magnesium ion
Kind.
Preferably, the pH value range of described electrolyte is 3-7.
Preferably, described electrolyte also include sulfate ion, chloride ion, acetate ion,
One or more in nitrate ion, formate ion and alkyl sulfonate ion.
Another technical problem to be solved by this invention is to provide a kind of water system battery, improves
The performance of battery, so that it is preferably applicable on energy device.
For achieving the above object, the technical solution adopted in the present invention is as follows: a kind of water system battery,
Including positive pole, negative pole and aqueous electrolyte, described electrolyte is above-mentioned electrolyte.
Preferably, described positive pole includes plus plate current-collecting body, positive active material, positive electrode binder
With positive conductive agent, described plus plate current-collecting body is the stainless steel cloth being coated with conducting film, described
Positive electrode binder is the mixture of butadiene-styrene rubber and carboxymethyl cellulose.
Compared with prior art, the invention has the beneficial effects as follows: there is the water system electricity of this electrolyte
Pond negative plate, dendrite and liberation of hydrogen are inhibited, it is thus possible to make floating current decrease, send out
Shoot more preferable battery performance, it is thus possible to better meet the such as electric motor car of high power electronic equipment,
The needs of hybrid electric vehicle development.
Accompanying drawing explanation
Fig. 1 is the battery that provides of embodiment 1-3 and comparative example 1 under 1C multiplying power for the 3rd, 6 times
Specific discharge capacity；
Fig. 2 be the floating charge 1 day under 2.1V of the battery that provides of embodiment 1-3 and comparative example 1,2
My god, the floating current density of 3 days；
Fig. 3 is the battery that provides of embodiment 4-6 and comparative example 2 under 1C multiplying power for the 3rd, 6 times
Specific discharge capacity；
Fig. 4 is the battery that provides of embodiment 4-6 and comparative example 2 under 1C multiplying power the 3rd time
Difference between capability retention and the capability retention of the 6th time；
Fig. 5 is battery floating charge 1 day under 2.1V that embodiment 4-6 and comparative example 2 provide
Floating current density；
Fig. 6 is the battery that provides of embodiment 7 and comparative example 3 floating charge 1 day floating under 2.1V
Charging current density；
Battery floating charge 3 days under 2.1V that Fig. 7 provides for embodiment 10-13 and comparative example 2
Floating current density；
Fig. 8 is that the battery that provides of embodiment 10-13 and comparative example 2 is under 1C multiplying power the 3rd, 6
Secondary specific discharge capacity；
Fig. 9 is the battery that provides of embodiment 10-13 and comparative example 2 under 1C multiplying power the 3rd time
Capability retention and the capability retention of the 6th time between difference；
Battery floating charge 1 day under 2.1V that Figure 10 provides for embodiment 14-15 and comparative example 2
Floating current density；
Figure 11 is that the battery that provides of embodiment 14-15 and comparative example 2 is under 1C multiplying power the 3rd, 6
Secondary specific discharge capacity；
Figure 12 is the battery that provides of embodiment 14-15 and comparative example 2 under 1C multiplying power the 3rd time
Capability retention and the capability retention of the 6th time between difference；
Battery floating charge analysis of 1 day under 2.1V that Figure 13 provides for embodiment 7 and comparative example 3
Tolerance.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer
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, is not intended to limit the present invention.
A kind of aqueous electrolyte, including the first metal ion.This first metal ion was charging
Being deposited as the first metal at cathodic reduction in journey, in discharge process, reversible oxidation is dissolved as first
Metal ion.Electrolyte also includes the compound of additive cyano-containing.
Electrolyte includes electrolyte and solvent.Wherein, in electrolyte, the purpose of solvent is to dissolve
Electrolyte, and make electrolyte ionize in a solvent, generate the most in the electrolytic solution and can move freely
Cation and anion.In the present invention, solvent is preferably aqueous solution.
The first metal ion in electrolyte, can reduce at negative pole in charging process and be deposited as
First metal, in discharge process, the first metal reversible oxidation is dissolved as the first metal ion.I.e.
When battery charges, the first reducing metal ions in electrolyte becomes the first metal, is deposited on negative
Extremely go up；When battery discharge, the first metal is oxidized into the first metal ion and again from negative
Extremely go up dissolution, enter electrolyte.Preferably, the first metal ion include zinc ion, iron ion,
One in manganese ion, chromium ion, copper ion or nickel ion.It is furthermore preferred that the first metal from
Son is zinc ion.
In a preferred embodiment, can at positive pole during electrolyte is additionally included in charge and discharge process
Second metal ion of reversible abjection-embedding.I.e. when battery charges, the second metal ion from
Positive active material is deviate from, enters electrolyte；When battery discharge, second in electrolyte
Metal ion embeds in positive active material.Preferably, the second metal ion selected from lithium ion,
Sodium ion or magnesium ion.It is furthermore preferred that the second metal ion is lithium ion.
