CN102903924B - Battery - Google Patents

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Publication number
CN102903924B
CN102903924B CN201210178722.7A CN201210178722A CN102903924B CN 102903924 B CN102903924 B CN 102903924B CN 201210178722 A CN201210178722 A CN 201210178722A CN 102903924 B CN102903924 B CN 102903924B
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battery
electrolyte
ion
active material
negative pole
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CN102903924A (en
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陈璞
王静
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Positec Power Tools Suzhou Co Ltd
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Positec Power Tools Suzhou Co Ltd
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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

Abstract

Present invention is disclosed a kind of battery, comprise positive pole, negative pole and electrolyte, described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, described positive active material can reversible deviate from-embedded ion; Described negative pole at least comprises negative current collector; Described electrolyte comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion that dissolves at described negative pole; Described negative terminal surface is formed with porous layer or graphene layer, and described porous layer has micron or sub-micron or nanoscale hole.Battery-operated safety provided by the invention, production cost is low, and cycle performance is excellent and the life-span permanent, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery.

Description

Battery
Technical field
The invention belongs to electrochemical energy storage field, be specifically related to a kind of battery.
Background technology
The mankind, to the extensive utilization of new forms of energy, result in the expansion rapidly in secondary cell market.Ubiquitous to the requirement of secondary cell in current new forms of energy system.No matter be electric automobile, wind energy, solar grid-connected or peak load regulation network, is all badly in need of a kind of cheap, reliably, the secondary cell of safety and life-span length.The secondary cell developed at present mainly concentrates on lithium ion battery, high temperature sodium-sulphur battery, sodium nickel chlorine battery and vanadium flow battery.These batteries all have respective advantage, such as lithium ion battery and high-temperature sodium sulphur battery life is long and energy density is high, and vanadium flow battery possesses the unlimited life-span etc. especially in theory.But no matter which kind of battery, all cannot meet cheapness simultaneously, reliably, safety and life-span long requirement.Traditional lithium ion battery is too expensive, and has potential safety hazard; High-temperature sodium sulphur cell manufacturing techniques threshold is high, fetch long price; The multinomial technical bottleneck of vanadium flow battery is all failed at present to obtain and is broken through.
Many researchers is all devoted to the research of aquo-lithium ion battery for this reason, ites is desirable to significantly reduce the cost of lithium ion battery with this and improve fail safe, and proposes some with LiMn 2o 4for positive pole, the oxide such as LiV of vanadium 3o 8deng being the battery of electrolyte for negative pole, water, but there is certain toxicity because of the poor stability of this type of negative pole discharge and recharge in water and vanadium, thus limit the development of this type of battery.So far, the structure of the aquo-lithium ion secondary cell proposed all is failed to break away from and is deviate from-the structure of embedding principle based on lithium ion, has such as had the VO of report 2/ LiMn 2o 4, LiV 3o 8/ LiNi 0.81co 0.19o 2, TiP 2o 7/ LiMn 2o 4, LiTi 2(PO 4) 3/ LiMn 2o 4, LiV 3o 8/ LiCoO 2deng.
Summary of the invention
The present invention aims to provide a kind of low cost, the safe and reliable and battery of function admirable.
The invention provides a kind of battery, comprise positive pole, negative pole and electrolyte, described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, described positive active material can reversible deviate from-embedded ion; Described negative pole at least comprises negative current collector; Described electrolyte comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion that dissolves at described negative pole; Described negative pole currect collecting surface is formed with porous layer or graphene layer, and described porous layer has micron or sub-micron or nanoscale hole.
Preferably, the thickness range of described porous layer or graphene layer is 0.05-1mm.
Preferably, described micron or submicron order hole account for the volume range of described porous layer is 50-95%.
Preferably, described nanoscale hole accounts for the volume range of described porous layer is 10-99%.
Preferably, the scope of the average diameter of described nanoscale hole is 1-150nm.
Preferably, the material of described porous layer is selected from carbon-based material.
Preferably, described carbon-based material is selected from least one in section's qin carbon black, activated carbon, carbon nano-tube, carbon fiber, graphite.
Preferably, described carbon-based material is the mixture of activated carbon powder and binding agent, and the weight percentage ranges that described activated carbon powder accounts for described porous layer is 20-99%.
Preferably, described negative pole also comprises the negative electrode active material being formed at described negative pole currect collecting surface, and described negative electrode active material can be oxidized-be dissolved as described active ion in described battery discharge procedure.
Preferably, material selected from metal Ni, Cu, Ag, Pb, Sn, Fe, Al of described negative current collector or the one in the above-mentioned metal of Passivation Treatment.
Preferably, the material of described negative current collector is selected from carbon-based material, stainless steel, silicon or has the metal of plating/coating, and described plating/coating contains at least one in the simple substance of C, Sn, In, Ag, Pb, Co, Zn, alloy or oxide.
Preferably, the thickness range of described plating/coating is between 1-1000nm.
Preferably, described active ion comprises metal ion, and described metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni.
Preferably, described metal ion is present in described electrolyte with at least one form in chlorate, sulfate, nitrate, acetate, formates, phosphate.
Preferably, lithium ion, sodium ion, zinc ion or magnesium ion can deviate from-embedded to described positive active material reversiblely.
Preferably, the material of described plus plate current-collecting body be selected from graphite, stainless steel, aluminium alloy, through the stainless steel of transpassivation or aluminium alloy.
Present invention also offers a kind of battery, comprise positive pole, negative pole, electrolyte, described positive pole comprises positive active material, described positive active material can reversible deviate from-embedded ion; Described negative pole comprises the negative electrode active material participating in electrochemical reaction; Described electrolyte comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte can ionize out at least one charge and discharge process described negative pole reduce-deposit and be oxidized-active ion that dissolves or/and can the reversible ion deviate from-embed at described positive pole at least one charge and discharge process, described negative electrode active material can be oxidized-be dissolved as described active ion in discharge process; Described negative pole also comprises the porous layer or graphene layer that are formed at described negative electrode active material surface, and described porous layer has micron or sub-micron or nanoscale hole.
Present invention also offers a kind of battery, comprise positive pole, negative pole, electrolyte and barrier film, described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, described positive active material be can reversible deviate from-compound of embedded ion; Described negative pole is the electrochemicaUy inert conductive electrode not participating in electrochemical reaction; Described electrolyte is the aqueous solution, at least reduces-deposit and be oxidized-the metal ion that dissolves containing in charge and discharge process at described negative pole; Described negative pole comprises negative current collector and is formed at the porous layer with micro-void of described negative pole currect collecting surface.
Battery-operated safety provided by the invention, production cost is low, negative terminal surface is formed with porous layer or graphene layer, larger deposition rate surface area can be provided on the one hand for the active ion in electrolyte, the generation of effective minimizing negative pole dendrite, also shorten active ion migration distance on the other hand, solve the diffusional resistance problem of active ion at charge and discharge process, make battery have good chemical property and cycle life, battery of the present invention is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery.
Accompanying drawing explanation
Fig. 1 is first embodiment of the invention battery structure schematic diagram;
Fig. 2 is first embodiment of the invention battery charging process schematic diagram;
Fig. 3 is first embodiment of the invention battery discharge procedure schematic diagram;
Fig. 4 is second embodiment of the invention battery structure schematic diagram;
Fig. 5 is the cyclic voltammetry curve figure of stainless steel 304 in stannous sulphate electrolyte of unpassivated process in embodiment 1-1;
Fig. 6 is through the cyclic voltammetry curve figure of the Stainless steel 316 of Passivation Treatment in stannous sulphate electrolyte in embodiment 1-2;
Fig. 7 is through the cyclic voltammetry curve figure of the Stainless steel 316 P of Passivation Treatment in nitrate electrolyte in embodiment 1-3;
Fig. 8 is the cyclic voltammetry curve figure of aluminium alloy in acetate electrolyte of passivation in embodiment 1-4;
Fig. 9 is the cyclic voltammetry curve figure of aluminium alloy in stannous sulphate electrolyte of passivation in embodiment 1-5;
Figure 10 is the cyclic voltammetry curve figure of graphite foil in hydrochloride electrolyte in embodiment 1-6;
Figure 11 is the cyclic voltammetry curve figure of non-passivation stainless steel in hydrochloride electrolyte in embodiment 1-7;
Figure 12 is the voltage of the battery that embodiment 3-1 provides and the graph of relation of discharge capacity;
Figure 13 is the discharge capacity of the battery that embodiment 3-1 provides and the graph of relation of cycle-index;
Figure 14 is the discharge capacity of the battery that embodiment 3-2 provides and the graph of relation of cycle-index;
Figure 15 is the discharge capacity of the battery that embodiment 3-3 provides and the graph of relation of cycle-index;
Figure 16 is the coulombic efficiency of the battery that embodiment 3-3 provides and the graph of relation of cycle-index;
Figure 17 is the discharge capacity of the battery that embodiment 3-4 provides and the graph of relation of cycle-index;
Figure 18 is the structural representation that in embodiment 4-1, negative pole currect collecting surface is formed with porous layer;
Figure 19 is the close-up schematic view of porous layer in Figure 18;
Figure 20 is the curve chart of the battery first charge-discharge voltage-capacity that embodiment 4-1 provides;
Figure 21 is the cyclic voltammetry curve figure of the battery that embodiment 5-1 provides;
Figure 22 is the cyclic voltammetry curve figure of the battery that embodiment 5-2 provides;
Figure 23 is the cyclic voltammetry curve figure of the battery that embodiment 5-3 provides;
Figure 24 is the cyclic voltammetry curve figure of the battery that embodiment 5-4 provides;
Figure 25 is the cyclic voltammetry curve figure of the battery that embodiment 5-6 provides;
Figure 26 is the cyclic voltammetry curve figure of the battery that embodiment 5-9 provides;
Figure 27 is the relation curve of the battery first charge-discharge that provides of embodiment 6-1 and voltage;
Figure 28 is the graph of relation of the discharge capacity of the cell that provides of embodiment 6-1 and cycle-index;
Figure 29 is the graph of relation of the battery coulombic efficiency that provides of embodiment 6-1 and cycle-index;
Figure 30 is the discharge capacity of the battery that embodiment 6-2 provides and the graph of relation of cycle-index;
Figure 31 is the graph of relation of the battery coulombic efficiency that provides of embodiment 6-2 and cycle-index;
Figure 32 is the discharge capacity of the battery that embodiment 6-4 provides and the graph of relation of cycle-index;
Figure 33 is the discharge capacity of the battery that embodiment 6-5 provides and the graph of relation of cycle-index.
