CN106450511A - Electrolyte and battery - Google Patents
Electrolyte and battery Download PDFInfo
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- CN106450511A CN106450511A CN201510489366.4A CN201510489366A CN106450511A CN 106450511 A CN106450511 A CN 106450511A CN 201510489366 A CN201510489366 A CN 201510489366A CN 106450511 A CN106450511 A CN 106450511A
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- electrolyte
- ion
- battery
- metal
- guanidine
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
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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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Abstract
The invention provides an electrolyte. A solvent of the electrolyte is water, wherein the electrolyte comprises first metal ions; the first metal ions are reduced and deposited into first metal on a negative electrode in a charging process; the first metal is reversibly oxidized and dissolved into the first metal ions in a discharging process; the electrolyte also comprises an additive guanidine salt; and the guanidine salt can be ionized in the electrolyte to generate guanidine cations. According to the aqueous electrolyte provided by the invention, positive electrode and negative electrode side reactions can be reduced, thereby improving the performance of a battery. The invention further provides an aqueous battery containing the electrolyte.
Description
Technical field
The invention belongs to electrochemical energy storage field and in particular to a kind of electrolyte and utilize this electricity
The battery of solution liquid.
Background technology
Lead-acid battery, its go out super century-old, have maturation battery technology, 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, and has price very
Cheap, the very high advantage of cost performance.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 new aqoue seconary battery occurred in recent years.The negative pole of this secondary cell being capable of base
Carry out reversible reduction deposition-oxidation dissolving reaction in the first metal ion, positive pole can be based on
Second metal ion carries out reversible abjection-insertion reaction, electrolyte contain participation cathode deposition-
First metal ion of dissolving reaction and the second metal ion participating in 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 very promises to be the energy-storage battery of future generation substituting lead-acid battery, greatly should have
With being worth.
But, in charge and discharge process, side reaction is more for this battery at present, leads to battery oneself
The hydraulic performance declines such as electric discharge, floating charge, multiplying power.
Content of the invention
The technical problem to be solved be provide a kind of electrolyte, can reduce positive pole and
The side reaction of negative pole, thus improve battery performance.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is as follows：A kind of electrolysis
Liquid, the solvent of described electrolyte is water, and described electrolyte includes to dissolve in negative pole reversible oxidation
The first metal ion depositing with reduction, described electrolyte also includes additive guanidinesalt, described guanidine
Salt can ionize generation guanidine cation in described electrolyte.
Preferably, mass percent in described electrolyte for the described guanidine cation exists
In the range of 0.01%-0.5%.
Preferably, described additive guanidinesalt is guanidine hydrochloride, Guanidine nitrate (1:1) or guanidine sulfate.
Preferably, described first metal ion include zinc ion, iron ion, manganese ion, chromium from
One of son, copper ion and nickel ion.
Preferably, described electrolyte also includes the second metal ion, and described second metal ion exists
Reversible can deviate from-embed in positive pole in charge and discharge process.
Preferably, described second metal ion includes in lithium ion, sodium ion or magnesium ion one
Kind.
Preferably, the pH value range of described electrolyte is 3-7.
Preferably, described electrolyte also includes sulfate ion, chloride ion, bromide ion, acetic acid
In radical ion, nitrate ion, carbonate, formate ion and alkyl sulfonate ion one
Plant or several.
Another technical problem to be solved by this invention is to provide a kind of battery, improves battery
Cycle life so that it is preferably applied on energy device.
For achieving the above object, the technical solution adopted in the present invention is as follows：A kind of battery, bag
Include positive pole, negative pole and electrolyte, described electrolyte is above-mentioned electrolyte.
Preferably, include being capable of the reversible positive-active deviating from-embedding metal ion for described positive pole
Material.
Compared with prior art, the invention has the beneficial effects as follows：There is the battery energy of this electrolyte
Enough reduce the side reaction of positive pole and negative pole, so as to make floating current reduce, gram volume improves,
High rate performance is lifted, and has given play to more preferable battery performance.
