CN102903924A - Battery - Google Patents

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Publication number
CN102903924A
CN102903924A CN2012101787227A CN201210178722A CN102903924A CN 102903924 A CN102903924 A CN 102903924A CN 2012101787227 A CN2012101787227 A CN 2012101787227A CN 201210178722 A CN201210178722 A CN 201210178722A CN 102903924 A CN102903924 A CN 102903924A
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battery
electrolyte
ion
active material
negative pole
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CN2012101787227A
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CN102903924B (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

The invention discloses a battery. The battery comprises an anode, a cathode and an electrolyte solution. The anode comprises an anode current collector and an anode active material which undergoes an electrochemical reaction and can realize reversible release of an embedded ion. The cathode at least comprises a cathode current collector. The electrolyte solution comprises at least one solvent which can dissolve electrolytes and ionize the electrolytes, and the electrolytes can be ionized into at least one type of active ions which can undergo a reduction-deposition reaction and an oxidation-dissolution reaction at the cathode in a charge-discharge process. A porous layer or a graphene layer is formed on the surface of the cathode and the porous layer has micron scale, submicron scale or nanoscale apertures. The battery can be operated safely, has a low production cost, a long service life and good cycling performances, and can be used as a substitute of an energy storage system and a lead acid battery in the field of large-scale energy storage.

Description

Battery
Technical field
The invention belongs to the electrochemical energy storage field, be specifically related to a kind of battery.
Background technology
Human extensive utilization to new forms of energy has caused the rapidly expansion in secondary cell market.In the current new forms of energy system to secondary cell require ubiquitous.No matter be electric automobile, wind energy, solar grid-connected or peak load regulation network all is badly in need of a kind of cheapness, and is reliable, the secondary cell that safety and life-span are long.The secondary cell that develops 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 advantages of separately, and such as lithium ion battery with high-temperature sodium sulphur battery life is long and energy density is high, vanadium flow battery possesses the unlimited life-span etc. especially in theory.But which kind of battery no matter, all can't satisfy simultaneously cheap, reliable, the requirement that safety and life-span are long.Traditional lithium ion battery is too expensive, and potential safety hazard is arranged; High-temperature sodium sulphur battery manufacture technical threshold is high, fetch long price; The multinomial technical bottleneck of vanadium flow battery all fails to obtain breakthrough etc. at present.
Many researchers all is devoted to the research of aquo-lithium ion battery for this reason, wishes significantly to reduce the cost of lithium ion battery and improve fail safe with this, and has proposed some with LiMn 2O 4Be positive pole, the oxide of vanadium is LiV for example 3O 8Deng being the battery of electrolyte for negative pole, water, but therefore the poor stability and the vanadium that discharge and recharge in water of class negative pole has certain toxicity, thereby limited the development of this type of battery.So far, the structure of the aquo-lithium ion secondary cell that has proposed is all failed to break away from based on lithium ion and is deviate from-structure of embedding principle, such as the VO that report is arranged 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 the battery of a kind of low cost, safe and reliable and 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, and described positive active material can be reversible be deviate from-embedded ion; Described negative pole comprises negative current collector at least; Described electrolyte comprises at least a solvent that can dissolve electrolyte and make described electrolyte ionization; Described electrolyte can ionize out at least a charge and discharge process at described negative pole and reduce-deposit and the active ion of oxidation-dissolving; 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, to account for the volume range of described porous layer be 50-95% for described micron or submicron order hole.
Preferably, to account for the volume range of described porous layer be 10-99% to described nanoscale hole.
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 a in section's qin carbon black, activated carbon, carbon nano-tube, carbon fiber, the 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 that is formed at described negative pole currect collecting surface, described negative electrode active material can oxidation in described battery discharge procedure-be dissolved as described active ion.
Preferably, the material of described negative current collector is selected from metal Ni, Cu, Ag, Pb, Sn, Fe, Al or a kind of through in the above-mentioned metal of Passivation Treatment.
Preferably, the metal that the material of described negative current collector is selected from carbon-based material, stainless steel, silicon or has plating/coating, described plating/coating contains in simple substance, alloy or the oxide of C, Sn, In, Ag, Pb, Co, Zn at least a.