In a preferred embodiment, electrolyte includes lithium ion and zinc ion.In discharge and recharge
During, lithium ion embeds at positive pole-deviates from, and zinc ion deposits at negative pole-dissolves.
In a preferred embodiment, electrolyte also including, one aoxidizes at anode
The ion of reduction reaction.When battery charges, this ion in electrolyte is oxidized；Battery is put
During electricity, active substance oxidized during charging is reduced again.Preferably, this ion selected from bromine from
At least one in son, vanadium ion.
In a preferred embodiment, electrolyte includes bromide ion and zinc ion.In discharge and recharge
During, bromide ion at positive pole generation oxidation-reduction reaction, zinc ion negative pole deposit-
Dissolve.
Electrolyte also includes the compound of additive cyano-containing.The compound of cyano-containing is also referred to as
Cyanide.In charging process, the compound of cyano-containing can be preferentially adsorbed on negative terminal surface, makes
The first metal ion in electrolyte is at cathode deposition, thus improves the deposition morphology of negative pole, presses down
The corrosion of negative pole processed and dendrite, improve the performance of battery.
In a preferred embodiment, the compound of cyano-containing is acrylonitrile, and the first metal is zinc.
Acrylonitrile is a kind of organic compound, and its molecular weight is 53, is a kind of colourless liquid being slightly soluble in water
Body.In battery makes, generally with its polymer (polyacrylonitrile) as one binding agent or
Prepare the gel of polymer dielectric.In a cell of this invention, at water system liquid electrolyte
The acrylonitrile that middle addition is appropriate, acrylonitrile molecule can be preferentially adsorbed on the surface of zinc load, make electricity
The zinc ion solved in liquid deposits thereon, improves the deposition morphology of zinc, the growth of dendrite inhibition,
Slow down zinc load corrosion in the electrolytic solution, thus improve the performance of battery, as floating in reduced
Charging stream, improves battery capacity and cycle life.Preferably, described acrylonitrile is at electrolyte
In volume fraction in the range of 1%-5%.
In a preferred embodiment, the compound of cyano-containing is acetonitrile.Acetonitrile is a kind of organic
Compound, its molecular weight is 41.05.Preferably, described acetonitrile in the electrolytic solution volume
Mark is in the range of 1%-5%.
In a preferred embodiment, the compound of cyano-containing is cyanamide.Cyanamide is a kind of organic
Compound, its molecular weight is 42.04, is a kind of solid soluble in water under room temperature.Preferably,
Described cyanamide in the electrolytic solution mass fraction in the range of 0.1%-1%.
In a preferred embodiment, the compound of cyano-containing is inorganic sulfur cyanide.Compared to
General cyanide, rhodanide has higher complexing power and has relatively low toxicity, more
Meet present environmental requirement.
In a preferred embodiment, the compound of cyano-containing is potassium rhodanate.Potassium rhodanate is one
Planting inorganic compound, its molecular weight is 97.18, is a kind of solid soluble in water under room temperature.
In the present invention, water system liquid electrolyte adds appropriate potassium rhodanate.Preferably, described
Potassium rhodanate in the electrolytic solution volume fraction in the range of 0.05%-0.1%.
The mode that additive adds in electrolyte does not limits, and can be to add solvent together with electrolyte；
It can be addition solvent before electrolyte；It can also be addition solvent after electrolyte.
Anion in electrolyte, can be any have substantially no effect on both positive and negative polarity reaction, Yi Ji electricity
Solve the anion that matter is dissolved in a solvent.Can be such as sulfate ion, chloride ion, acetic acid
Radical ion, nitrate ion, phosphate anion, formate ion, alkyl sulfonate ion and
Its mixing etc..
The concentration of each ion in electrolyte, can be according to different electrolyte, solvent and battery
The different situations such as application and be changed allotment.
Preferably, in the electrolytic solution, the concentration of the first metal ion is 0.1～10mol/L.
Preferably, in the electrolytic solution, the concentration of the second metal ion is 0.5～15mol/L.
Preferably, in the electrolytic solution, the concentration of anion is 0.5～12mol/L.
In order to make battery performance more optimize, the pH value range of electrolyte is 3～7.The model of pH
Enclose and can be adjusted by buffer agent.The pH of electrolyte is too high, may affect in electrolyte
The concentration of zinc ion, the pH of electrolyte is too low, then can aggravate the corrosion of electrode material.And incite somebody to action
The pH scope of electrolyte is maintained at 3～7, and in electrolyte metal ion both can be effectively ensured
Concentration, it is also possible to avoid electrode corrosion.