Brief description
The battery that Fig. 1 provides for embodiment 1 and comparative example 1 at room temperature respectively successively with 0.2C,
0.5C, 1C, 2C, 4C, 0.2C multiplying power carries out the high rate performance after constant current charge-discharge 5 times；
The battery that Fig. 2 provides for embodiment 1 and comparative example 1 1C multiplying power discharge capacity,
Battery efficiency and cycle-index graph of a relation；
The battery that Fig. 3 provides for embodiment 1 and comparative example 1 under 2.1V floating charge 24h floating
Charging current density；
Fig. 4 is the open-circuit voltage of the battery placement 24h of embodiment 1 and comparative example 1 offer；
The battery that Fig. 5 provides for embodiment 2 and comparative example 2 4C multiplying power discharge capacity,
Battery efficiency and cycle-index graph of a relation；
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are clearer
Understand, with reference to embodiments, the present invention will be described in further detail.It 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 electrolyte, including the first metal ion.This first metal ion is in charging process
It is deposited as the first metal in cathodic reduction, reversible oxidation is dissolved as the first metal in discharge process
Ion.Electrolyte also includes additive guanidinesalt.
Electrolyte includes electrolyte and solvent.Wherein, in electrolyte, the purpose of solvent is dissolving
Electrolyte, and so that electrolyte is ionized in a solvent, finally generate 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 in 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 become the first metal, are deposited on negative
Extremely go up；In 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 of 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, be additionally included in charge and discharge process can in positive pole for electrolyte
Second metal ion of reversible abjection-embedded.I.e. when battery charges, the second metal ion from
Deviate from positive active material, enter electrolyte；In battery discharge, in electrolyte second
Metal ion embeds in positive active material.Preferably, the second metal ion be 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, there is embedded-abjection in positive pole in lithium ion, zinc ion deposits-dissolves in negative pole.
In a preferred embodiment, also include one kind in electrolyte to aoxidize in anode
The ion of reduction reaction.When battery charges, this ion in electrolyte is oxidized；Battery is put
When electric, during charging, oxidized active substance is reduced again.Preferably, this ion be 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, there is oxidation-reduction reaction in positive pole in bromide ion, and zinc ion deposits in negative pole-
Dissolving.
Additive guanidinesalt is also included in electrolyte.Guanidinesalt can ionize out in the electrolytic solution guanidine sun from
Son.Preferably, guanidine cation has below general formula：
Guanidine cation also includes the derivant of above-mentioned formula.The present invention reduces both positive and negative polarity by guanidine cation
Side reaction, thus improving the performance of battery.
Additive guanidinesalt is added, guanidinesalt ionizes generation guanidine cation in the electrolytic solution in electrolyte,
On the one hand guanidine cation absorption in negative terminal surface, can reduce burn into dendrite and the product of metal negative electrode
Gas, on the other hand can also be adsorbed onto positive electrode surface, play mechanical isolation effect, slow down electricity
The solution corrosion to conductive agent for the liquid.By adding guanidine cation, further suppress water in electrolyte point
Solution, decreases the generation of gas, improves the security performance of battery.Therefore, the floating charge of battery
The chemical properties such as performance, high rate performance, gram volume are improved.
Preferably, mass percent in described electrolyte for the guanidinesalt is in the range of 0.01%-0.5%.
In a preferred embodiment, electrolysis additive guanidinesalt is guanidine hydrochloride.Preferably, hydrochloric acid
The mass fraction that the addition of guanidine accounts for electrolyte total amount is 0.2%.
In a preferred embodiment, electrolysis additive guanidinesalt is Guanidine nitrate (1:1) or guanidine sulfate.When
So, other such as guanidine carbonate, formic acid guanidine, bromination guanidine etc. can go out guanidine cation in electrolyte ionization
Compound is also the preferable additives of the present invention.
Additive adds the mode in electrolyte not limit, 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
The anion that solution matter dissolves in a solvent.Can be for example 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 allocating.
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 that battery performance more optimizes, 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, can also avoid electrode corrosion.
Present invention also offers a kind of 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 metal from
Son can occur reversible reduction deposition-oxidation to dissolve reaction on negative pole；Described positive pole includes
Being capable of the reversible positive active material deviating from-embedding the second metal ion；Described electrolyte includes
First metal ion and the second metal ion, in charge and discharge process, described first metal ion exists
Negative pole can reduce and be deposited as the first metal and the first metal energy reversible oxidation is dissolved as the first gold medal
Belong to ion, described second metal ion can be in the reversible abjection of positive pole-embedded.