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 a among Zn, Fe, Cr, Cu, Mn, the Ni.
Preferably, described metal ion is present in the described electrolyte with at least a form in chlorate, sulfate, nitrate, acetate, formates, the phosphate.
Preferably, lithium ion, sodium ion, zinc ion or magnesium ion can be reversible deviate from-embed to described positive active material.
Preferably, the material of described plus plate current-collecting body be selected from graphite, stainless steel, aluminium alloy, through stainless steel or the aluminium alloy of transpassivation.
The present invention also provides a kind of battery, comprises positive pole, negative pole, electrolyte, and described positive pole comprises positive active material, and described positive active material can be reversible be deviate from-embedded ion; Described negative pole comprises the negative electrode active material that participates in electrochemical reaction; Described electrolyte comprises at least a solvent that can dissolve electrolyte and make described electrolyte ionization; Described electrolyte can ionize out at least a charge and discharge process described negative pole reduce-deposit and the active ion of oxidation-dissolving or/and the ion of can be reversible deviate from-embedding at described positive pole at least a charge and discharge process, described negative electrode active material can oxidation in discharge process-be dissolved as described active ion; Described negative pole also comprises porous layer or the graphene layer that is formed at described negative electrode active material surface, and described porous layer has micron or sub-micron or nanoscale hole.
The present invention also provides a kind of battery, comprises positive pole, negative pole, electrolyte and barrier film, and described positive pole comprises plus plate current-collecting body and participate in the positive active material of electrochemical reaction, and described positive active material is can be reversible to deviate from-compound of embedded ion; Described negative pole is the electrochemistry inertia conductive electrode that does not participate in electrochemical reaction; Described electrolyte is the aqueous solution, contains at least in charge and discharge process at described negative pole to reduce-deposit and the metal ion of oxidation-dissolving; Described negative pole comprises negative current collector and is formed at the porous layer with micron hole 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, can provide for the active ion in the electrolyte larger deposition rate surface area on the one hand, effectively reduce the generation of negative pole dendrite, also shorten on the other hand the active ion migration distance, solved the diffusional resistance problem of active ion at charge and discharge process, so that battery has 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.
Description of drawings
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 that unpassivated is processed among the embodiment 1-1;
Fig. 6 is the cyclic voltammetry curve figure of Stainless steel 316 in stannous sulphate electrolyte of process Passivation Treatment among the embodiment 1-2;
Fig. 7 is the cyclic voltammetry curve figure of Stainless steel 316 P in nitrate electrolyte of process Passivation Treatment among the embodiment 1-3;
Fig. 8 is the cyclic voltammetry curve figure of aluminium alloy in acetate electrolyte of passivation among the embodiment 1-4;
Fig. 9 is the cyclic voltammetry curve figure of aluminium alloy in stannous sulphate electrolyte of passivation among the embodiment 1-5;
Figure 10 is the cyclic voltammetry curve figure of graphite foil in hydrochloride electrolyte among the embodiment 1-6;
Figure 11 is the cyclic voltammetry curve figure of passivation stainless steel in hydrochloride electrolyte not among the embodiment 1-7;
Figure 12 is the voltage of the battery that provides of embodiment 3-1 and the graph of relation of discharge capacity;
Figure 13 is the discharge capacity of the battery that provides of embodiment 3-1 and the graph of relation of cycle-index;
Figure 14 is the discharge capacity of the battery that provides of embodiment 3-2 and the graph of relation of cycle-index;
Figure 15 is the discharge capacity of the battery that provides of embodiment 3-3 and the graph of relation of cycle-index;
Figure 16 is the enclosed pasture efficient of the battery that provides of embodiment 3-3 and the graph of relation of cycle-index;
Figure 17 is the discharge capacity of the battery that provides of embodiment 3-4 and the graph of relation of cycle-index;
Figure 18 is the structural representation that the negative pole currect collecting surface is formed with porous layer among the embodiment 4-1;
Figure 19 is the local enlarged diagram of porous layer among Figure 18;
Figure 20 is the curve chart of battery first charge-discharge voltage-capacity of providing of embodiment 4-1;
Figure 21 is the cyclic voltammetry curve figure of the battery that provides of embodiment 5-1;
Figure 22 is the cyclic voltammetry curve figure of the battery that provides of embodiment 5-2;