Wherein:
10. positive pole 20. negative pole 28. active ion
12. plus plate current-collecting body 22. negative current collector 30. porous layers
14. positive active material 24. negative electrode active materials
The 16. reversible ion 26. active ion sedimentary deposits deviate from-embed
Embodiment
Battery provided by the invention has higher energy density, stable cycle performance, and at the such as portable type electronic product such as mobile phone, notebook computer, electric automobile, the fields such as electric tool have considerable application prospect.
A kind of battery, comprises positive pole 10, negative pole 20 and electrolyte (not shown).Positive pole 10 comprises plus plate current-collecting body 12 and participates in the positive active material 14 of electrochemical reaction, positive active material 14 can reversible deviate from-embedded ion; Negative pole 20 at least comprises negative current collector 22; Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion 28 that dissolves at negative pole.
Refer to shown in Fig. 1, Fig. 1 is first embodiment of the invention battery structure schematic diagram, and in the first embodiment, battery cathode 20 only comprises negative current collector 22.
Positive active material 14 participates in positive pole reaction, and can reversible deviate from-embedded ion or functional group.Concrete, lithium ion, sodium ion, zinc ion or magnesium ion can deviate from-embedded to positive active material 14 reversiblely.
Positive active material 14 can be meet general formula Li 1+xmn ym zo kcan the reversible compound deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al.Preferably, positive active material 14 is containing LiMn 2o 4.Preferred, positive active material 14 is containing the LiMn through overdoping or coating modification 2o 4.
Positive active material 14 can be meet general formula Li 1+xm ym ' zm " co 2+ncan the reversible compound deviating from-embed the layer structure of lithium ion, wherein,-1 < x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material 14 is containing LiCoO 2.
Positive active material 14 can be meet general formula Li xm 1-ym ' y(XO 4) ncan the reversible compound deviating from-embed the olivine structural of lithium ion, wherein, 0 < x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.Preferably, positive active material 14 is containing LiFePO 4.
In current Lithium Battery Industry, nearly all positive active material 14 all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn 2o 4can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li 1+xmn ym zo kbe as the criterion, comprise the LiMn through various modification widely 2o 4.Same, LiFePO 4and LiCoO 2also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively xm 1-ym ' y(XO 4) nand Li 1+xm ym ' zm " co 2+npositive active material.
Positive active material of the present invention 14 for reversible deviate from-embed lithium ion compound time, can select as LiMn 2o 4, LiFePO 4, LiCoO 2, LiM xpO 4, LiM xsiO ycompounds such as (wherein M are a kind of variable valency metal).In addition, the compound of sodium ion can be deviate from-embed as NaVPO 4f, can deviate from-embed the compound of zinc ion as γ-MnO 2, can deviate from-embed the compound of magnesium ion as MgM xo y(wherein M is a kind of metal, 0.5 < x < 3,2 < y < 6) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive active material 14 of battery of the present invention.
In concrete execution mode, when preparing anode sizing agent, in anode sizing agent except positive active material 14, also need to add conductive agent and binding agent.
Conductive agent be selected from conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and sheet metal one or more.
Binding agent is selected from polyethylene oxide, polypropylene oxide, the mixture of a kind of or above-mentioned polymer in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, poly-divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates and derivative.In a specific embodiment, binding agent is selected from polytetrafluoroethylene (PTFE) or Kynoar (PVDF).
Plus plate current-collecting body 12 is only as the carrier of electrical conductivity and collection, do not participate in electrochemical reaction, namely within the scope of battery operating voltage, what plus plate current-collecting body 12 can be stable is present in electrolyte does not have other side reactions to occur, thus ensures that battery has stable cycle performance.The material of plus plate current-collecting body 12 is selected from the one in carbon-based material, metal or alloy.
Concrete, the one that carbon-based material is selected from vitreous carbon, graphite, carbon felt, carbon fiber or has in the electric conducting material of 3D bicontinuous structure.Wherein, the electric conducting material with 3D bicontinuous structure includes but are not limited to foamy carbon.Graphite includes but are not limited to graphite foil and graphite cake.
Metal is selected from Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.
Alloy is selected from stainless steel, aluminium alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned alloy of Passivation Treatment.Stainless steel comprises stainless steel foil or stainless (steel) wire, concrete, and stainless model can be but be not limited to the stainless steel of 300 series, as stainless steel 304,316,316L or 316P.The model of aluminium alloy can be but be not limited to the aluminium alloy of 6000 series, as aluminium alloy 6061.
Negative pole 20 only comprises negative current collector 22, and negative current collector 22 is only as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.
Material selected from metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al, Zn of negative current collector 22 or at least one in the above-mentioned metal of Passivation Treatment, or elemental silicon, or carbon-based material, wherein, carbon-based material comprises graphite material, the such as paper tinsel of business-like graphite compacting, the part by weight scope wherein shared by graphite is 90-100%.The material of negative current collector 22 can also be selected from stainless steel or the stainless steel through Passivation Treatment.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, same, and stainless model can be but be not limited to the stainless steel of 300 series, as stainless steel 304,316,316L or 316P.
In addition, negative current collector 22 can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy, or at least one in oxide.The thickness range of plating/coating is 1-1000nm.Such as: tin on the negative current collector plated surface of Copper Foil or graphite foil, plumbous or silver-colored.
The main purpose that plus plate current-collecting body 12 or negative current collector 22 are carried out Passivation Treatment is the oxide-film making the surface of collector form one deck passivation, thus in battery charge and discharge process, stable collection and the effect of conduction electron can be played, and cell reaction can not be participated in, ensure that battery performance is stablized.Collector deactivating process for the treatment of comprises chemical passivation process or electrochemical passivation process.
Chemical passivation process comprises by oxidizing collector, makes collection liquid surface form passivating film.The principle that oxidant is selected is that oxidant can make collection liquid surface form one deck passivating film and can not dissolve collector.Oxidant is selected from but is not limited only to red fuming nitric acid (RFNA) or ceric sulfate (Ce (SO 4) 2).
Concrete, chemical passivation treatment step is: inserted by collector in oxidizing agent solution, maintains 0.5-1 hour, makes collection liquid surface form passivating film, and finally taking-up collector cleaning is also dry.
In an embodiment with chemical passivation process stainless (steel) wire or stainless steel foil, concrete Passivation Treatment process is: at 50 DEG C, stainless steel is inserted the concentrated nitric acid solution of 20%, maintain 0.5 hour, make stainless steel surfaces form passivating film, finally take out the cleaning of stainless steel use water and drying in the drying box of 50 DEG C.
In another embodiment with chemical passivation process stainless (steel) wire or stainless steel foil, concrete Passivation Treatment process is: Ce (SO stainless steel being inserted 0.75mol/L 4) 2in solution, maintain 0.5 hour, make stainless steel surfaces form passivating film, finally take out the cleaning of stainless steel use water and drying in the drying box of 50 DEG C.
Electrochemical passivation process comprises to be carried out discharge and recharge to collector or carries out discharge and recharge process to the battery containing collector, makes collection liquid surface form passivating film.
Directly discharge and recharge is carried out to collector, namely collector be used for the process of battery assembling advance row pre-passivating, concrete, carry out discharge and recharge to using collector as the three-electrode system of work electrode, more corresponding selection suitable to electrode and reference electrode.During charging, voltage is all charged to 2.35-2.45V, and during electric discharge, voltage is all put to 1.35-1.45V.Collector can be metal, as metallic aluminium; Collector also can be alloy, as stainless steel or aluminium alloy.Certainly, also can adopt with collector is that two electrode systems of work electrode carry out discharge and recharge, and during charging, voltage is all charged to 2.35-2.45V, and during electric discharge, voltage is all put to 1.35-1.45V.
In the execution mode of a direct passivation aluminium alloy collector, using aluminium alloy as work electrode, zinc paper tinsel is as to electrode and reference electrode, electrolyte is the aqueous solution containing 1.5mol/L zinc acetate and 3mol/L lithium acetate, discharge and recharge is carried out to three-electrode system, during charging, voltage is charged to 2.4V, and make aluminum alloy surface under 2.4V, be oxidized the oxide-film forming one deck passivation, during electric discharge, cut-ff voltage is 1.4V.
Also can carry out discharge and recharge to the battery containing collector thus reach the object of collector being carried out to passivation, during charging, voltage be all charged to 2.35-2.45V, and during electric discharge, voltage is all put to 1.35-1.45V, and discharge and recharge number of times is not less than 1.Collector can be metal, as metallic aluminium; Collector also can be alloy, as stainless steel or aluminium alloy.
Carry out after being assembled into battery at one to collector in the execution mode of Passivation Treatment, positive active material 14 is LiMn 2o 4, plus plate current-collecting body 12 is aluminium alloy, and negative current collector 22 is Copper Foil, electrolyte is the aqueous solution containing 1.5mol/L zinc acetate and 3mol/L lithium acetate, during charging, voltage is all charged to 2.4V, and cut-ff voltage when namely charging is 2.4V, aluminum alloy surface is oxidized under 2.4V and forms one deck passivating film; During electric discharge, cut-ff voltage is 1.4V, carries out discharge and recharge number of times be not less than 1 time to battery.The number of times of battery charging and discharging is more, and the effect of aluminium alloy passivation is better, more stable in the electrolytic solution.
In the method adopting electrochemical passivation process aluminium alloy, keep a period of time after voltage reaches 2.4V during charging, the corrosion current of aluminium alloy significantly can reduce along with the increase of holding time.Concrete, charging voltage is held time after reaching 2.4V from 10 minutes and is progressively extended to 1 hour, the corrosion current of aluminium alloy can significantly decline, hold time from 1 hour and progressively extend to 24 hours, it is not clearly that corrosion current declines, therefore, preferred, charging voltage also maintains at least 1 hour after reaching 2.4V.