Present invention also offers a kind of water system battery, including positive pole, negative pole and aqueous electrolyte,
Wherein electrolyte is above-mentioned electrolyte.Under the preferred embodiment for the present invention, described first gold medal
Belonging to ion can occur reversible reduction deposition-oxidation to dissolve reaction on negative pole；Described positive pole
Including the positive active material that reversible can deviate from-embed the second metal ion；Described electrolyte
Including the first metal ion and the second metal ion, in charge and discharge process, described first metal from
Son can reduce at negative pole and be deposited as the first metal and the first metal energy reversible oxidation is dissolved as the
One metal ion, described second metal ion can be in the reversible abjection-embedding of positive pole.
The charge-discharge principle of battery is: during charging, and positive active material deviates from the second metal ion,
Simultaneously oxidized with positive active material, and ejected electron；Electronics arrives electricity via external circuit
Pond negative pole, the first metal ion in electrolyte obtains electronics on negative pole and is reduced simultaneously, and
It is deposited on negative pole.During electric discharge, the first metal being deposited on negative pole is oxidized, loses electronics
It is changed into the first metal ion to enter in electrolyte；Electronics arrives positive pole through external circuit, and positive pole is lived
Property material accept electronics and be reduced, during the second metal ion embeds positive active material simultaneously.
The negative pole of battery can occur reversible reduction deposition-oxidation to dissolve reaction.During charging,
The first metal ion in electrolyte can be reduced to the first metal in negative side, and is deposited on
On negative pole, during electric discharge, the first metal being deposited on negative pole be reoxidized into the first metal from
Son enters in electrolyte.Preferably, the first metal ion is zinc ion.Now, battery is negative
Pole material, again can be to be divided into following three kinds of different forms according to structure and the difference of effect:
In the first preferred embodiment, negative pole only includes negative current collector, and negative pole currect collecting
Body is only used as electronics conduction and the carrier collected, and is not involved 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 substrate
Material；Wherein, carbon-based material includes graphite material, the paper tinsel of the most business-like graphite compacting, its
Part by weight scope shared by middle graphite is 90～100%.The material of negative current collector can also select
From rustless steel or the rustless steel of passivated process.Rustless steel include but are not limited to stainless (steel) wire and
Stainless steel foil, same, stainless model can be the rustless steel of 300 series, as stainless
Steel 304 or Stainless steel 316 or Stainless steel 316 L.It addition, negative current collector can also select
From the metal of the plating/coating high containing hydrogen-evolution overpotential, thus reduce the generation of negative pole side reaction.Plating
/ coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, alloy, or oxide
In at least one.The thickness range of plating/coating is 1～1000nm.Such as: at Copper Foil or graphite
Stannum on the negative current collector plated surface of paper tinsel, lead or silver.
In the second preferred implementation, negative pole, except negative current collector, also includes being supported on negative
Negative electrode active material metal on the collector of pole.
Preferably, negative electrode active material is metallic zinc.
Wherein, negative current collector is referred to the first preferred implementation, does not repeats them here.
Negative electrode active material exists with lamellar or powder.
When using the negative electrode active material of lamellar, sheet metal forms composite bed with negative current collector.
When using the negative electrode active material of powder, metal dust is made slurry, then will
Slurry is coated on negative current collector makes negative pole.In specific embodiment, when preparing negative pole,
In addition to negative electrode active material metal dust, according to practical situation, add negative always according to needs
Pole conductive agent and negative electrode binder promote the performance of negative pole.
In the 3rd preferred implementation, sheet metal is directly used both to make as negative pole, sheet metal
For negative current collector, also it is negative electrode active material simultaneously.
In a preferred embodiment, positive pole include reversible can deviating from-embed the second metal from
The positive active material of son, it is preferred that the second metal ion is selected from lithium ion, sodium ion or magnesium
Ion.It is furthermore preferred that the second metal ion is lithium ion.
Preferably, positive active material has spinel structure, layer structure or olivine structural.
Positive active material can be to meet formula Li1+xMnyMzOkCan reversible deviate from-embedding
Enter the compound of the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z
≤ 0.5,3≤k≤6, M selected from Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si,
At least one in Al.Preferably, positive active material contains LiMn2O4.It is furthermore preferred that
Positive active material contains the LiMn through overdoping or coating modification2O4。
Positive active material can be to meet formula Li1+xMyM′zM″cO2+nCan reversible take off
Go out-embed the compound of 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 " be respectively selected from Ni, Mn, Co, Mg,
In Ti, Cr, V, Zn, Zr, Si or Al at least one.Preferably, positive active material
Containing LiCoO2。
Positive active material can also is that and meets formula LixM1-yM′y(XO4)nCan reversible take off
Go out-embed the compound of 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, and M ' is selected from Mg, Ti, Cr, V or Al
In at least one, at least one in S, P or Si of X.Preferably, positive electrode active material
Matter contains LiFePO4。
In current battery industry, nearly all positive active material all can be through overdoping, cladding etc.