Figure 23 is the cyclic voltammetry curve figure of the battery that provides of embodiment 5-3;
Figure 24 is the cyclic voltammetry curve figure of the battery that provides of embodiment 5-4;
Figure 25 is the cyclic voltammetry curve figure of the battery that provides of embodiment 5-6;
Figure 26 is the cyclic voltammetry curve figure of the battery that provides of embodiment 5-9;
Figure 27 is the battery first charge-discharge that provides of embodiment 6-1 and the relation curve of voltage;
Figure 28 is the discharge capacity of the cell that provides of embodiment 6-1 and the graph of relation of cycle-index;
Figure 29 is the battery enclosed pasture efficient that provides of embodiment 6-1 and the graph of relation of cycle-index;
Figure 30 is the discharge capacity of the battery that provides of embodiment 6-2 and the graph of relation of cycle-index;
Figure 31 is the battery enclosed pasture efficient that provides of embodiment 6-2 and the graph of relation of cycle-index;
Figure 32 is the discharge capacity of the battery that provides of embodiment 6-4 and the graph of relation of cycle-index;
Figure 33 is the discharge capacity of the battery that provides of embodiment 6-5 and the graph of relation of cycle-index.
Wherein:
10. anodal 20. negative poles, 28. active ions
12. plus plate current-collecting body 22. negative current collectors 30. porous layers
14. positive active material 24. negative electrode active materials
16. the reversible ion 26. active ion sedimentary deposits of deviating from-embedding
Embodiment
Battery provided by the invention has higher energy density, stable cycle performance, and such as portable type electronic products such as mobile phone, notebook computers, 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).Anodal 10 comprise plus plate current-collecting body 12 and participate in the positive active material 14 of electrochemical reaction, and positive active material 14 can be reversible be deviate from-embedded ion; Negative pole 20 comprises negative current collector 22 at least; Electrolyte comprises at least a solvent that can dissolve electrolyte and make electrolyte ionization; Electrolyte can ionize out at least a charge and discharge process and reduce at negative pole-deposits and the active ion 28 of oxidation-dissolving.
See also shown in Figure 1ly, 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 anodal reaction, and can be reversible deviates from-embedded ion or functional group.Concrete, lithium ion, sodium ion, zinc ion or magnesium ion can be reversible deviate from-embed to positive active material 14.
Positive active material 14 can be to meet general formula Li 1+xMn yM zO kCan be reversible deviate from-embed the compound of the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least a among Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, the Al.Preferably, positive active material 14 contains LiMn 2O 4Preferred, positive active material 14 contains the LiMn through overdoping or coating modification 2O 4
Positive active material 14 can be to meet general formula Li 1+xM yM ' zM " cO 2+nCan be reversible deviate from-embed the compound of the layer structure of lithium ion, wherein ,-1＜x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1 ,-0.2≤n≤0.2, M, M ', M " be selected from respectively Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al at least a.Preferably, positive active material 14 contains LiCoO 2
Positive active material 14 can be to meet general formula Li xM 1-yM ' y(XO 4) nCan be reversible deviate from-embed the compound of the olivine structural of lithium ion, wherein, 0＜x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' be selected from Mg, Ti, Cr, V or Al at least a, X is selected from least a among S, P or the Si.Preferably, positive active material 14 contains LiFePO 4
In present Lithium Battery Industry, nearly all positive active material 14 all can be through modifications such as overdoping, coatings.But mix, it is complicated that the means such as coating modification cause the chemical general formula of material to express, such as LiMn 2O 4Can not represent the general formula of now widely used " LiMn2O4 ", and should be with general formula Li 1+xMn yM zO kBe as the criterion, comprise widely the LiMn through various modifications 2O 4Same, LiFePO 4And LiCoO 2Also should be interpreted as widely to comprise through modifications such as various doping, coatings, general formula meets respectively Li 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 is deviate from-when embedding the lithium ion compound, can be selected such as LiMn for reversible 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, can deviate from-embed compound such as the NaVPO of sodium ion 4F can deviate from-embed compound such as the γ-MnO of zinc ion 2, can deviate from-embed compound such as the MgM of magnesium ion xO y(wherein M is a kind of metal, 0.5＜x＜3,2＜y＜6) and have similar functions, can deviate from-compound of embedded ion or functional group can be as the positive active material 14 of battery of the present invention.