Electrolyte is weak acid or neutral aqueous solution, as chlorate, sulfate, nitrate, acetate, formates or phosphate, plus plate current-collecting body 12 and negative current collector 22 can keep stable in the electrolytic solution, namely under battery operating voltage window, do not have side reaction to occur, thus ensure the stability of battery performance.The deactivating process for the treatment of of collector provided by the invention, to plus plate current-collecting body 12 and negative current collector 22 all applicable.
In order to make more even at negative pole 20 surface deposition of active ion 28 in electrolyte, negative pole 20 surface is formed with porous layer 30, and as modes such as coating, compactings, to be formed at negative pole 20 surperficial in any suitable manner for porous layer 30.
The thickness range of porous layer 30 is 0.05-1mm, and porous layer 30 has micron or sub-micron or nanoscale hole, and the volume range that micron or submicron order hole account for porous layer 30 is 50-95%.Nanoscale hole accounts for the 10-99% of porous layer 30 volume range, and the scope of the average diameter of nanoscale hole is 1-999nm, and preferably, the scope of the average diameter of nanoscale hole is 1-150nm.
Porous layer 30 does not participate in the electrochemical reaction of negative pole 20, porous layer 30 has very large specific area, larger deposition rate surface area can be provided for the active ion 28 depositing in charging process-reduce, make active ion 28 more even on negative current collector 22 surface deposition ground, the effective generation reducing negative pole dendrite.In addition, by being formed at the porous layer 30 on negative current collector 22 surface, migration distance in active ion 28 charge and discharge process can also be shortened, active ion 28 needs the shorter distance of diffusion just can complete charge and discharge process, solves the problem that there is diffusional resistance in active ion 28 course of reaction.Meanwhile, owing to being provided with porous layer 30 at negative pole 20, can use thinner barrier film when preparing battery, making in battery charging process, the oxygen that especially during overcharge, positive pole produces more easily can move to negative pole 20 and reduce, and strengthens the invertibity of battery.
The material of porous layer 30 is selected from carbon-based material, and carbon-based material is selected from least one in carbon black, activated carbon, carbon nano-tube, carbon fiber, graphite.
Carbon black includes but are not limited to section's qin carbon black (KB), acetylene black.KB has very large specific area and very strong adsorption capacity, can make active ion on negative pole 20, deposit ground more even, and chemical property when the very strong conductive capability of KB can improve the high current charge-discharge of whole battery.
Carbon-based material can be the mixture of activated carbon and binding agent, and the weight range that activated carbon accounts for porous layer 30 is 20-99%.The specific area scope of activated carbon is 200-3000m 2/ g.Concrete, by commercialization activated carbon powder (particle size range 1-200mm) and Kynoar (PVDF) Homogeneous phase mixing, add 1-METHYLPYRROLIDONE (NMP) and be dissolved into pasty state, be coated on negative current collector 22 surface.Porous layer 30 thickness range is the weight range that 0.1-0.2mm, NMP account for porous layer mixture is 50-70%.
The form of activated carbon includes but are not limited to activated carbon powder, active carbon particle, activated carbon-fiber felt or activated carbon fiber cloth, and the specific area scope of activated carbon-fiber felt or activated carbon fiber cloth is 100-2200m 2/ g.
Concrete, active carbon particle is mixed with electrically conductive graphite, then with PVDF, NMP Homogeneous phase mixing, be coated in negative current collector 22 surperficial.The thickness of porous layer 30 is between 0.1-0.2mm.The effect of electrically conductive graphite is the electronic conduction ability increasing negative pole porous layer 30.Wherein, the weight range that activated carbon accounts for porous layer 30 is 20-80%, and the weight range that electrically conductive graphite accounts for porous layer 30 is 5-20%, and the weight range that bonding agent PVDF accounts for porous layer 30 is 5-15%.Active carbon material has loose structure and larger specific area, and also the carbon-based material of carbon nano-tube class is cheap relatively for price.And the technique of the negative pole of concrete making containing porous layer is also relatively simple, easy industrialization.
Preferably, negative pole 20 surface is formed with graphene layer.Graphene has outstanding heat conductivility and mechanical property, and theoretical specific surface area is up to 2600m 2/ g, and electron mobility at a high speed under room temperature, therefore, the graphene layer being formed at negative pole 20 surface can not only provide larger surface area for the deposition of active ion 28, that can also improve negative pole 20 further leads electronic capability simultaneously, thus improves the chemical property of battery big current.
In the first embodiment, because negative pole 20 only comprises negative current collector 22, therefore, porous layer or graphene layer are formed at negative current collector 22 surface.
Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized, and solvent comprises at least one in the aqueous solution or alcoholic solution, and alcoholic solution includes but are not limited to ethanol or methyl alcohol.
Electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion 28 that dissolves at negative pole 20.
The concentration range of active ion 28 is 0.5-15mol/L.In a particular embodiment, active ion 28 comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Metal ion is present in electrolyte with forms such as chlorate, sulfate, nitrate, acetate, formates, phosphate.Preferably, metal ion is present in electrolyte with the form of the mixture of sulfate, acetate or sulfate and acetate.
Preferably, a kind of electrolyte is also comprised in electrolyte, electrolyte can ionize out at the ion 16 that positive pole 10 can reversiblely be deviate from-embed at least one charge and discharge process, thus improves positive active material 14 and the ion-exchange speed in electrolyte, improves the high rate charge-discharge performance of battery.Concrete, positive active material 14 is can the reversible compound deviating from-embed lithium ion, and what electrolyte was corresponding can also ionize out lithium ion.The reversible ion 16 deviate from-embed comprises lithium ion or sodium ion or magnesium ion or zinc ion, and the reversible ion 16 deviate from-embed concentration range is in the electrolytic solution 0.1-30mol/L.
In order to ensure battery capacity, the concentration of the active ion 28 in electrolyte must reach certain limit, when alkali crossed by electrolyte, can affect the solubility of active ion 28 in electrolyte; When electrolyte peracid, then there will be the problems such as proton embeds altogether in electrode material corrosion and charge and discharge process, therefore, in the present invention, the pH value range of electrolyte is 3-7.
Please refer to shown in Fig. 2, the charge-discharge principle of battery is: during charging, deviates from the reversible ion 16 deviate from-embed in positive active material 14, simultaneously oxidized with variable valency metal in positive active material 14, and ejected electron; Electronics arrives battery cathode 20 via external circuit, and the active ion 28 simultaneously in electrolyte obtains electronics at negative pole 20 and is reduced, and is deposited on negative current collector 22 surface, forms active ion sedimentary deposit 26.Discharge process is then the inverse process of charging, as shown in Figure 3.
In the first embodiment, working first of battery deviates from reversible ion 16, the active ion 28 deviate from-embed in positive active material 14 to reduce-be deposited as the charging process of active ion sedimentary deposit 26 at negative pole 20.The capacity of battery depends on the capacity of positive active material 14, therefore, during battery initial charge, needs to comprise enough reversible ions 16 deviate from-embed in positive active material 14.User's battery before not carrying out charging process can not use as power supply, therefore ensure that the capacity of battery is not subject to any type of loss before use.
Second execution mode
Please refer to shown in Fig. 4, second embodiment of the invention provides a kind of battery, with the difference of the battery disclosed in the first execution mode be: in the second execution mode, negative pole 20 also comprises the negative electrode active material 24 being formed at negative current collector 22 surface, and negative electrode active material 24 can be oxidized-be dissolved as active ion 28 in discharge process.
Negative current collector 22 only as the carrier of electrical conductivity and collection, does not participate in negative pole 20 and reacts, and negative electrode active material 24 to be formed on negative current collector 22 by the method for coating, plating or sputtering, and sputtering method includes but are not limited to magnetron sputtering.Concrete, negative current collector 22 is Copper Foil, and negative electrode active material 24 is zinc, and zinc is formed at copper foil surface by electric plating method.
Preferably, negative electrode active material 24 is formed on the negative current collector 22 of surface preparation, and the method for surface preparation comprises at least one in mechanical treatment, chemical treatment or electrochemical treatments.Concrete, when negative current collector 22 is Cu, carrying out pretreated method to Cu can be manual/mechanical grinding, remove the dim part in its surface makes its surface have certain roughness simultaneously, but can not remove the impurity on Cu surface thoroughly due to hand sand, as CuO, therefore further chemical treatment is needed to Cu, chemically treated method can be that the mixed liquor preparing different acid soaks it, as sulfuric acid, and nitric acid and hydrochloric acid.Pretreated concrete grammar depends on the selection of negative current collector 22, normally machinery, chemistry, electrochemistry three kinds of methods combining.
In present embodiment, negative pole 20 comprises negative current collector 22 and negative electrode active material 24, and therefore, porous layer or graphene layer are formed at negative current collector 22 surface.Negative electrode active material is formed at porous layer or graphene layer surface by modes such as coating, plating or sputterings.
Same, positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14.Plus plate current-collecting body 12 does not participate in electrochemical reaction, positive active material 14 can reversible deviate from-embedded ion, as lithium ion, sodium ion, zinc ion or magnesium ion, but in this second embodiment, positive active material 14 itself need not be limited whether containing lithium ion when preparing battery, sodium ion, zinc ion or magnesium ion, specifically, positive active material 14 can have four kinds of states: not containing the reversible ion 16 deviate from-embed, contain and the reversible ion 16 deviate from-embed can be embedded further, containing the reversible ion 16 deviate from-embed and the reversible ion 16 deviate from-embed reaches capacity state, containing the reversible ion 16 deviating from-embed and the reversible ion 16 deviate from-embed reaches hypersaturated state.
Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized, and solvent comprises the aqueous solution or alcoholic solution, and alcoholic solution includes but are not limited to ethanol and methyl alcohol.
Now, electrolyte can ionize out at least one charge and discharge process negative pole 20 reduce-deposit and be oxidized-active ion 28 that dissolves or at least one charge and discharge process in the ion 16 that can reversiblely deviate from-embed at positive pole 10 or simultaneously containing active ion 28 and the reversible ion 16 deviate from-embed.