The charge-discharge principle of battery is：During charging, positive active material deviates from the second metal ion,
Simultaneously oxidized with positive active material, and ejected electron；Electronics reaches electricity via external circuit
Pond negative pole, simultaneously the first metal ion in electrolyte electronics obtained on negative pole be reduced, 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 reaches positive pole through external circuit, and positive pole is lived
Property material accept electronics and be reduced, the second metal ion embeds in 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 of 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, according to the difference of structure and effect, can be divided into following three kinds of different forms again：
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 such as 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
Rustless steel from rustless steel or passivated process.Rustless steel include but are not limited to stainless (steel) wire and
Stainless steel foil, likewise, stainless model can be the rustless steel of 300 series, such as stainless
Steel 304 or Stainless steel 316 or Stainless steel 316 L.In addition, negative current collector can also select
From the metal of the plating/coating high containing hydrogen-evolution overpotential, thus reducing 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
At least one of.The thickness range of plating/coating is 1～1000nm.For example：In Copper Foil or graphite
Stannum, lead or silver on the negative current collector plated surface of paper tinsel.
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 may be referred to the first preferred implementation, will not be described here.
Negative electrode active material is existed with lamellar or powder.
When the negative electrode active material using lamellar, sheet metal forms composite bed with negative current collector.
When the negative electrode active material using 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, bear always according to needing to add
Pole conductive agent and negative electrode binder are lifting the performance of negative pole.
In the 3rd preferred implementation, directly adopt sheet metal as negative pole, sheet metal was both made
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 is 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 be 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,
At least one of Ti, Cr, V, Zn, Zr, Si or Al.Preferably, positive active material
Containing LiCoO2.
Positive active material can also be 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
At least one of, X is selected from least one in S, P or Si.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, it is complicated that the means such as coating modification cause the chemical general formula of material to express,
As LiMn2O4The formula of now widely used " LiMn2O4 " can not have been represented, and should
With formula Li1+xMnyMzOkIt is defined, widely include through various modified LiMn2O4Just
Pole active substance.Likewise, LiFePO4And LiCoO2Also should be construed broadly to include
Modified through various doping, cladding etc., formula corresponds with LixM1-yM′y(XO4)nWith
Li1+xMyM′zM″cO2+nPositive active material.
When positive active material is the material of the reversible abjection of energy-embedded 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 are similar functions, can deviate from-compound of 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 lift the performance of positive pole.In positive pole material
In material, the purpose using conductive agent is to reduce the resistance of overall positive pole, strengthens positive electrode simultaneously
Conductive path between grain.Positive conductive agent be selected from conducting polymer, activated carbon, Graphene,
One or more of carbon black, graphite, carbon fiber.Binding agent is conducive to making positive active material
Uniformly it is bonded together with conductive agent, thus processing formation 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
The mixture of one of dimethacrylate or above-mentioned polymer and derivant.It is furthermore preferred that
Positive electrode binder is selected from politef (PTFE), Kynoar (PVDF) or butadiene-styrene rubber
(SBR).
Specifically, positive pole also includes loading the plus plate current-collecting body of positive active material, anode collection
Body is only used as electronics conduction and the carrier collected, and is not involved in electrochemical reaction, that is, battery operated
In voltage range, what plus plate current-collecting body can be stable be present in electrolyte there is not pair substantially
Reaction, thus ensure that battery has stable cycle performance.
The material of plus plate current-collecting body is selected from one of carbon-based material, metal or alloy.
Carbon-based material be selected from vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth,
One of carbon fiber.
Metal includes Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or through blunt
Change one of above-mentioned metal processing.
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 stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to
Stainless steel 304 or one of Stainless steel 316 or Stainless steel 316 L.
Preferably, plus plate current-collecting body is passivated processing, its main purpose is to make positive pole collection
The surface of fluid forms the oxide-film of one layer of passivation, thus in battery charge and discharge process, can rise
To the effect of stable collection and conduction electronics, without participating in cell reaction it is ensured that cell performance
Can be stable.Plus plate current-collecting body deactivating process for the treatment of is included at chemical passivation process or electrochemical passivation
Reason.