In the concrete execution mode, when the preparation anode sizing agent, except positive active material 14, also need add conductive agent and binding agent in the anode sizing agent.
Conductive agent is selected from one or more in conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and the sheet metal.
Binding agent is selected from polyethylene oxide, polypropylene oxide, mixture and the derivative of a kind of or above-mentioned polymer in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, poly-divinyl polyethylene glycol, polyethyleneglycol diacrylate, the polyethylene glycol dimethacrylate.In 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 in battery operated voltage range, plus plate current-collecting body 12 can be stable is present in the electrolyte and does not have other side reactions to occur, thereby guarantees that battery has stable cycle performance.The material of plus plate current-collecting body 12 is selected from a kind of in carbon-based material, the metal or alloy.
Concrete, carbon-based material is selected from vitreous carbon, graphite, carbon felt, carbon fiber or has a kind of in the electric conducting material of 3D bicontinuous structure.Wherein, the electric conducting material that has a 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 a kind of through 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 a kind of through in the above-mentioned alloy of Passivation Treatment.Stainless steel comprises stainless steel foil or stainless (steel) wire, and is concrete, and stainless model can be but be not limited to the stainless steel of 300 series, such 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, such as aluminium alloy 6061.
Negative pole 20 only comprises negative current collector 22, and negative current collector 22 does not participate in electrochemical reaction only as the carrier of electrical conductivity and collection.
The material of negative current collector 22 is selected from metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al, Zn or at least a through in the above-mentioned metal of Passivation Treatment, perhaps elemental silicon, perhaps carbon-based material, wherein, carbon-based material comprises graphite material, such as the paper tinsel of business-like graphite compacting, wherein the shared part by weight scope of graphite is 90-100%.The material of negative current collector 22 can also be selected from stainless steel or through the stainless steel of Passivation Treatment.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, and is same, and stainless model can be but be not limited to the stainless steel of 300 series, such as stainless steel 304,316,316L or 316P.
In addition, negative current collector 22 can also be selected from the metal that contains the high plating/coating of hydrogen-evolution overpotential, thereby reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance that contains C, Sn, In, Ag, Pb, Co, Zn, and alloy is perhaps at least a in the oxide.The thickness range of plating/coating is 1-1000nm.For example: 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 to make the surface of collector form the oxide-film of one deck passivation, thereby in battery charge and discharge process, can play stable collection and the effect of conduction electron, and can not participate in cell reaction, guarantee that battery performance is stable.The collector deactivating process for the treatment of comprises chemical passivation processing or electrochemical passivation processing.
Chemical passivation is processed and is comprised by oxidant oxidation collector, makes collection liquid surface form passivating film.The principle that oxidant is selected is that oxidant can make collection liquid surface formation 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, the chemical passivation treatment step is: collector is inserted in the oxidizing agent solution, kept 0.5-1 hour, make collection liquid surface form passivating film, take out at last collector and clean also dry.
In an embodiment with chemical passivation processing stainless (steel) wire or stainless steel foil, concrete Passivation Treatment process is: under 50 ℃, stainless steel inserted 20% concentrated nitric acid solution, kept 0.5 hour, make stainless steel surfaces form passivating film, take out at last stainless steel water cleaning and dry in 50 ℃ drying box.
Process with chemical passivation among the embodiment of stainless (steel) wire or stainless steel foil at another, concrete Passivation Treatment process is: the Ce (SO that stainless steel is inserted 0.75mol/L 4) 2In the solution, kept 0.5 hour, make stainless steel surfaces form passivating film, take out at last stainless steel water cleaning and dry in 50 ℃ drying box.