The battery that second execution mode discloses, positive active material 14 in charge and discharge process can reversible deviate from-embedded ion, but for positive active material 14 itself, the reversible ion 16 deviate from-embed can not be comprised, the reversible ion 16 deviating from-embed can be comprised and the hole accepting the reversible ion 16 deviate from-embed in internal structure, can also be had, can also be self comprise the reversible ion 16 deviating from-embed and the state even hypersaturated state that reaches capacity, therefore, the positive active material 14 of battery has very large selection space in selection, further, active ion 28 and/or the reversible ion 16 deviate from-embed can be comprised in electrolyte, make the battery in the present invention can select different battery operated mode according to different application scenarios, battery strong adaptability.Set forth the mode of operation of the positive active material 14 of different conditions and the battery of electrolyte formation below further.
A kind of battery, comprises positive pole 10, negative pole 20, electrolyte (not shown).Positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14, positive active material 14 can reversible deviate from-embedded ion.Negative pole 20 comprises negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction.Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized.Electrolyte can ionize out at least one can there is the reversible ion 16 deviate from-embed at positive pole 10; Positive active material 14 is not containing the reversible ion 16 deviate from-embed; Working first of battery is the discharge process that in electrolyte, the reversible ion 16 deviate from-embed is embedded into positive active material 14, negative electrode active material 24 is oxidized-is dissolved as active ion 28.
Concrete, positive active material 14 is Mn 2o 4, negative electrode active material 24 is Metal Zn, comprises LiAc in electrolyte.Owing to not containing lithium in positive active material 14, and comprise lithium ion in electrolyte, therefore, battery works as Lithium-ion embeding in electrolyte is to positive active material 14 first, and negative electrode active material 24 Metal Zn is oxidized-is dissolved as Zn 2+discharge process.
Preferably, in electrolyte, also comprise the electrolyte that can ionize out active ion 28, active ion 28 negative pole 20 can reduce-deposit and be oxidized-dissolve, like this, when battery discharge, negative pole 20 and electrolyte intermediate ion exchange velocity can be accelerated.
As long as positive active material 14 to meet in charge and discharge process can reversible deviate from-this condition of embedded ion gets final product work, and positive active material 14 need not be limited must contain the reversible ion 16 deviate from-embed.Although positive active material 14 does not comprise the ion 16 that can reversiblely deviate from-embed, discharge process is required to be when battery works first, but user is when buying the battery in the present invention, can directly use as power supply equally, battery is very long simultaneously.
A kind of battery, comprises positive pole 10, negative pole 20, electrolyte.Positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14, negative pole 20 comprises negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction, electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized, electrolyte can ionize out at least one negative pole 20 reduce-deposit and be oxidized-the reversible ion 16 deviate from-embed can be there is at positive pole 10 in the active ion 28 that dissolves and at least one; The reversible ion 16 deviate from-embed can be deviate from and embed to positive active material 14; Working first of battery is that the reversible ion 16 deviate from-embed is deviate from from positive active material 14, active ion 28 to reduce and the charging process deposited or the reversible ion 16 deviate from-embed embed positive active material 14, negative electrode active material 24 is oxidized and is dissolved as the discharge process of active ion 28 at negative pole 20.
Concrete, positive active material 14 is containing Li 1-xmn 2o 4, negative electrode active material 24 is Metal Zn, comprises zinc acetate and lithium acetate in electrolyte.Positive active material 14 can deviate from Li +, meanwhile, in the spinel structure of positive active material 14, also have hole can Li in electrolysis liquid +embed, therefore, battery first mode of operation can be electric discharge: the Li in electrolyte +be embedded into Li 1-xmn 2o 4, negative electrode active material 24 Metal Zn is oxidized and is dissolved as Zn 2+; Battery first mode of operation can be charging: i.e. Li 1-xmn 2o 4in deviate from Li +, the Zn in electrolyte 2+reduce at negative pole 20 and deposit and form active ion sedimentary deposit 26.
Therefore, it both can be charging process that battery works first, also can be discharge process.User, when buying the battery in the present invention, is charge to battery or discharge to battery, can use, and battery of the present invention is very long before considering use.
Preferably, battery works as the reversible ion 16 deviate from-embed is deviate from from positive active material 14 first, the charging process that active ion 28 reduces at negative pole 20-deposits.
A kind of battery, comprise positive pole 10, negative pole 20, electrolyte, positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14, and negative pole 20 comprises negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction; Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte can ionize out at least one can there is the reversible ion 16 deviate from-embed at positive pole 10; The reversible ion 16 deviate from-embed can be deviate from and embed to positive active material 14; Working first of battery is the discharge process that the reversible ion 16 deviate from-embed embeds positive active material 14, negative electrode active material 24 is oxidized-is dissolved as active ion 28.
Concrete, positive active material 14 is containing Li 1-xmn 2o 4, negative electrode active material 24 is Metal Zn, comprises lithium acetate in electrolyte.Positive active material 14 can deviate from Li +, also can embed Li +, containing Li in electrolyte +, therefore, it is Li that battery works first +be embedded into Li 1-xmn 2o 4, Metal Zn is oxidized-is dissolved as Zn 2+discharge process.
Although battery works first and is required to be discharge process, but user is when buying the battery in the present invention, directly can uses as power supply equally, and not affecting the performance of battery, and can discharge and recharge normally after battery works first, battery is very long simultaneously.
A kind of battery, comprise positive pole 10, negative pole 20, electrolyte, positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14, positive active material 14 can reversible deviate from-embedded ion; Negative pole 20 comprises negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction; Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte can ionize out at least one and reduce-deposit and be oxidized-the active ion 28 that dissolves at negative pole 20; Battery work first be reversible deviate from-embedded ion is deviate from from positive active material 14, active ion 28 reduces at negative pole 20-deposits charging process.
Concrete, positive active material 14 is containing Li 1-xmn 2o 4, negative electrode active material 24 is Metal Zn, and containing zinc acetate in electrolyte, positive active material 14 can deviate from Li +, also can embed Li +, therefore, it is Li that battery works first +from Li 1-xmn 2o 4in deviate from, Zn in electrolyte 2+in the charging process that negative pole 20 reduces-deposits.
A kind of battery, comprise positive pole 10, negative pole 20, electrolyte, positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14, positive active material 14 can reversible deviate from-embedded ion; Negative pole 20 comprises negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction; Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte can ionize out the active ion 28 that at least one is reduced at negative pole 20-deposited; In positive active material 14, the reversible ion 16 deviate from-embed reaches capacity state; Working first of battery is the reversible charging process that ion 16 is deviate from from positive pole 10, active ion 28 reduces at negative pole 20-deposits of deviating from-embedding.
As well known to those skilled in the art, in positive active material 14, the reversible ion 16 deviate from-embed is in saturation condition, namely the reversible ion 16 deviate from-embed occupies the VOID POSITIONS in positive active material 14 structure substantially, and positive active material 14 Stability Analysis of Structures, can steady operation in battery charge and discharge process.
Battery works first and is required to be charging process, and namely the reversible ion 16 deviate from-embed is deviate from from positive active material 14, and the active ion 28 in electrolyte reduces at negative pole 20-deposits.Although user need carry out charging operations to it when buying this battery, just because of this, battery capacity can not be subject to any type of loss before first use, thus ensure that the performance that battery used in the later stage.
Preferably, in electrolyte, also comprise the electrolyte that can ionize out and the reversible ion 16 deviate from-embed can occur at positive pole 10, like this, when battery discharge, positive pole 10 and the exchange velocity of electrolyte intermediate ion can be accelerated, improve battery high rate charge-discharge performance.
Therefore, as long as electrolyte comprise can reduce-deposit at negative pole 20 and be oxidized-active ion that dissolves 28 can be able to allow battery operated, that is, in the electrolyte of this battery, only need to add active ion 28, and mandatory requirement does not need, containing the ion 16 that can reversiblely deviate from-embed, can make normal battery operation.The bath composition of battery is simple, and low cost of manufacture, battery has to be applied widely.
A kind of battery, comprise positive pole 10, negative pole 20, electrolyte, positive pole 10 comprises plus plate current-collecting body 12 and positive active material 14, positive active material 14 can reversible deviate from-embedded ion; Negative pole 20 comprises negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction; Electrolyte comprises at least one can dissolve electrolyte and the solvent that electrolyte is ionized; Electrolyte can ionize out the active ion 28 that at least one is reduced at negative pole 20-deposited; In positive active material 14, the reversible ion 16 deviate from-embed is in hypersaturated state; Working first of battery is the charging process that the reversible ion 16 deviate from-embed is deviate from from positive pole 10, active ion 28 reduces at negative pole 20-be deposited as negative electrode active material 24.
As well known to those skilled in the art, in positive active material 14, the reversible ion 16 deviate from-embed is in hypersaturated state, when namely preparing positive active material 14, be on saturated basis at positive active material 14, further embedding ion processing is carried out to positive active material 14, to improve the capacity of positive active material 14, in order to ensure the Stability Analysis of Structures of positive active material 14, the surface of positive active material 14 is modified by metal or metal oxide or coated.Concrete, metal includes but are not limited to Al, and metal oxide includes but are not limited to Al 2o 3.
Concrete, positive active material 14 is Al 2o 3coated Li 1+xmn 2o 4(0 < x < 0.5), negative electrode active material 24 is Metal Zn, comprises zinc acetate in electrolyte.Li in positive active material 14 +content reach hypersaturated state, therefore, it is Li that battery works first +from Li 1+xmn 2o 4in deviate from, Zn in electrolyte 2+the charging process of active ion sedimentary deposit 26 is reduced-is deposited as at negative pole 20.
Preferably, in electrolyte, also comprise the electrolyte that can ionize out and the reversible ion 16 deviate from-embed can occur at positive pole 10, like this, when battery charges, positive pole 10 and electrolyte intermediate ion exchange velocity can be accelerated, improve battery charging and discharging performance.
Comprise negative current collector 22 due to the negative pole 20 of battery in the second execution mode and participate in the negative electrode active material 24 of electrochemical reaction, so the mode of operation first of battery has had more selection, thus, the producer can according to the application scenario of user, select the collocation of positive pole 10, negative pole 20 and electrolyte in battery, produce the battery with different charge and discharge mode.