Modification.But doping, the means such as coating modification cause the chemical general formula of material to express complexity,
Such as LiMn2O4Can not represent the formula of now widely used " LiMn2O4 ", and should
With formula Li1+xMnyMzOkIt is as the criterion, includes the LiMn through various modifications widely2O4Just
Pole active substance.Same, LiFePO4And LiCoO2Also should be construed broadly to include
Through modifications such as various doping, claddings, formula corresponds with LixM1-yM′y(XO4)nWith
Li1+xMyM′zM″cO2+nPositive active material.
When positive active material is the material of energy reversible abjection-embedding lithium ion, preferably can select
With such as LiMn2O4、LiFePO4、LiCoO2、LiMxPO4、LiMxSiOy(wherein M is one
Kind of variable valency metal) etc. compound.
Additionally, the compound N aVPO of sodium ion can be deviate from-embed4F, can deviate from-embed magnesium from
The compound Mg M of sonxOy(wherein M is a kind of metal, 0.5 < x < 3,2 < y < 6) and tool
There is similar functions, it is possible to the compound of abjection-embedded ion or functional group can serve as this
The positive active material of bright battery, therefore, the invention is not limited in lithium ion battery.
In a particular embodiment, when preparing positive electrode, in addition to positive active material,
Generally also can add positive conductive agent and positive electrode binder to promote the performance of positive pole.At positive pole material
The purpose using conductive agent in material is to reduce the resistance of overall positive pole, strengthens positive electrode simultaneously
Conductive path between Li.Positive conductive agent selected from conducting polymer, activated carbon, Graphene,
One or more in carbon black, graphite, carbon fiber.Binding agent is conducive to making positive active material
It is bonded together uniformly with conductive agent, thus is processed to form positive pole.Positive electrode binder can select
From polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers,
Fluorinated polymer, poly-divinyl Polyethylene Glycol, polyethyleneglycol diacrylate, Polyethylene Glycol
Dimethacrylate, butadiene-styrene rubber (SBR), sodium carboxymethyl cellulose (CMC), polytetrafluoro
One in ethylene (PTFE), Kynoar (PVDF) and the derivant of above-claimed cpd or
Person is multiple.It is furthermore preferred that positive electrode binder is selected from butadiene-styrene rubber, sodium carboxymethyl cellulose, gathers
One or more in tetrafluoroethene, Kynoar.
Concrete, positive pole also includes the plus plate current-collecting body loading positive active material, anode collection
Body is only used as electronics conduction and the carrier collected, and is not involved in electrochemical reaction, i.e. battery operated
In voltage range, the most there is not pair in being present in electrolyte that plus plate current-collecting body can be stable
Reaction, thus ensure that battery has stable cycle performance.
The material of plus plate current-collecting body one in carbon-based material, metal or alloy.
Carbon-based material selected from vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth,
One in carbon fiber.
Metal includes Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or through blunt
One in the above-mentioned metal that change processes.
Alloy include rustless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy,
Co alloy, Ti-Pt alloy, Pt-Rh alloy or in the above-mentioned metal of Passivation Treatment one
Kind.
Rustless steel includes that stainless (steel) wire, stainless steel foil, stainless model include but are not limited to
One in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.Preferably, just
Pole collector selects the rustless steel being coated with conducting film.
In a preferred embodiment, the present invention proposes a kind of water system battery, including positive pole, bears
Pole and aqueous electrolyte, wherein electrolyte is above-mentioned electrolyte.Positive pole include plus plate current-collecting body,
Positive electrode active materials, positive electrode binder, positive conductive agent.Positive electrode binder is selected from butadiene-styrene rubber
With the mixture of sodium carboxymethyl cellulose (CMC), plus plate current-collecting body selects graphite foil.Have
The water system battery of above-mentioned positive electrode binder and plus plate current-collecting body shows higher specific capacity, slower
Capacity attenuation and less floating current.
More preferably, positive pole also includes the composite current collector loading positive active material, compound
Collector is the plus plate current-collecting body being coated with conducting film.
Conducting film meets in aqueous electrolyte can be with stable existence, insoluble in electrolyte, do not send out
Raw swelling, high voltage can not oxidized, be easily processed into densification, waterproof and wanting of conducting electricity
Ask.On the one hand, plus plate current-collecting body can be played a protective role by conducting film, it is to avoid water system is electrolysed
The liquid corrosion to plus plate current-collecting body.On the other hand, positive plate and plus plate current-collecting body are advantageously reduced
Between contact internal resistance, improve battery energy.
Preferably, the thickness of conducting film is 10 μm～2mm.
Plus plate current-collecting body has first and second being oppositely arranged, it is preferred that anode collection
First of body and second is all coated with conducting film.
Conducting film comprises the polymer as necessary component, and polymer accounts for the weight proportion of conducting film
It is 50～95%, it is preferred that polymer is selected from thermoplastic polymer.In order to enable conducting film
Conduction, has two kinds of feasible forms: (1) polymer is conducting polymer；(2) except polymer
Outside, conducting film also comprises conductive filler.