Electrochemical passivation is processed and to be comprised collector is discharged and recharged or the battery that contains collector is discharged and recharged processing, makes collection liquid surface form passivating film.
Directly collector is discharged and recharged, namely is used for the battery assembling pre-Passivation Treatment of row of advancing at collector, concrete, to discharging and recharging with the three-electrode system of collector as work electrode, more corresponding selection suitable to electrode and reference electrode.Voltage all is charged to 2.35-2.45V during charging, and voltage is all put to 1.35-1.45V during discharge.Collector can be metal, such as metallic aluminium; Collector also can be alloy, such as stainless steel or aluminium alloy.Certainly, also can adopt two electrode systems take collector as work electrode to discharge and recharge, voltage all is charged to 2.35-2.45V during charging, and voltage is all put to 1.35-1.45V during discharge.
In the execution mode of a direct passivation aluminium alloy collector, with aluminium alloy as work electrode, the conduct of zinc paper tinsel is to electrode and reference electrode, electrolyte is the aqueous solution that contains 1.5mol/L zinc acetate and 3mol/L lithium acetate, three-electrode system is discharged and recharged, voltage is charged to 2.4V during charging, so that aluminum alloy surface oxidation under 2.4V forms the oxide-film of one deck passivation, cut-ff voltage is 1.4V during discharge.
Reach the purpose of collector being carried out passivation thereby also can discharge and recharge the battery that contains collector, voltage all is charged to 2.35-2.45V during charging, and voltage is all put to 1.35-1.45V during discharge, discharges and recharges number of times and is not less than 1.Collector can be metal, such as metallic aluminium; Collector also can be alloy, such as stainless steel or aluminium alloy.
Carry out in the execution mode of Passivation Treatment after one is assembled into battery to collector, positive active material 14 is LiMn 2O 4, plus plate current-collecting body 12 is aluminium alloy, negative current collector 22 is Copper Foil, electrolyte is the aqueous solution that contains 1.5mol/L zinc acetate and 3mol/L lithium acetate, voltage all is charged to 2.4V during charging, and the cut-ff voltage when namely charging is 2.4V, so that aluminum alloy surface oxidation under 2.4V forms one deck passivating film; Cut-ff voltage is 1.4V during discharge, battery is discharged and recharged number of times be not less than 1 time.The number of times of battery charging and discharging is more, and the effect of aluminium alloy passivation is better, and is more stable in electrolyte.
Adopting electrochemical passivation to process in the method for aluminium alloy, voltage reaches behind the 2.4V and keeps a period of time during charging, and the corrosion current of aluminium alloy can significantly reduce along with the increase of holding time.Concrete, charging voltage reaches to hold time behind the 2.4V and progressively extended to 1 hour from 10 minutes, the corrosion current of aluminium alloy can significantly descend, hold time and progressively extended to 24 hours from 1 hour, it is not clearly that corrosion current descends, therefore, preferred, charging voltage reaches behind the 2.4V and kept at least 1 hour.
Electrolyte is weak acid or neutral aqueous solution, such as chlorate, sulfate, nitrate, acetate, formates or phosphate, plus plate current-collecting body 12 and negative current collector 22 can keep stable in electrolyte, namely under battery operated voltage window, do not have side reaction to occur, thereby guarantee the stability of battery performance.The deactivating process for the treatment of of collector provided by the invention all is suitable for plus plate current-collecting body 12 and negative current collector 22.
In order to make more even at negative pole 20 surface depositions of active ion 28 in the electrolyte, negative pole 20 surfaces are formed with porous layer 30, and porous layer 30 is formed at negative pole 20 surfaces in any suitable mode such as modes such as coating, compactings.