3rd execution mode
Third embodiment of the invention further discloses a kind of battery, the difference of the battery disclosed with the second execution mode is: in the 3rd execution mode, negative pole 20 only comprises negative current collector 22, but negative current collector 22 is not only as the carrier of electrical conductivity and collection, also be equivalent to negative electrode active material can participate in negative pole 20 and react simultaneously, can be oxidized-be dissolved as active ion 28 in battery discharge procedure, namely the material of negative current collector 22 is identical with the pure metals of active ion 28, such as: active ion 28 is zinc ion, corresponding negative current collector 22 is metallic zinc.
In the third embodiment, negative pole 20 comprises the negative current collector 22 participating in electrochemical reaction, and therefore, porous layer or graphene layer are formed at negative current collector 22 surface.Specific in the 3rd execution mode, the positive active material 14 of anode 10 is LiMn 2o 4, plus plate current-collecting body 12 is stainless (steel) wire, and negative current collector 22 is metallic zinc, and electrolyte is the aqueous solution containing zinc salt.Preferably, electrolyte is the aqueous solution containing zinc salt and lithium salts.Metallic zinc can participate in negative pole 20 and react.
When battery in the present invention is as used barrier film, barrier film can be the porous material of organic or inorganic, and the porosity ranges of barrier film is 20-95%, and pore diameter range is 0.001-100 μm.
Battery provided by the invention, there is energy density high (can reach the 60%-80% of lithium ion battery), power density (is expected reach lithium ion battery 200% greatly, even higher), be easy to manufacture, totally nontoxic, environmental protection, easy recovery and with low cost (battery of same capacity, is expected reach lead-acid battery 60%, 20% of lithium ion battery, even lower) etc. feature, and have good cycle performance, in a specific embodiment, battery still maintains more than 90% at circulation 4000 weeks rear capacity.Therefore, the battery in the present invention, as the green energy resource of a new generation, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery very much.
Weight in the present invention, the unit in percent by volume are well-known to those skilled in the art, and such as percent by volume refers to the weight of solute in the solution of 100 milliliters.Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Below in conjunction with embodiment, further illustrate content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.In the present invention, if not refer in particular to, all parts, percentage are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is conventional.
By cyclic voltammetry (CV), build three-electrode system and test different collector stability in the electrolytic solution.
Embodiment 1-1
Take stainless steel as work electrode, stainless steel model is 304, and zinc electrode is to electrode and reference electrode, at stannous sulphate electrolyte 2mol/LZnSO 4and 2mol/LLi 2sO 4in study stainless electrochemical behavior by cyclic voltammetry, voltage range is 1.0-2.4V.Stainless steel is not through Passivation Treatment.
Fig. 5 is the cyclic voltammetry curve of the stainless steel 304 of unpassivated process in embodiment 1-1.As can be seen from the figure stainless steel first anodic scan time, there is a wide oxidation peak at 1.9V (Vs.Zn) place, then occurred obvious O 2separate out peak, increase along with electric current.In cathodic scan subsequently, there is relatively little reduction peak at 1.4V place.The oxidation peak at the 1.9V place of circulating after 1 time is hindered, mean first time circulation in define oxide layer at stainless steel surfaces, oxide layer inhibits the further oxidation of stainless steel surfaces internal layer.But perhaps oxide layer can cause O 2precipitation.Therefore cause the precipitation peak of oxygen to low potential migration and become increasing.
Embodiment 1-2
With the stainless steel of passivation for work electrode, stainless steel model is 316, and zinc electrode is to electrode and reference electrode, at stannous sulphate electrolyte 2mol/LZnSO 4and 2mol/LLi 2sO 4in to be studied the stainless electrochemical behavior of passivation by cyclic voltammetry, voltage range is 1.0-2.4V.
The stainless method of passivation is chemical passivation, and detailed process is: at 50 DEG C, Stainless steel 316 is inserted the concentrated nitric acid solution of 20%, maintains 0.5h, makes stainless steel surfaces form passivating film, finally takes out stainless steel use water and cleans also dry.
Fig. 6 is the stainless cyclic voltammetry curve through Passivation Treatment in embodiment 1-2.
Experimental result is presented at solution containing oxidant as dense HNO 3in solution after passivation, stainless steel becomes more stable, and O 2precipitation peak favorable reproducibility, at different cycle period O 2precipitation peak shape significantly do not distinguish.On the other hand, O 2evolution or deposition potential moves slightly to high potential, and does not occur the precipitation of obvious oxygen before 2.0V.This result is extremely important to water system battery, because highly stable within the scope of water system battery operating voltage through the stainless steel of transpassivation.
Embodiment 1-3
With the stainless steel of passivation for work electrode, stainless steel model is 316P, and zinc electrode is to electrode and reference electrode, at nitrate electrolyte 3mol/LZn (NO 3) 2and 6mol/LLiNO 3in to be studied the stainless electrochemical behavior of passivation by cyclic voltammetry, voltage range is 1.0-2.4V.
The stainless method of passivation is with embodiment 1-2.
Fig. 7 is through Stainless steel 316 P CV curve in nitrate electrolyte of Passivation Treatment.
Embodiment 1-4
Take aluminium alloy as work electrode, zinc electrode is to electrode and reference electrode, at acetate electrolyte 1.5mol/LZn (Ac) 2with the electrochemical behavior being studied aluminium alloy in 3mol/LLiAc by cyclic voltammetry, voltage range is 1.0-2.4V, and aluminium alloy is in 2.4V lower surface generation passivation.
Embodiment 1-5
Take aluminium alloy as work electrode, zinc electrode is to electrode and reference electrode, at stannous sulphate electrolyte 2mol/LZnSO 4and 2mol/LLi 2sO 4in to be studied the electrochemical behavior of aluminium alloy by cyclic voltammetry, voltage range is 1.0-2.4V, and aluminium alloy is in 2.4V lower surface generation passivation.
Fig. 8 and Fig. 9 is respectively the CV curve of aluminium alloy in acetate and stannous sulphate electrolyte in embodiment 1-4 and 1-5.In fig. 8, having occurred significant oxidation peak first during anodic scan, there is fluctuation in electric current slightly, the nonfaradaic current that this phenomenon may produce owing to the oxidation of aluminum alloy surface or ionic adsorption or other processes.Aluminium alloy is electrochemically oxidized on surface when 2.4V, forms passivating film, for the first time after anodic scan, at 1.0-2.1V all without any peak, and O 2evolution or deposition potential moves to high potential, analyses oxygen electric current and diminishes.Show that the aluminium alloy after electrochemical passivation is highly stable within the scope of water system battery operating voltage.
Embodiment 1-6
Take graphite foil as work electrode, zinc electrode is to electrode and reference electrode, at hydrochloride electrolyte 4mol/LZnCl 2with the electrochemical behavior being studied graphite foil in 3mol/LLiCl by cyclic voltammetry.
Embodiment 1-7
With the stainless steel of unpassivated process for work electrode, zinc electrode is to electrode and reference electrode, at hydrochloride electrolyte 4mol/LZnCl 2with the stainless electrochemical behavior being studied unpassivated process in 3mol/LLiCl by cyclic voltammetry.
Figure 10 and Figure 11 is respectively the CV curve of embodiment 1-6 and 1-7.Can find out that graphite foil is relatively stable in solution of chlorate by CV curve, except there is the precipitation of oxygen under high potential except, significantly oxidation or reduction peak is there is not under whole electrochemical window, this phenomenon demonstrates carbon-based material and is adapted at as collector in solution of chlorate, and the stainless steel of unpassivated process is not too suitable for solution of chlorate.
By Tafel curve, build three-electrode system and test the corrosion rate of different collector in acetate electrolyte.
Embodiment 2-1
Take aluminium foil as work electrode, zinc is to electrode and reference electrode, at acetate electrolyte 1.5mol/LZn (Ac) 2with in 3mol/LLiAc, studied the corrosion behavior of aluminium foil by Tafel curve.
Embodiment 2-2
Using stainless steel 304 rod as work electrode, its excess-three electrode composition and test condition are with embodiment 2-1.
Embodiment 2-3
Using graphite rod as work electrode, its excess-three electrode composition and test condition are with embodiment 2-1.
Embodiment 2-4
Using aluminium alloy as work electrode, its excess-three electrode composition and test condition are with embodiment 2-1.
Embodiment 2-5
Using the stainless steel 304 of passivation as work electrode, its excess-three electrode composition and test condition are with embodiment 2-1.Concrete stainless steel is by chemical passivation process.
Embodiment 2-6
With the aluminium alloy of passivation for work electrode, its excess-three electrode composition and test condition are with embodiment 2-1.Aluminium alloy, by electrochemical passivation process, carries out discharge and recharge to aluminium alloy, charge and discharge cycles 1 time.
Embodiment 2-7
Using the aluminium alloy of passivation as work electrode, its excess-three electrode composition and test condition are with embodiment 2-1.Concrete aluminium alloy, by electrochemical passivation process, carries out discharge and recharge to aluminium alloy, electrochemical passivation charge and discharge cycles 50 times.
Corrosion current can obtain from Tafel curve and formula 1.Based on the area of work electrode, density and possible corrosion mechanism (quantity of electron transfer in corrosion process), obtain the corrosion rate of several different plus plate current-collecting body as shown in table 1, wherein.R is corrosion resistance, I corrfor corrosion current.
Formula 1: i = nFA k 0 { - c O exp [ - &alpha; nF RT ( E - E 0 ) ] + c R exp [ ( 1 - &alpha; ) nF RT ( E - E 0 ) ) ] }
Table 1
As can be seen from Table 1: the corrosion rate of aluminium foil is the highest, stainless steel and the aluminium alloy corrosion rate in Acetate Solution is little compared to aluminium foil 10 times.Respectively through the stainless steel after chemical passivation and electrochemical passivation process and aluminium alloy corrosion rate decline 6-12 doubly.Further, the corrosion rate after the further electrochemical oxidation of aluminium alloy also can decline further, and electrochemicial oxidation 50 the post-etching speed that circulate decline 150 times.This result and CV result are coincide, and CV result is analysed oxygen curve after showing circulation for several times and died down.