Chemical passivation processes and includes, by oxidizing plus plate current-collecting body, making anode collection body surface
Face forms passivating film.The principle that oxidant selects can make plus plate current-collecting body surface be formed for oxidant
One layer of passivating film is without dissolving plus plate current-collecting body.Oxidant be selected from but be not limited only to concentrated nitric acid or
Ceric sulfate (Ce (SO4)2).
Electrochemical passivation processes and includes plus plate current-collecting body being carried out with electrochemical oxidation or to containing just
The battery of pole collector carries out charge and discharge electric treatment, makes plus plate current-collecting body surface form passivating film.
More preferred, positive pole also includes loading the composite current collector of positive active material, is combined
Collector includes plus plate current-collecting body and the conducting film being coated on plus plate current-collecting body.
Conducting film meet in aqueous electrolyte can with stable existence, insoluble in electrolyte, do not send out
The swelling, high voltage of life can not oxidized, be easily processed into fine and close, waterproof and conductive will
Ask.On the one hand, conducting film can play a protective role to plus plate current-collecting body, it is to avoid water system is electrolysed
The corrosion to plus plate current-collecting body for the liquid.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 the first face being oppositely arranged and the second face it is preferred that anode collection
First face of body and the second face are all coated with conducting film.
Conducting film comprises the polymer as necessary component, and polymer accounts for the weight proportion of conducting film
For 50～95% it is preferred that polymer is selected from thermoplastic polymer.In order that conducting film can
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 is to have conductive capability but electrochemicaUy inert, that is, will not conduct
The ionic conduction of charge transfer medium.Specifically, conducting polymer includes but are not limited to poly- second
Alkynes, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, poly- right
Penylene (polyparaphenylene) and its any mixture.Conducting polymer inherently has leads
Electrically, it is also possible to be doped to conducting polymer or modification is to improve its conductive energy further
Power.Stable use from electric conductivity and battery is considered, the preferred polyaniline of conducting polymer,
Polypyrrole, polythiophene and polyacetylene.
Likewise, the choice requirement of conductive filler be that surface area is little, be difficult to aoxidize, degree of crystallinity is high,
There is electric conductivity but electrochemicaUy inert, that is, will not be used 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
Close 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.
Specifically, 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 combined by hot pressing, is attached to anode collection by way of evacuation or spraying
On body.
In order to provide more preferable security performance, preferably it is located in the electrolytic solution between positive pole and negative pole
It is additionally provided with barrier film.The both positive and negative polarity that other unexpected factors that can avoid barrier film cause is connected and causes
Short circuit.
Barrier film does not have particular/special requirement, as long as allow electrolyte by and the barrier film of electronic isolation be
Can.The various barrier films that organic series 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
Press mass ratio 86:7:7 by LiMn2O4 LMO, graphite agent KS-6, binding agent PVDF
NMP mixes, forms uniform anode sizing agent.Anode sizing agent is coated in anode collection
Form active material layer in body graphite foil, subsequently carried out tabletting, be cut into a diameter of 12mm
The disk of size, makes positive plate, and in positive plate, the load capacity of LMO is 5mg/cm2.Negative
Pole adopts the zinc metal sheet that thickness is 0.2mm as negative current collector.Barrier film is AGM glass fibre
Barrier film.Barrier film and negative pole size are suitable with positive pole.
Weigh a certain amount of zinc sulfate, lithium sulfate is dissolved in deionized water, then be added thereto to salt
Sour guanidine, stirring, be configured to sulphuric acid zinc concentration be 2mol/L, sulphuric acid lithium concentration be 1mol/L,
Guanidine hydrochloride mass fraction in the electrolytic solution is 0.2% electrolyte, i.e. guanidine sun in described electrolyte
Ion mass fraction in the electrolytic solution is 0.126%.
Positive plate, negative plate and membrane layer stacked group are dressed up battery core, loads in housing, then
Injection electrolyte, sealing, it is assembled into battery.