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%.The nanoscale hole accounts for the 10-99% of porous layer 30 volume ranges, and the scope of the average diameter of nanoscale hole is 1-999nm, and preferred, 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 that deposits in the charging process-reduce, so that active ion 28 is more even on negative current collector 22 surface deposition ground, effectively reduce the generation of negative pole dendrite.In addition, by being formed at the porous layer 30 on negative current collector 22 surfaces, can also shorten migration distance in active ion 28 charge and discharge process, 28 of active ions need the shorter distance of diffusion just can finish charge and discharge process, have solved the problem that has diffusional resistance in active ion 28 courses of reaction.Simultaneously, owing to being provided with porous layer 30 at negative pole 20, can use thinner barrier film when the preparation battery, make in the battery charging process, the anodal oxygen that produces can more easily move to negative pole 20 and reduce the invertibity of enhancing battery when especially overcharging.
The material of porous layer 30 is selected from carbon-based material, and carbon-based material is selected from least a in carbon black, activated carbon, carbon nano-tube, carbon fiber, the 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 more even on negative pole 20 deposition ground, and the chemical property of the very strong conductive capability of KB can improve the high current charge-discharge of whole battery the time.
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, commercialization activated carbon powder (particle size range 1-200mm) and Kynoar (PVDF) are evenly mixed, add 1-METHYLPYRROLIDONE (NMP) and be dissolved into pasty state, be coated on negative current collector 22 surfaces.Porous layer 30 thickness ranges are 0.1-0.2mm, and the weight range that NMP accounts for the 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, with PVDF, NMP evenly mixes again, is coated in negative current collector 22 surfaces.The thickness of porous layer 30 is between 0.1-0.2mm.The effect of electrically conductive graphite is to increase the electronic conduction ability of 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 specifically making the negative pole that contains porous layer is also relatively simple, easily industrialization.
Preferably, negative pole 20 surfaces are formed with graphene layer.Graphene has outstanding heat conductivility and mechanical property, and theoretical specific area is up to 2600m 2/ g, and at a high speed electron mobility under the room temperature, therefore, the graphene layer that is formed at negative pole 20 surfaces can not only provide for the deposition of active ion 28 larger surface area, can also further improve simultaneously the sub-ability of conduction of negative pole 20, thereby improve the chemical property of the large electric current of battery.
In the first embodiment, because negative pole 20 only comprises negative current collector 22, therefore, porous layer or graphene layer are to be formed at negative current collector 22 surfaces.
Electrolyte comprises at least a solvent that can dissolve electrolyte and make electrolyte ionization, and solvent comprises at least a in the aqueous solution or the alcoholic solution, and alcoholic solution includes but are not limited to ethanol or methyl alcohol.
Electrolyte can ionize out at least a charge and discharge process at negative pole 20 and reduce-deposit and the active ion 28 of oxidation-dissolving.
The concentration range of active ion 28 is 0.5-15mol/L.In concrete execution mode, active ion 28 comprises metal ion, and metal is selected from least a among Zn, Fe, Cr, Cu, Mn, Ni, the Sn.
Metal ion is present in the electrolyte with forms such as chlorate, sulfate, nitrate, acetate, formates, phosphate.Preferably, metal ion is present in the electrolyte with the form of the mixture of sulfate, acetate or sulfate and acetate.
Preferably, also comprise a kind of electrolyte in the electrolyte, electrolyte can ionize out at least a charge and discharge process ion 16 of can be reversible deviate from-embedding anodal 10, thereby improves the ion-exchange speed in positive active material 14 and the electrolyte, the high rate charge-discharge performance of raising battery.Concrete, positive active material 14 for can be reversible deviate from-embed the compound of lithium ion, what electrolyte was corresponding can also ionize out lithium ion.The reversible ion 16 of deviating from-embedding comprises lithium ion or sodium ion or magnesium ion or zinc ion, and the reversible concentration range of ion 16 in electrolyte of deviating from-embedding is 0.1-30mol/L.
In order to guarantee battery capacity, the concentration of the active ion 28 in the electrolyte must reach certain limit, when electrolyte is crossed alkali, can affect the solubility of active ion 28 in the electrolyte; When the electrolyte peracid, the problems such as proton embeds altogether in electrode material corrosion and the charge and discharge process then can appear, and therefore, the pH value scope of electrolyte is 3-7 among the present invention.