Further, the chemical property of battery is studied by specific embodiment.
Embodiment 3-1
With LiMn 2o 4for positive active material, positive active material, conductive agent acetylene black (AB), binding agent Kynoar (PVDF) are mixed according to the part by weight of 83: 10: 7 and are dissolved in obtained anode sizing agent in 1-METHYLPYRROLIDONE (NMP).Plus plate current-collecting body is graphite foil, is evenly coated on plus plate current-collecting body by anode sizing agent, dryly at 110 DEG C in atmosphere within 24 hours, makes positive pole.Battery cathode collector is stainless steel.Electrolyte is be the aqueous solution of 4mol/L zinc chloride and 3mol/L lithium chloride containing concentration, by the pH value of electrolyte being adjusted to 4 toward titration 0.1mol/L lithium hydroxide in electrolyte.Barrier film is glass felt-cloth.Positive pole, negative pole are assembled into battery, and centre separates with barrier film, injects electrolyte.Treat battery pack install after leave standstill within 12 hours, start subsequently with 4C multiplying power charging and discharging.Charging/discharging voltage interval is 1.4-2.15V.
The voltage of the battery that Figure 12 provides for embodiment of the present invention 3-1 and the relation curve of discharge capacity, the coulombic efficiency of battery is about 97%, also shows the excellent electrochemical performance of battery and does not almost have side reaction to occur in cyclic process simultaneously.
The discharge capacity of the battery that Figure 13 provides for embodiment of the present invention 3-1 and the relation curve of cycle-index, as can be seen from the figure, battery initial capacity is 0.35mAh, specific capacity based on positive electrode is 117mAhg-1, and the volumetric efficiency of circulating battery after 1000 weeks still has 90%, show that the cycle performance of battery is very good.
Embodiment 3-2
In embodiment 3-6, battery positive electrode active material is Li 1.08co 0.03al 0.03mn 1.94o 4, all the other batteries form identical with embodiment 3-1 with assemble method.
The discharge capacity of the battery that Figure 14 provides for embodiment 3-2 and the relation curve of cycle-index, as can be seen from the figure, the volumetric efficiency of circulating battery after 4000 weeks still has 95%, shows the LiMn adopting doping vario-property process 2o 4the cycle life of the battery of positive active material obtains raising further.
Embodiment 3-3
With Li 1.05mn 1.89co 0.03al 0.03o 4for positive active material, positive active material, binding agent PVDF, super-p carbon black are mixed according to the part by weight of 83: 10: 7 and are dissolved in obtained anode sizing agent in 1-METHYLPYRROLIDONE (NMP), plus plate current-collecting body is the graphite cake of thickness 1mm.Charging/discharging voltage interval is 1.5-2.1V.All the other formations of battery and method of testing are with embodiment 3-1.
Figure 15 is the discharge capacity of the battery that embodiment 3-3 provides and the relation curve of cycle-index, can clearly find out from figure, the discharge capacity that circulating battery is 4000 times is with discharge capacity is almost equal first, and battery not only cycle performance is highly stable, and has extended cycle life.
Figure 16 is the coulombic efficiency of the battery that embodiment 3-3 provides and the relation curve of cycle-index, and as can be seen from the figure after circulating battery 4000 times, coulombic efficiency, still close to 100%, shows that the charge-discharge performance of the battery in the present invention is highly stable.
Embodiment 3-4
With LiMn 2o 4for positive active material, positive active material, polyfluortetraethylene of binding element (PTFE), super-p carbon black are mixed according to the ratio of 83: 10: 7 and are dissolved in obtained anode sizing agent in 1-METHYLPYRROLIDONE (NMP).Plus plate current-collecting body is the stainless (steel) wire of thickness 30 μm, and anode sizing agent, without passivation, is evenly coated on plus plate current-collecting body by stainless steel, dryly at 110 DEG C in atmosphere within 24 hours, makes positive pole.Battery cathode collector is thickness 10 μm of Copper Foils.Electrolyte is be the aqueous solution of 1mol/L lithium acetate and 1.5mol/L zinc acetate containing concentration, by the pH value of electrolyte being adjusted to 4 toward titration 0.1mol/L lithium hydroxide in electrolyte and 0.1mol/LHAc.Barrier film is glass felt-cloth.Positive pole, negative pole are assembled into battery, and centre separates with barrier film, injects electrolyte.Treat battery pack install after leave standstill within 12 hours, start subsequently with 0.5C multiplying power charging and discharging.Charging/discharging voltage interval is 1.5-2.1V.
Figure 17 is the discharge capacity of the battery that embodiment 3-4 provides and the relation curve of cycle-index.Can clearly see from figure: battery first discharge capacity is, the discharge capacity after 250 times that circulates and discharge capacity first almost do not have difference, and show that the cycle performance of battery is highly stable, battery provided by the invention has excellent chemical property.
Embodiment 4-1
With LiMn 2o 4for positive active material, according to the ratio of positive active material 90%, conductive carbon black 6%, bonding agent SBR (butadiene-styrene rubber breast) 2%, thickener CMC (sodium carboxymethylcellulose) 2%, first CMC is mixed with certain water gaging, add positive active material and conductive carbon black again, stir 2 hours, finally add SBR and stir and obtain anode sizing agent in 10 minutes.Plus plate current-collecting body is the graphite foil of thickness 0.1mm, is evenly coated on plus plate current-collecting body by anode sizing agent, thickness 0.3mm, and 120 degree of oven dry make positive plate in 12 hours.Battery cathode collector is the graphite foil of thickness 0.1mm.By activated carbon powder, (coconut husk is fired, specific area 1500m 2/ g), conductive carbon black, PVDF mixes with the ratio of 90: 5: 5, adds NMP and is dissolved, and be evenly coated in obtained porous layer in negative current collector graphite foil, thickness is 0.1mm.Electrolyte is be the aqueous solution of 4mol/L zinc chloride and 3mol/L lithium chloride containing concentration, and barrier film is nonwoven fabrics barrier film.By positive plate, negative plate is assembled into battery, and centre separates with barrier film.Inject electrolyte, electrolyte major part is stored in porous layer, the Zn in charge and discharge process in electrolyte 2+/ Zn reduces-deposits at negative pole and oxidation-solubilizing reaction, especially reduces-deposits and oxidation-solubilizing reaction on porous layer inside and the interface between porous layer and negative current collector.Figure 18 is the structural representation that negative pole currect collecting surface of the present invention is formed with porous layer.In charge and discharge process, zinc is in cathode deposition/dissolving.In activated carbon, micron-sized hole effectively can adsorb a large amount of electrolyte and provide zinc to deposit basic point.Figure 19 is the partial enlarged drawing of porous layer in Figure 18, obviously can see the active ion sedimentary deposit 26 being deposited on porous layer inside.Treat battery pack install after leave standstill within 12 hours, start subsequently with 1C multiplying power charging and discharging.Charging/discharging voltage interval is 1.4-2.15V (namely with the electric current constant current charge of 100mAh to 2.15V, then constant-current discharge is to 1.4V, cycling like this).Figure 20 is the LiMn of embodiment of the present invention 4-1 2o 4/ Zn battery first charge-discharge voltage-capacity curve chart.
Embodiment 4-2
The mode identical with embodiment 4-1 manufactures battery, unlike zinc-plated as battery cathode collector using Copper Foil.Relative graphite foil, Copper Foil electric conductivity is better, and mechanical strength is higher, also thinner.Adopt Copper Foil to be conducive to improving the negative discharge performance of battery, also can reduce battery volume simultaneously, improve the volume energy density of battery.But simple Copper Foil can not as the negative pole of ion-exchange battery, because at copper foil surface, the efficiency of zinc deposition is very low.Therefore, one deck tin can be plated at copper foil surface, to improve deposition efficiency.
Because negative current collector itself can not affect the performance of battery greatly, with this execution mode do charging and discharging curve and execution mode one basic simlarity of battery.
Embodiment 4-3
The mode identical with embodiment 4-1 manufactures battery, unlike using commercially available activated carbon fiber cloth as battery porous layer.Microstructure and the activated carbon of this active carbon cloth are similar, and thickness (uncompressed) is about 0.5mm, after compression between 0.1-0.2mm.The specific area of this activated carbon fiber cloth is 800m 2/ g.Activated carbon fiber cloth and negative current collector are cut into onesize, overlapping successively according to negative current collector-activated carbon fiber cloth-nonwoven fabrics barrier film-anode electrode.The structure of the battery formed with this is identical with the battery structure shown in Figure 15, and just the material of porous layer comprises activated carbon fiber cloth.Clearly, the structure of the battery that method above manufactures is simple, can carry out suitability for industrialized production at faster speed.The same with the porous layer be made up of activated carbon mentioned in execution mode one and execution mode two, activated carbon fiber cloth also can provide enough large negative pole specific area.
Embodiment 5-1
With LiMn 2o 4for positive active material, mix according to positive active material, active carbon black, bonding agent PVDF weight ratio 8: 1: 1, be cut into the disk of diameter 12mm, thickness 0.1-0.2mm, be compressed on aluminium alloy collector, make positive pole.Negative pole is the metallic zinc of diameter 12mm, thickness 1mm, and metallic zinc doubles as negative electrode active material and negative current collector.Interval 5mm between positive and negative electrode, barrier film is filter paper.Electrolyte is containing 4mol/L lithium ion and the lithium sulfate of 2mol/L zinc ion and the mixed aqueous solution of zinc sulfate, and the LiOH being added 0.1mol/L by titration regulates the pH of electrolyte to be 5.
Carry out discharge and recharge to battery, voltage range is 1.4-2.4V, and sweep speed is 0.5mV/s.Plus plate current-collecting body aluminium alloy surface when high voltage 2.4V forms passivating film.
Embodiment 5-2
In embodiment 5-2, plus plate current-collecting body is the alloy foil of thickness 50 μm, and negative pole is the metallic zinc paper tinsel of thickness 50 μm, and electrolyte is 1.5mol/LZn (Ac) 2and 2mol/LLiAc, barrier film is glass felt-cloth, and all the other batteries composition and method of testing are with embodiment 5-1.