Embodiment 2
With embodiment 1 except that, sulphuric acid zinc concentration is that 1mol/L, sulphuric acid lithium concentration are
2mol/L, other parts, with embodiment 1, are assembled into battery.
Embodiment 3
With embodiment 1 except that, sulphuric acid zinc concentration is that 1mol/L, sulphuric acid lithium concentration are
2mol/L, in electrolyte the mass fraction of guanidine hydrochloride be 0.1%, that is, in described electrolyte guanidine sun from
Son mass fraction in the electrolytic solution is 0.063%.Other parts, with embodiment 1, are assembled into electricity
Pond.
Embodiment 4
With embodiment 1 except that, sulphuric acid zinc concentration is that 1mol/L, sulphuric acid lithium concentration are
2mol/L, in electrolyte the mass fraction of guanidine hydrochloride be 0.5%, that is, in described electrolyte guanidine sun from
Son mass fraction in the electrolytic solution is 0.315%.Other parts, with embodiment 1, are assembled into electricity
Pond.
Comparative example 1
With embodiment 1 except that, do not add guanidine hydrochloride in electrolyte, other parts with
Embodiment 1, is assembled into battery.
Comparative example 2
With comparative example 1 except that, sulphuric acid zinc concentration is that 1mol/L, sulphuric acid lithium concentration are
2mol/L, other parts, with comparative example 1, are assembled into battery.
Electrochemical property test
Respectively chemical property detection is carried out to the battery of embodiment 1-4 and comparative example 1-2,
Carry out constant current with 0.2C, 0.5C, 1C, 2C, 4C, 0.2C multiplying power successively respectively under room temperature to follow
Ring discharge and recharge 5 times, voltage range be 1.4-2.1V, then by battery under 2.1V floating charge 24h,
Again by battery under 1C multiplying power cycle charge-discharge, then the placement 24h that opens a way, then discharged.
The battery that Fig. 1 provides for embodiment 1 and comparative example 1 at room temperature respectively successively with 0.2C,
0.5C, 1C, 2C, 4C, 0.2C multiplying power carries out the high rate performance of constant current cycle discharge and recharge 5 times
Figure.It can be seen that after electrolyte adds the guanidine hydrochloride of 0.2%wt, the high rate performance of battery
It is improved.
The battery that Fig. 2 provides for embodiment 1 and comparative example 1 1C multiplying power discharge capacity,
Battery efficiency and cycle-index graph of a relation.As seen from the figure, at the beginning of electrolyte adds the battery of guanidine hydrochloride
Beginning capacity 132mAh/g, electrolyte is without battery initial capacity 122mAh/g of guanidine hydrochloride.
Described above, electrolyte adds the guanidine hydrochloride of 0.2%wt, and the initial capacity of battery is improved.
The battery that Fig. 3 provides for embodiment 1 and comparative example 1 under 2.1V floating charge 24h floating
Charging current density.From in figure it can also be seen that, electrolyte add 0.2%wt guanidine hydrochloride after, electricity
The floating current in pond is declined.
Fig. 4 is the open-circuit voltage of the battery placement 24h of embodiment 1 and comparative example 1 offer.From
In figure it can also be seen that, electrolyte add 0.2%wt guanidine hydrochloride after, the open-circuit voltage of battery obtains
To rising.
The battery that embodiment 2-4 and comparative example 2 are provided at room temperature respectively successively with 0.2C,
0.5C, 1C, 2C, 4C, 0.2C multiplying power carries out the high rate performance of constant current cycle discharge and recharge 5 times
Figure.Test result shows, electrolyte add 0.5%wt guanidine hydrochloride after, battery forthright again
Can be improved.
The floating charge of battery floating charge 24h under 2.1V that embodiment 2-4 and comparative example 2 are provided
Electric current density.Test result shows, electrolyte adds the guanidine hydrochloride of 0.1%wt or 0.2%wt
Afterwards, the floating current of battery is declined.
24h test open-circuit voltage placed by the battery that embodiment 2-4 and comparative example 2 are provided.Survey
Test result shows, after electrolyte adds guanidine hydrochloride, the open-circuit voltage of battery is risen.