Conducting polymer choice requirement, i.e. will not conduct for having conductive capability but electrochemicaUy inert
The ionic conduction of charge transfer medium.Concrete, conducting polymer includes but are not limited to poly-second
Alkynes, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, poly-right
Penylene (polyparaphenylene) and any mixture thereof.Conducting polymer inherently has leads
Electrically, it is also possible to conducting polymer is doped or modification is to improve further its conduction energy
Power.Stable use from electric conductivity and battery is considered, the preferred polyaniline of conducting polymer,
Polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler is that surface area is little, be difficult to aoxidize, degree of crystallinity is high,
There is electric conductivity but electrochemicaUy inert, i.e. will not be as the ionic conduction of charge transfer medium.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxygen
Compound.Conductive filler mass percent scope in the conductive film is 5～50%.Conductive filler
Mean diameter 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 and plays knot
Closing the non-conductive polymer of conductive filler effect, non-conductive polymer enhances the knot of conductive filler
Close, improve the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.
Concrete, thermoplastic polymer includes but are not limited to polyolefin such as polyethylene, polypropylene,
Polybutene, polrvinyl chloride, polystyrene, polyamide, Merlon, poly-methyl methacrylate
Ester, polyformaldehyde, polyphenylene oxide, polysulfones, in polyether sulfone, butadiene-styrene rubber or Kynoar
Plant or multiple.Wherein, preferably polyolefin, polyamide and Kynoar.These polymer
Melt easily by heat, be therefore easily combined with each other with plus plate current-collecting body.Additionally, these
Polymer has big potential window, so that positive stabilizer pole for battery output density saving weight.
Preferably, conducting film is compound by hot pressing, be attached to anode collection by the way of evacuation or spraying
On body.
In a more preferred embodiment, the present invention proposes a kind of water system battery, including positive pole,
Negative pole and aqueous electrolyte, wherein electrolyte is above-mentioned electrolyte.Positive pole includes anode collection
Body, positive electrode active materials, positive electrode binder, positive conductive agent.Positive electrode binder is selected from butylbenzene
Rubber and the mixture of sodium carboxymethyl cellulose (CMC), plus plate current-collecting body is selected to be coated with and is led
The stainless steel cloth of electrolemma.There is the water system battery exhibition of above-mentioned positive electrode binder and plus plate current-collecting body
Less floating current is shown.
In order to provide more preferable security performance, the most in the electrolytic solution between positive pole and negative pole
It is additionally provided with barrier film.The both positive and negative polarity that barrier film can avoid other unexpected factors to cause is connected and causes
Short circuit.
Barrier film does not has particular/special requirement, as long as permission electrolyte passes through and the barrier film of electronic isolation is
Can.The various barrier films that organic system lithium ion battery uses, all go for the present invention.Barrier film
Can also is that the other materials such as micropore ceramics dividing plate.
Below by embodiment, the present invention is further described.
Embodiment 1
Press LiMn2O4 LMO, graphite agent KS-6, binding agent PVDF mass ratio 86:7:7
NMP mixes, forms uniform anode sizing agent.Anode sizing agent is coated in anode collection
Form active material layer in body graphite foil, carried out tabletting subsequently, be cut into a diameter of 12mm
The disk of size, makes positive plate, and the load capacity of positive plate is 5mg.Negative pole employing thickness is
The zinc metal sheet of 0.2mm is as negative current collector.Barrier film is AGM fibreglass diaphragm.Barrier film and
Negative pole size is suitable with positive pole.
Weigh a certain amount of zinc sulfate, lithium sulfate is dissolved in deionized water, then is added thereto to third
Alkene nitrile, stirring, be configured to zinc sulfate concentration be 2mol/L, lithium sulfate concentration be 1mol/L,
Acrylonitrile (AN) volume fraction in the electrolytic solution is 1%.
Positive plate, negative plate and membrane layer stacked group are dressed up battery core, loads in housing, then
Inject electrolyte, sealing, be assembled into battery.
Embodiment 2
With embodiment 1 except that, acrylonitrile (AN) volume fraction in the electrolytic solution is
3%, other parts, with embodiment 1, are assembled into battery.
Embodiment 3
With embodiment 1 except that, acrylonitrile (AN) volume fraction in the electrolytic solution is
5%, other parts, with embodiment 1, are assembled into battery.
Embodiment 4
With embodiment 1 except that, binding agent used by positive pole is styrene butadiene rubber sbr and carboxymethyl
The mixture of cellulose CMC, wherein the mass ratio of SBR Yu CMC is 1, and other parts are with real
Execute example 1, be assembled into battery.
Embodiment 5
With embodiment 4 except that, acrylonitrile (AN) volume fraction in the electrolytic solution is
3%, other parts, with embodiment 4, are assembled into battery.