Figure 21 and Figure 22 is respectively the CV curve chart of the battery that embodiment 5-1 and 5-2 provides.As can be seen from the figure, anode and cathodic scan are all to having two significant oxidation peak (1.95V and 1.85V) and two reduction peak (1.85V and 1.7V) each time, and this and lithium ion deviating from organic bath/embed mechanism is consistent.Except these two obvious oxidation-reduction pairs, have also appeared less oxidation peak after circulation primary, peak current appears at 1.6V, and the cause of this oxidation peak may be deviating from-embedding of proton.The stability that this result demonstrates battery of the present invention is further fine, and has excellent charge-discharge performance.
In addition, the coulombic efficiency of the battery in embodiment 5-2 after circulation 600 times, still close to 90%, shows that the efficiency for charge-discharge of battery is very high.
Embodiment 5-3
In embodiment 5-3, plus plate current-collecting body is the stainless steel 304 through transpassivation, and the thickness of stainless steel 304 is 50 μm, and electrolyte is 2mol/LZnSO 4and 2mol/LLi 2sO 4, barrier film is glass felt-cloth, and all the other batteries composition is with embodiment 5-1, and charging/discharging voltage interval is 1.4-2.1V.The stainless method of concrete passivation is: at 50 DEG C, and the red fuming nitric acid (RFNA) of stainless steel being inserted 20% reaches half an hour, makes stainless steel surfaces form one deck passivating film.
Figure 23 is the CV curve of battery in embodiment 5-3.
Embodiment 5-4
In embodiment 5-4, plus plate current-collecting body is the stainless steel 304 through transpassivation, and electrolyte is 3mol/LZn (NO 3) 2and 6mol/LLiNO 3, all the other batteries composition is with embodiment 5-1, and charging/discharging voltage interval is 1.4-2.2V.The stainless method of concrete passivation is with embodiment 5-3.
Figure 24 is the CV curve of battery in embodiment 5-4.
Embodiment 5-5
The mode identical with embodiment 5-1 manufactures battery, difference be with thickness be 1mm through Passivation Treatment 304 type stainless steels replace graphite foil as plus plate current-collecting body, concrete Passivation Treatment process is: at 50 DEG C, the nitric acid of stainless steel being inserted 20% reaches half an hour, makes stainless steel surfaces form one deck passivating film.Electrolyte is be the aqueous solution of 1.5mol/L zinc acetate and 3mol/L lithium acetate containing concentration.Battery cathode is metallic zinc.Treat that battery pack leaves standstill 12 hours after installing, start subsequently to carry out charging and discharging with 1mA constant current to battery.Charging/discharging voltage interval is 1.4-2.2V.
Embodiment 5-6
The mode identical with embodiment 5-1 manufactures battery, and difference replaces 304 type stainless steels as plus plate current-collecting body using 316 type stainless steels of Passivation Treatment, and concrete Passivation Treatment process is with embodiment 5-5.Treat that battery pack leaves standstill 12 hours after installing, start subsequently to carry out charging and discharging with the constant current of 1mA and 3mA to battery respectively.Charging/discharging voltage interval is 1.4-2.2V.
Figure 25 is the CV curve of battery in embodiment 5-6.
Embodiment 5-7
The mode identical with embodiment 5-6 manufactures battery, and to be electrolyte be difference is the aqueous solution of 3mol/L zinc sulfate and 3mol/L lithium sulfate containing concentration.Treat that battery pack leaves standstill 12 hours after installing, start subsequently to carry out charging and discharging with the constant current of 1mA, 2mA, 3mA to battery respectively.Charging/discharging voltage interval is 1.4-2.2V.
Embodiment 5-8
The mode identical with embodiment 5-7 manufactures battery, and difference is using the metallic aluminium of Passivation Treatment as plus plate current-collecting body.To the process of metallic aluminium Passivation Treatment be: treat that battery pack leaves standstill 12 hours after installing, start subsequently to carry out charging and discharging with 1mA constant current to battery, during charging, voltage is all charged to 2.4V, and namely charging/discharging voltage interval is 1.4-2.4V, makes metallic aluminum surface form one deck passivating film.
Capability retention is tested
By carrying out discharge and recharge operation to the battery in embodiment 5-1 to 5-8, to detect the cycle performance of battery.
Table 2 is the battery discharge and recharge under 1mA constant current in embodiment 5-1 to 5-8, and circulate the battery performance of 80 times:
Table 2
As can be seen from Table 2, through Passivation Treatment stainless steel as plus plate current-collecting body battery performance from capability retention and efficiency for charge-discharge two aspect all more excellent.
Embodiment 5-6 is tested with the constant current charge-discharge of 3mA, the capability retention after 80 times that circulates is 94%, efficiency for charge-discharge is 98%, and battery performance is better than with 1mA constant current charge-discharge test result, illustrates that the battery in the present invention has excellent battery performance under big current.
Test with the constant current charge-discharge of 2mA, 3mA embodiment 5-7, the capability retention after 80 times that circulates is respectively 92% and 72%, and efficiency for charge-discharge is 99%, and the battery that embodiment 5-7 provides is best with the battery performance of 2mA constant current charge-discharge.
Embodiment 5-9
With LiMn 2o 4for positive active material, mix according to positive active material, active carbon black, bonding agent PVDF weight ratio 8: 1: 1, be coated on the stainless steel collector of passivation, make positive pole.Passivation for stainless steel method is with embodiment 5-3.Negative pole is the metallic zinc paper tinsel of thickness 50 μm, and metallic zinc doubles as negative electrode active material and negative current collector.Barrier film is glass felt-cloth.Electrolyte is the mixed aqueous solution containing 2mol/L lithium acetate, 1.5mol/L zinc acetate and 1mol/L zinc sulfate, regulates electrolyte pH to be 5.
Carry out discharge and recharge to battery, voltage range is 1.4-2.1V, and sweep speed is 0.5mV/s.
The CV curve of the battery that Figure 26 provides for embodiment 5-9, experimental result shows, and battery, shows to adopt the battery of mixed electrolyte salt to have stable charge-discharge performance close to 100% at the coulombic efficiency of circulation 200 times.
Embodiment 6-1
With LiMn 2o 4for positive active material, positive active material, super-p carbon black, bonding agent PVDF are mixed according to part by weight 83: 10: 7, using NMP as dispersant, obtained anode sizing agent, evenly be coated in the plus plate current-collecting body graphite foil of thickness 80 μm, dry, compacting subsequently obtains positive pole.Negative pole is the metallic zinc paper tinsel of thickness 50 μm, and metallic zinc is negative electrode active material, simultaneously also doublely does negative current collector.Barrier film is glass felt-cloth.Electrolyte is the deionized water solution containing 3mol/L lithium chloride and 4mol/L zinc chloride, regulates the pH of electrolyte to be 4 by the LiOH solution dripping 0.1mol/L in electrolyte.Under room temperature, with 4C multiplying power, discharge and recharge is carried out to battery at voltage range 1.5-2.1V.
Figure 27 is the relation curve of battery first charge-discharge in embodiment 6-1 and voltage, as can be seen from the figure battery first discharge capacity be about 0.35mAh.
Figure 28 is the relation curve of discharge capacity of the cell and cycle-index, and the capacity of battery battery after circulation 1000 times still remains on more than 85%, and capacity attenuation is very little, shows that battery has extraordinary stability.
Figure 29 is the relation curve of battery coulombic efficiency and cycle-index, and as can be seen from the figure the coulombic efficiency of battery after circulation 1000 times is more than 80%.
Embodiment 6-2
With LiMn 2o 4for positive active material, positive active material, super-p carbon black, bonding agent PVDF are mixed according to part by weight 83: 10: 7, using NMP as dispersant, obtained anode sizing agent, evenly be coated in the plus plate current-collecting body graphite foil of thickness 80 μm, dry, compacting subsequently obtains positive pole.Negative pole is the metallic zinc paper tinsel of thickness 50 μm, and metallic zinc is negative electrode active material, simultaneously also doublely does negative current collector.Barrier film is non-woven fibre cloth.Electrolyte is the aqueous solution containing 3mol/L lithium chloride and 4mol/L zinc chloride, regulates the pH of electrolyte to be 4 by the LiOH solution dripping 0.1mol/L in electrolyte.Under room temperature, with 1C multiplying power, discharge and recharge is carried out to battery at voltage range 1.5-2.1V.
The discharge capacity of the battery that Figure 30 provides for embodiment 6-2 and the relation curve of cycle-index, battery capacity after circulation 30 times is slightly decayed, but rate of decay is very slow.
Figure 31 is the relation curve of battery coulombic efficiency and cycle-index, the coulombic efficiency of battery after circulation 30 times nearly 90%.
Embodiment 6-3
With LiMn 2o 4for positive active material, positive active material, super-p carbon black, bonding agent CMC-SBR are mixed according to part by weight 83: 10: 7, using NMP as dispersant, obtained anode sizing agent, evenly be coated on the plus plate current-collecting body stainless steel foil of thickness 50 μm, stainless steel is without passivation, and dry, compacting subsequently obtains positive pole.Negative pole is the metallic zinc paper tinsel of thickness 40 μm, and metallic zinc is negative electrode active material, simultaneously also doublely does negative current collector.Barrier film is glass felt-cloth.Electrolyte is the aqueous solution containing 1mol/L lithium acetate and 1.5mol/L zinc acetate, regulates the pH of electrolyte to be 4 by LiOH and the 0.1mol/LHAc solution dripping 0.1mol/L in electrolyte.Under room temperature, with 0.5C multiplying power, discharge and recharge is carried out to battery at voltage range 1.5-2.1V.
Cell Experimentation An result display in embodiment 6-3, the discharge capacitance that circulating battery is 320 times and coulombic efficiency, all close to 100%, show that battery has very excellent cycle performance and life-span.
Embodiment 6-4
In embodiment 6-4, carry out discharge and recharge at battery being placed in 55 DEG C, to study battery charge-discharge performance at high temperature, other compositions of battery and method of testing are with embodiment 6-3.