The battery that Fig. 5 provides for embodiment 2 and comparative example 2 4C multiplying power discharge capacity,
Battery efficiency and cycle-index graph of a relation.As seen from the figure, the battery initial capacity of embodiment 2 is about
For 113mAh/g, the capability retention when circulating 100,200,500,700,1000 circle
It is respectively 89.2%, 83.2%, 71.1%, 65.9%, 57.1%；The battery of comparative example 2 is initial
Capacity is about 114mAh/g, the capacity when circulating 100,200,500,700,1000 circle
Conservation rate is respectively 89.3%, 86.5%, 73.3%, 63.4%, 53.9%.Described above, electricity
Solution liquid adds the guanidine hydrochloride of 0.2%wt, and the capability retention observing battery from long-term tendency obtains
Lifting.
Although inventor has done elaboration in greater detail and has enumerated to technical scheme,
It should be appreciated that to those skilled in the art, above-described embodiment is modified and/or becomes
Logical or be obvious using equivalent replacement scheme, all can not depart from the essence of spirit of the present invention,
The term occurring 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 (10)
1. a kind of electrolyte, the solvent of described electrolyte is water, and described electrolyte includes the first metal
Ion, described first metal ion is deposited as the first gold medal in cathodic reduction in charging process
Belong to, described first metal reversible oxidation in discharge process is dissolved as the first metal ion；
It is characterized in that, described electrolyte also includes additive guanidinesalt, and described guanidinesalt can be in institute
State ionization in electrolyte and produce guanidine cation.
2. electrolyte according to claim 1 it is characterised in that：Described guanidine cation is in institute
State mass percent in electrolyte in the range of 0.01%-0.5%.
3. electrolyte according to claim 1 it is characterised in that：Described additive guanidinesalt is
Guanidine hydrochloride, Guanidine nitrate (1:1) or guanidine sulfate.
4. electrolyte 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.
5. electrolyte according to claim 1 it is characterised in that：Described electrolyte also includes
Second metal ion, described second metal ion can in positive pole in charge and discharge process
Inverse abjection-embedded.
6. electrolyte according to claim 5 it is characterised in that：Described second metal ion
Including one of lithium ion, sodium ion and magnesium ion.
7. electrolyte according to claim 1 it is characterised in that：The pH of described electrolyte
Value scope is 3-7.
8. electrolyte according to claim 1 it is characterised in that：Described electrolyte also includes
Sulfate ion, chloride ion, bromide ion, acetate ion, nitrate ion, carbonic acid
One or more of root, formate ion and alkyl sulfonate ion.
9. a kind of battery, including positive pole, negative pole and electrolyte it is characterised in that：Described electrolyte
Electrolyte described in claim 1-8 any one.
10. battery according to claim 9 it is characterised in that：Described positive pole includes can
The positive active material of inverse abjection-embedded metal ion.
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| CN201510489366.4A CN106450511A (en) | 2015-08-11 | 2015-08-11 | Electrolyte and battery |
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| CN201510489366.4A CN106450511A (en) | 2015-08-11 | 2015-08-11 | Electrolyte and battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115961141A (en) * | 2023-02-01 | 2023-04-14 | 中国地质科学院郑州矿产综合利用研究所 | Eutectic solvent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101420053A (en) * | 2008-11-27 | 2009-04-29 | 上海交通大学 | Guanidinium type ionic liquid electrolyzing solution for lithium secondary cell |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
| CN104282952A (en) * | 2013-07-12 | 2015-01-14 | 苏州宝时得电动工具有限公司 | Electrolyte and battery |
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2015
- 2015-08-11 CN CN201510489366.4A patent/CN106450511A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
| CN101420053A (en) * | 2008-11-27 | 2009-04-29 | 上海交通大学 | Guanidinium type ionic liquid electrolyzing solution for lithium secondary cell |
| CN104282952A (en) * | 2013-07-12 | 2015-01-14 | 苏州宝时得电动工具有限公司 | Electrolyte and battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115961141A (en) * | 2023-02-01 | 2023-04-14 | 中国地质科学院郑州矿产综合利用研究所 | Eutectic solvent and preparation method and application thereof |
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Application publication date: 20170222 |