Embodiment 6
With embodiment 4 except that, acrylonitrile (AN) volume fraction in the electrolytic solution is
5%, other parts, with embodiment 4, are assembled into battery.
Embodiment 7
With embodiment 5 except that, the load capacity of positive plate is 500mg, and other parts are with real
Execute example 5, be assembled into battery.
Embodiment 8
With embodiment 6 except that, plus plate current-collecting body is the stainless steel silk being coated with conducting film
Net, other parts, with embodiment 6, are assembled into battery.
Embodiment 9
With embodiment 8 except that, electrolysis additive is acetonitrile, and acetonitrile is in the electrolytic solution
Volume fraction be 5%, other parts, with embodiment 1, are assembled into battery.
Embodiment 10
With embodiment 4 except that, electrolysis additive is cyanamide, and cyanamide is in the electrolytic solution
Mass fraction be 0.1%, other parts, with embodiment 1, are assembled into battery.
Embodiment 11
With embodiment 4 except that, electrolysis additive is cyanamide, and cyanamide is in the electrolytic solution
Mass fraction be 0.2%, other parts, with embodiment 1, are assembled into battery.
Embodiment 12
With embodiment 4 except that, electrolysis additive is cyanamide, and cyanamide is in the electrolytic solution
Mass fraction be 0.5%, other parts, with embodiment 1, are assembled into battery.
Embodiment 13
With embodiment 4 except that, electrolysis additive is cyanamide, and cyanamide is in the electrolytic solution
Mass fraction be 1.0%, other parts, with embodiment 1, are assembled into battery.
Embodiment 14
With embodiment 4 except that, electrolysis additive is potassium rhodanate, and potassium rhodanate exists
Mass fraction in electrolyte is 0.05%, and other parts, with embodiment 1, are assembled into battery.
Embodiment 15
With embodiment 4 except that, electrolysis additive is potassium rhodanate, and potassium rhodanate exists
Mass fraction in electrolyte is 0.1%, and other parts, with embodiment 1, are assembled into battery.
Comparative example 1
With embodiment 1 except that, electrolyte does not add acrylonitrile, other parts with
Embodiment 1, is assembled into battery.
Comparative example 2
With embodiment 4 except that, electrolyte does not add acrylonitrile, other parts with
Embodiment 4, is assembled into battery.
Comparative example 3
With embodiment 7 except that, electrolyte does not add acrylonitrile, other parts with
Embodiment 7, is assembled into battery.
Comparative example 4
With embodiment 8 except that, electrolyte does not add acrylonitrile, other parts with
Embodiment 8, is assembled into battery.
Electrochemical property test
Respectively the battery of embodiment 1-6, embodiment 8-15 and comparative example 1,2,4 is carried out electricity
Chemical property detects, and at room temperature carries out constant current cycle discharge and recharge 3 times with 1C multiplying power, voltage
Scope is 1.4-2.1V, then by battery floating charge 3 days under 2.1V, then by battery at 1C times
Cycle charge-discharge 3 times under rate.
Respectively the battery of embodiment 7 and comparative example 3 is carried out chemical property detection, in room temperature
Under with 0.2C (10mA) circulation discharge and recharge 1 time, voltage range is 1.4-2.1V, so
After by battery floating charge 1 day under 2.1V, then battery is discharged to 1.4V under 0.2C multiplying power.
Fig. 1 is the battery that provides of embodiment 1-3 and comparative example 1 under 1C multiplying power for the 3rd, 6 times
Specific discharge capacity.It can be seen that after electrolyte adds acrylonitrile, the electric discharge specific volume of battery
Amount significantly improves.
Fig. 2 be the floating charge 1 day under 2.1V of the battery that provides of embodiment 1-3 and comparative example 1,2
My god, the floating current density of 3 days.As seen from the figure, along with the increase of acrylonitrile addition, electricity
The floating current in pond significantly reduces, and floating current is the least, illustrates that the side reaction that battery occurs is the fewest,
Performance is the best, illustrates that additive acrylonitrile can reduce the side reaction of battery, improves the floating charge of battery
Performance.
Fig. 3 is the battery that provides of embodiment 4-6 and comparative example 2 under 1C multiplying power for the 3rd, 6 times
Specific discharge capacity.From figure it can also be seen that, electrolyte adds after acrylonitrile, the electric discharge of battery
Specific capacity is improved.
Fig. 4 is the battery that provides of embodiment 4-6 and comparative example 2 under 1C multiplying power the 3rd time
Difference between capability retention and the capability retention of the 6th time.In cyclic process, although
Along with cycle-index increases, the capability retention of each battery is reducing, but its amplitude reduced
Can as seen in Figure 4, capability retention and the capacity of the 6th time that battery is the 3rd time keep it
Between difference be not added with the little of acrylonitrile adding after acrylonitrile the most substantially ratio, illustrate that battery is adding
Add the slack-off cycle performance of the capacity attenuation after acrylonitrile to improve.