Please refer to shown in Figure 2ly, the charge-discharge principle of battery is: during charging, deviate from the reversible ion 16 of deviating from-embedding in the positive active material 14, follow simultaneously positive active material 14 interior variable valency metals oxidized, and ejected electron; Electronics arrives battery cathode 20 via external circuit, and the active ion 28 in the while electrolyte obtains electronics at negative pole 20 and is reduced, and is deposited on negative current collector 22 surfaces, forms active ion sedimentary deposit 26.Discharge process is the inverse process for charging then, as shown in Figure 3.
In the first embodiment, working first of battery is to deviate from the reversible ion 16 of deviating from-embedding, active ion 28 in the 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 the battery initial charge, needs to comprise enough reversible ions 16 of deviating from-embedding in the positive active material 14.User's battery before not carrying out charging process can not use as power supply, has therefore guaranteed that the capacity of battery is not subject to any type of loss before use.
The second execution mode
Please refer to shown in Figure 4, second embodiment of the invention provides a kind of battery, with the difference of the battery that discloses in the first execution mode be: negative pole 20 also comprises the negative electrode active material 24 that is formed at negative current collector 22 surfaces in the second execution mode, negative electrode active material 24 can oxidation in discharge process-be dissolved as active ion 28.
Negative current collector 22 is only as the carrier of electrical conductivity and collection, do not participate in negative pole 20 reactions, and the method for negative electrode active material 24 by coating, plating or sputter is formed on the negative current collector 22, 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 through surface preparation, and the method for surface preparation comprises at least a in mechanical treatment, chemical treatment or the electrochemical treatments.Concrete, when negative current collector 22 is Cu, it can be manual/mechanical grinding that Cu is carried out pretreated method, remove the dim part in its surface and make simultaneously its surface have certain roughness, but because hand sand can not be removed the lip-deep impurity of Cu thoroughly, such as CuO, therefore Cu is needed further chemical treatment, chemically treated method can be that the mixed liquor of the different acid of preparation soaks it, such as sulfuric acid, and nitric acid and hydrochloric acid.Pretreated concrete grammar depends on the selection of negative current collector 22, normally machinery, chemistry, three kinds of method combinations of electrochemistry.
In the present embodiment, negative pole 20 comprises negative current collector 22 and negative electrode active material 24, and therefore, porous layer or graphene layer are to be formed at negative current collector 22 surfaces.Negative electrode active material is formed at porous layer or graphene layer surface by modes such as coating, plating or sputters.
Same, anodal 10 comprise 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 be reversible be deviate from-embedded ion, such as lithium ion, sodium ion, zinc ion or magnesium ion, but in the second execution mode, when the preparation battery, need not limit positive active material 14 and itself whether contain lithium ion, sodium ion, zinc ion or magnesium ion, specifically, positive active material 14 can have four kinds of states: do not contain the reversible ion 16 of deviating from-embedding, contain and can further embed the reversible ion 16 of deviating from-embedding, contain the reversible ion 16 of deviating from-embedding and the reversible ion 16 of deviating from-the embedding state that reaches capacity, contain the reversible ion 16 of deviating from-embedding and the reversible ion 16 of deviating from-embedding reaches hypersaturated state.
Electrolyte comprises at least a solvent that can dissolve electrolyte and make electrolyte ionization, and solvent comprises the aqueous solution or alcoholic solution, and alcoholic solution includes but are not limited to ethanol and methyl alcohol.
At this moment, electrolyte can ionize out at least a charge and discharge process negative pole 20 reduce-deposit and the active ion 28 of oxidation-dissolving or at least a charge and discharge process at anodal 10 ions 16 of can be reversible deviate from-embedding or contain simultaneously active ion 28 and the reversible ion 16 of deviating from-embedding.