The discharge capacity of the battery that Figure 32 provides for embodiment 6-4 and the relation curve of cycle-index, as can be seen from the figure, battery, under 55 DEG C of high temperature, still has good discharge capacitance, and circulating battery does not almost have obvious capacity attenuation 160 times.
Embodiment 6-5
With LiMn 2o 4for positive active material, positive active material, super-p carbon black, bonding agent PVDF are mixed according to part by weight 83: 10: 7, using NMP as dispersant, obtained anode sizing agent, evenly be coated on the plus plate current-collecting body stainless (steel) wire of thickness 30 μm, stainless steel is without passivation, and dry, compacting subsequently obtains positive pole.Negative pole is the metallic zinc paper tinsel of thickness 10 μm, and metallic zinc is negative electrode active material, simultaneously also doublely does negative current collector.Barrier film is glass felt-cloth.Electrolyte is the aqueous solution containing 1mol/L lithium acetate and 1.5mol/L zinc acetate, regulates the pH of electrolyte to be 4 by LiOH and the 0.1mol/LHAc solution dripping 0.1mol/L in electrolyte.Under room temperature, with 0.5C multiplying power, discharge and recharge is carried out to battery at voltage range 1.5-2.1V.
The discharge capacity of the battery that Figure 33 provides for embodiment 6-5 and the graph of relation of cycle-index, as can be seen from the figure, circulating battery 30 discharge capacities almost do not decay, and show that battery charging and discharging stability provided by the invention is good.
Embodiment 7-1
With LiMn 2o 4for positive active material, by positive active material, super-p carbon black, bonding agent PVDF according to part by weight 8: 1: mix, using NMP as dispersant, obtained anode sizing agent, evenly be coated in the plus plate current-collecting body graphite foil of thickness 80 μm, dry, compacting subsequently obtains positive pole.Negative current collector is the graphite foil of thickness 50 μm, and metallic zinc is plated in graphite foil as negative electrode active material.Barrier film is glass felt-cloth.Electrolyte is the aqueous solution containing 2mol/L lithium acetate and 1.5mol/L zinc acetate, regulates the pH of electrolyte to be 4 by the LiOH solution dripping 0.1mol/L in electrolyte.Under room temperature, with 0.5C multiplying power, discharge and recharge is carried out to battery at voltage range 1.5-2.1V.
Embodiment 7-2
The mode identical with embodiment 7-1 manufactures battery, and difference is that 316 type stainless steels replace graphite foil as negative current collector.
Embodiment 7-3
The mode identical with embodiment 7-1 manufactures battery, and difference is that Copper Foil replaces graphite foil as negative current collector.
The battery that embodiment 7-1 to 7-3 provides, battery has good cycle performance.
Although inventor has done more detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, to those skilled in the art, above-described embodiment to be modified and/or flexible or adopt equivalent replacement scheme to be obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.

Claims (18)

1. a battery, comprises positive pole, and negative pole and electrolyte, is characterized in that:
Described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, and lithium ion, sodium ion or magnesium ion can deviate from-embedded to described positive active material reversiblely;
Described negative pole at least comprises negative current collector;
Described electrolyte comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes; Described electrolyte can ionize out at least one charge and discharge process and reduce-deposit and be oxidized-the active ion that dissolves at described negative pole, and described active ion comprises metal ion, and described metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni;
Described negative pole currect collecting surface is formed with porous layer, and described porous layer has micron or sub-micron or nanoscale hole.
2. battery according to claim 1, is characterized in that: described porous layer is graphene layer.
3. battery according to claim 1 and 2, is characterized in that: the thickness range of described porous layer or graphene layer is 0.05-1mm.
4. battery according to claim 1, is characterized in that: the volume range that described micron or submicron order hole account for described porous layer is 50-95%.
5. battery according to claim 1, is characterized in that: the volume range that described nanoscale hole accounts for described porous layer is 10-99%.
6. battery according to claim 1, is characterized in that: the scope of the average diameter of described nanoscale hole is 1-150nm.
7. battery according to claim 1, is characterized in that: the material of described porous layer is selected from carbon-based material.
8. battery according to claim 7, is characterized in that: described carbon-based material is selected from least one in section's qin carbon black, activated carbon, carbon nano-tube, carbon fiber, graphite.
9. battery according to claim 7, is characterized in that: described carbon-based material is the mixture of activated carbon powder and binding agent, and the weight percentage ranges that described activated carbon powder accounts for described porous layer is 20-99%.
10. battery according to claim 1, is characterized in that: described negative pole also comprises the negative electrode active material being formed at described negative pole currect collecting surface, and described negative electrode active material can be oxidized-be dissolved as described active ion in described battery discharge procedure.
11. batteries according to claim 1, is characterized in that: material selected from metal Ni, Cu, Ag, Pb, Sn, Fe, Al of described negative current collector or the one in the above-mentioned metal of Passivation Treatment.
12. batteries according to claim 1, it is characterized in that: the material of described negative current collector is selected from carbon-based material, stainless steel, silicon or has the metal of plating/coating, described plating/coating contains at least one in the simple substance of C, Sn, In, Ag, Pb, Co, Zn, alloy or oxide.
13. batteries according to claim 12, is characterized in that: the thickness range of described plating/coating is between 1-1000nm.
14. batteries according to claim 1, is characterized in that: described metal ion is present in described electrolyte with at least one form in chlorate, sulfate, nitrate, acetate, formates, phosphate.
15. batteries according to claim 1, is characterized in that: the material of described plus plate current-collecting body be selected from graphite, stainless steel, aluminium alloy, through the stainless steel of transpassivation or aluminium alloy.
16. 1 kinds of batteries, comprise positive pole, negative pole, electrolyte, it is characterized in that:
Described positive pole comprises positive active material, and lithium ion, sodium ion or magnesium ion can deviate from-embedded to described positive active material reversiblely;
Described negative pole comprises the negative electrode active material participating in electrochemical reaction;
Described electrolyte comprises at least one and can dissolve electrolyte and make the solvent that described electrolyte ionizes;
Described electrolyte can ionize out at least one charge and discharge process described negative pole reduce-deposit and be oxidized-active ion that dissolves is or/and can the reversible ion deviate from-embed at described positive pole at least one charge and discharge process, described negative electrode active material can be oxidized-be dissolved as described active ion in discharge process, described active ion comprises metal ion, and described metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni;
Described negative pole also comprises the porous layer being formed at described negative electrode active material surface, and described porous layer has micron or sub-micron or nanoscale hole.
17. batteries according to claim 16, is characterized in that: described porous layer is graphene layer.
18. 1 kinds of batteries, comprise positive pole, negative pole, electrolyte and barrier film, it is characterized in that:
Described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, and described positive active material is can the reversible compound deviating from-embed lithium ion, sodium ion or magnesium ion;
Described negative pole is the electrochemicaUy inert conductive electrode not participating in electrochemical reaction;
Described electrolyte is the aqueous solution, and at least reduce-deposit and be oxidized-the metal ion that dissolves containing in charge and discharge process at described negative pole, described metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni;
Described negative pole comprises negative current collector and is formed at the porous layer with micro-void of described negative pole currect collecting surface.
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Publication number Priority date Publication date Assignee Title
CN104681846A (en) * 2013-11-29 2015-06-03 苏州宝时得电动工具有限公司 Battery and electrolytic solution thereof
CN104733787B (en) * 2013-12-20 2017-05-03 苏州宝时得电动工具有限公司 Battery
CN103943380B (en) * 2014-04-24 2018-09-04 陆艾珍 The preparation method of carbon porous electrode
CN105336956A (en) * 2014-06-06 2016-02-17 苏州宝时得电动工具有限公司 Battery
CN105449240A (en) * 2014-09-28 2016-03-30 苏州宝时得电动工具有限公司 Flow battery system
CN105895923A (en) * 2016-05-18 2016-08-24 河南田园新能源科技有限公司 Preparation method of primer used for coating cathode piece of copper foil current collector
CN106384838A (en) * 2016-11-03 2017-02-08 上海空间电源研究所 Atomic layer deposition modified lithium-ion battery and preparation method thereof
WO2018119957A1 (en) * 2016-12-29 2018-07-05 深圳先进技术研究院 Porous tinfoil anode and method for preparing same, and sodium-ion secondary battery
CN107871861A (en) * 2017-05-15 2018-04-03 中国科学院金属研究所 A kind of water system sodium ion electrochemical energy storage device
JP6662353B2 (en) * 2017-07-18 2020-03-11 トヨタ自動車株式会社 Negative electrode current collector, negative electrode, and aqueous lithium ion secondary battery
CN107482224A (en) * 2017-08-04 2017-12-15 珠海光宇电池有限公司 Negative plate and preparation method thereof and lithium battery
JP2019053930A (en) * 2017-09-15 2019-04-04 トヨタ自動車株式会社 Aqueous lithium ion secondary battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201450056U (en) * 2009-07-01 2010-05-05 江苏双登集团有限公司 Polyester lithium ion electrokinetic cell pole piece
CN102055029A (en) * 2010-12-17 2011-05-11 复旦大学 High-safety aqueous and organic mixed lithium ion battery
CN102208598A (en) * 2011-05-12 2011-10-05 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2412484B (en) * 2004-07-27 2006-03-22 Intellikraft Ltd Improvements relating to electrode structures in batteries
CN101540417B (en) * 2009-04-15 2011-01-26 清华大学深圳研究生院 Rechargeable zinc ion battery
WO2011079482A1 (en) * 2009-12-29 2011-07-07 万向电动汽车有限公司 Battery
CN102005615B (en) * 2010-09-29 2013-01-09 清华大学深圳研究生院 Rechargeable nickel ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201450056U (en) * 2009-07-01 2010-05-05 江苏双登集团有限公司 Polyester lithium ion electrokinetic cell pole piece
CN102055029A (en) * 2010-12-17 2011-05-11 复旦大学 High-safety aqueous and organic mixed lithium ion battery
CN102208598A (en) * 2011-05-12 2011-10-05 中国科学院宁波材料技术与工程研究所 Electrode plate of graphene coating modified lithium secondary battery and manufacturing method thereof

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