Fig. 5 is battery floating charge 1 day under 2.1V that embodiment 4-6 and comparative example 2 provide
Floating current density, the battery that Fig. 6 provides for embodiment 7 and comparative example 3 is floated downward at 2.1V
Fill the floating current density of 1 day, all can learn from Fig. 5 and 6, use CMC/SBR bonding instead
Agent, acrylonitrile additive remains to reduce floating current.
Contrasted it is known that use by the floating current density of embodiment 4-6 with embodiment 1-3
The battery of SBR/CMC binding agent uses the battery of PVDF binding agent to show lower floating charge
Electric current density.
Battery floating charge 3 days under 2.1V that embodiment 8 and comparative example 4 are provided, test electricity
The floating current density in pond.Test result is: the battery float electric current density of embodiment 8 is
0.289 ± 0.141mA/g, the battery float electric current density of comparative example 4 is 0.656 ± 0.291mA/g.
Illustrating further above, acrylonitrile additive can reduce floating current.
Contrasted by embodiment 8 and embodiment 6 and learn, use the stainless steel cloth of conducting film cladding
As plus plate current-collecting body than using graphite foil to demonstrate lower floating charging as plus plate current-collecting body
Current density.
Battery floating charge 3 days under 2.1V that embodiment 9 and comparative example 4 are provided, test electricity
The floating current density in pond.Test result is: the battery float electric current density of embodiment 9 is
0.336 ± 0.175mA/g, the battery float electric current density of comparative example 4 is 0.656 ± 0.291mA/g.
Described above, acetonitrile additive can reduce floating current.
Battery floating charge 3 days under 2.1V that Fig. 7 provides for embodiment 10-13 and comparative example 2
Floating current density with the variation relation figure of cyanamide addition.From Fig. 7 it is known that be electrolysed
Liquid adds cyanamide the floating current of battery can be greatly reduced.
Fig. 8 is that the battery that provides of embodiment 10-13 and comparative example 2 is under 1C multiplying power the 3rd, 6
Secondary specific discharge capacity is with the variation relation figure of cyanamide addition.From Fig. 8 it is known that be electrolysed
Adding cyanamide in liquid and affect little on the discharge capacity of battery, battery can keep original appearance substantially
Amount is discharged.Wherein, the discharge capacity of the battery of embodiment 10-12 is more than comparative example 2
Discharge capacity.
Fig. 9 is the battery that provides of embodiment 10-13 and comparative example 2 under 1C multiplying power the 3rd time
Capability retention and the capability retention of the 6th time between difference (i.e. capacity in the present invention
Loss rate) with the variation relation figure of cyanamide addition.From Fig. 9 it is known that electrolyte adds
Adding cyanamide and affect the capacitance loss under the different cycle-indexes of battery little, battery is the most permissible
Original capacitance loss rate is kept to discharge.
Battery floating charge 1 day under 2.1V that Figure 10 provides for embodiment 14-15 and comparative example 2
Floating current density with the variation relation figure of potassium rhodanate addition.From Fig. 8 it is known that
Electrolyte adds potassium rhodanate and can reduce the floating current of battery.
Figure 11 is that the battery that provides of embodiment 14-15 and comparative example 2 is under 1C multiplying power the 3rd, 6
Secondary specific discharge capacity is with the variation relation figure of potassium rhodanate addition.From Figure 11 it is known that
Adding potassium rhodanate in electrolyte, the discharge capacity of battery increased.
Figure 12 is the battery that provides of embodiment 14-15 and comparative example 2 under 1C multiplying power the 3rd time
Capability retention and the capability retention of the 6th time between difference (i.e. capacity in the present invention
Loss rate) with the variation relation figure of potassium rhodanate addition.From Figure 12 it is known that be electrolysed
Adding potassium rhodanate in liquid, battery can keep original capacitance loss rate to discharge substantially.
Wherein, when adding the potassium rhodanate of 0.1%wt in electrolyte, the capacitance loss rate of battery is relatively low.
Gassing is tested
Battery floating charge 1 day under room temperature 2.1V embodiment 7 and comparative example 3 provided, tests it
Total gassing rate.
Battery floating charge analysis of 1 day under 2.1V that Figure 13 provides for embodiment 7 and comparative example 3
Tolerance.As seen from the figure, after adding acrylonitrile, gas production can reduce more than 50%.
To sum up showing, the compound of additive cyano-containing passes through adsorption mechanism, it is possible to substantially suppress
The aerogenesis of zinc load and corrosion, improve specific capacity and the cycle performance of battery, reduces battery float
Electric current, reduces side reaction, improves battery combination property.
Although technical scheme has been done elaboration in greater detail and has enumerated by inventor,
Should be appreciated that to those skilled in the art, above-described embodiment is modified and/or becomes
Logical or employing equivalent replacement scheme is obvious, all can not depart from the essence of spirit of the present invention,
The term occurred in the present invention is used for the elaboration to technical solution of the present invention and understanding, can not structure
Become limitation of the present invention.
Claims (12)
1. an aqueous electrolyte, described electrolyte includes the first metal ion, described first metal
Ion is deposited as the first metal at cathodic reduction in charging process, and described first metal exists
In discharge process, reversible oxidation is dissolved as the first metal ion；It is characterized in that, described electricity
Solve liquid and also include the compound of cyano-containing.
Electrolyte the most according to claim 1, it is characterised in that: the chemical combination of described cyano-containing
Thing is acrylonitrile, and described acrylonitrile volume fraction in described electrolyte is at 1%-5%
In the range of.
Electrolyte the most according to claim 1, it is characterised in that: the chemical combination of described cyano-containing
Thing is acetonitrile, and described acetonitrile volume fraction in described electrolyte is in the range of 4-6%.
Electrolyte the most according to claim 1, it is characterised in that: the chemical combination of described cyano-containing
Thing is cyanamide, and described cyanamide mass fraction in described electrolyte is in 0.1%-1% scope
In.
Electrolyte the most according to claim 1, it is characterised in that: the chemical combination of described cyano-containing
Thing is potassium rhodanate, and described potassium rhodanate mass fraction in described electrolyte exists
In the range of 0.05%-0.1%.
Electrolyte the most according to claim 1, it is characterised in that: described first metal ion
Including in zinc ion, iron ion, manganese ion, chromium ion, copper ion and nickel ion
Kind.
Electrolyte the most according to claim 1, it is characterised in that: described electrolyte also includes
Second metal ion, described second metal ion can at positive pole in charge and discharge process
Inverse abjection-embed.
Electrolyte the most according to claim 1, it is characterised in that: described second metal ion
Including the one in lithium ion, sodium ion and magnesium ion.
Electrolyte the most according to claim 1, it is characterised in that: the pH of described electrolyte
Value scope is 3-7.
Electrolyte the most according to claim 1, it is characterised in that: described electrolyte also includes
Sulfate ion, chloride ion, acetate ion, nitrate ion, formate ion and
One or more in alkyl sulfonate ion.
11. 1 kinds of batteries, including positive pole, negative pole and aqueous electrolyte, it is characterised in that: described electricity
Solving liquid is the electrolyte described in claim 1-10 any one.
12. batteries according to claim 11, it is characterised in that: described positive pole includes positive pole
Collector, positive active material, positive electrode binder and positive conductive agent, described positive pole collection
Fluid is the stainless steel cloth being coated with conducting film, and described positive electrode binder is butadiene-styrene rubber
Mixture with carboxymethyl cellulose.
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| CN2014106633807 | 2014-11-19 | ||
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| CN107069116A (en) * | 2017-03-01 | 2017-08-18 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of the zinc-nickel secondary batteries of high power density |
| CN108428926A (en) * | 2018-03-01 | 2018-08-21 | 复旦大学 | Positive and negative polarities are copper-manganese aqoue seconary battery of deposition/dissolving reaction |
| CN108448168A (en) * | 2018-03-14 | 2018-08-24 | 华中科技大学 | A kind of electrolyte and its preparation method and application for water system zinc ion secondary cell |
| CN108598572A (en) * | 2018-05-31 | 2018-09-28 | 佛山市高明区爪和新材料科技有限公司 | A kind of preparation method of resistance to pyrolysis-type lithium battery electrolytes material |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN113299987A (en) * | 2021-05-25 | 2021-08-24 | 哈尔滨工业大学 | Preparation method of solid polymer electrolyte of zinc ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107069116A (en) * | 2017-03-01 | 2017-08-18 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of the zinc-nickel secondary batteries of high power density |
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| CN108428926B (en) * | 2018-03-01 | 2020-10-30 | 复旦大学 | Copper-manganese water system secondary battery with positive and negative poles both undergoing deposition/dissolution reaction |
| CN108448168A (en) * | 2018-03-14 | 2018-08-24 | 华中科技大学 | A kind of electrolyte and its preparation method and application for water system zinc ion secondary cell |
| CN108598572A (en) * | 2018-05-31 | 2018-09-28 | 佛山市高明区爪和新材料科技有限公司 | A kind of preparation method of resistance to pyrolysis-type lithium battery electrolytes material |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN113299987A (en) * | 2021-05-25 | 2021-08-24 | 哈尔滨工业大学 | Preparation method of solid polymer electrolyte of zinc ion battery |
| CN113299987B (en) * | 2021-05-25 | 2022-07-05 | 哈尔滨工业大学 | Preparation method of solid polymer electrolyte of zinc ion battery |
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