The battery that the second execution mode discloses, positive active material 14 can be reversible in charge and discharge process be deviate from-embedded ion, but for positive active material 14 itself, can not comprise the reversible ion 16 of deviating from-embedding, can comprise the hole of accepting the reversible ion 16 of deviating from-embedding can also be arranged in the reversible ion 16 of deviating from-embedding and the internal structure, can also be self to comprise reversiblely to deviate from-ion 16 that embeds and reach capacity state even hypersaturated state, therefore, the positive active material 14 of battery has very large selection space in selection, further, can comprise active ion 28 and/or the reversible ion 16 of deviating from-embedding in the electrolyte, so that the battery among the present invention can be selected different battery operated patterns, battery strong adaptability according to different application scenarios.Below further set forth the mode of operation of positive active material 14 and the battery that electrolyte consists of of different conditions.
A kind of battery comprises positive pole 10, negative pole 20, electrolyte (not shown).Anodal 10 comprise plus plate current-collecting body 12 and positive active material 14, and positive active material 14 can be reversible be 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 a solvent that can dissolve electrolyte and make electrolyte ionization.Electrolyte can ionize out and at least aly anodal 10 the reversible ion 16 of deviating from-embedding can occur; Positive active material 14 does not contain the reversible ion 16 of deviating from-embedding; Working first of battery is that the ion 16 of deviating from-embedding reversible in the electrolyte is embedded into positive active material 14, negative electrode active material 24 oxidations-the be dissolved as discharge process of active ion 28.
Concrete, positive active material 14 is Mn 2O 4, negative electrode active material 24 is Metal Zn, comprises LiAc in the electrolyte.Because do not contain lithium in the positive active material 14, and comprise lithium ion in the electrolyte, therefore, battery is worked first as lithium ion in the electrolyte is embedded into positive active material 14, negative electrode active material 24 Metal Zn oxidations-be dissolved as Zn 2+Discharge process.
Preferably, also comprise the electrolyte that can ionize out active ion 28 in the electrolyte, active ion 28 can reduce-deposit and oxidation-dissolving at negative pole 20, like this, when battery discharge, can accelerate negative pole 20 and electrolyte intermediate ion exchange velocity.
As long as positive active material 14 meets in charge and discharge process and can be reversible to deviate from-this condition of embedded ion gets final product work, must contain the reversible ion 16 of deviating from-embedding and need not limit positive active material 14.Although positive active material 14 does not comprise the ion 16 of can be reversible deviate from-embedding, battery is required to be discharge process when working first, but during the battery of user in buying 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.Anodal 10 comprise 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 a solvent that can dissolve electrolyte and make electrolyte ionization, and electrolyte can ionize out and at least aly reduce-deposit and the active ion 28 of oxidation-dissolving and at least aly at positive pole 10 the reversible ion 16 of deviating from-embedding can occur at negative pole 20; The reversible ion 16 of deviating from-embedding can be deviate from and embed to positive active material 14; Working first of battery is that the reversible ion 16 of deviating from-embedding is deviate from from positive active material 14, active ion 28 is in the charging process of negative pole 20 reduction and deposition or reversiblely deviate from-ion 16 embedding positive active material 14, negative electrode active material 24 oxidations that embed and the discharge process that is dissolved as active ion 28.
Concrete, positive active material 14 contains Li 1-xMn 2O 4, negative electrode active material 24 is Metal Zn, comprises zinc acetate and lithium acetate in the electrolyte.Positive active material 14 can be deviate from Li +, simultaneously, but also have Li in the electrolysis liquid of hole in the spinel structure of positive active material 14 +Embed, therefore, battery first mode of operation can be discharge: the Li in the electrolyte +Be embedded into Li 1-xMn 2O 4, negative electrode active material 24 Metal Zn oxidations also are 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 the electrolyte 2+Form active ion sedimentary deposit 26 in negative pole 20 reduction and deposition.
Therefore, it both can be charging process that battery is worked first, also can be discharge process.During the battery of user in buying the present invention, be that battery is charged or battery is discharged before need not to consider to use, can use, and battery of the present invention be very long.
Preferably, battery is worked first and is deviate from the charging process that active ion 28 reduces-deposits at negative pole 20 for the reversible ion 16 of deviating from-embedding from positive active material 14.
A kind of battery comprises positive pole 10, negative pole 20, electrolyte, and anodal 10 comprise 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 a solvent that can dissolve electrolyte and make electrolyte ionization; Electrolyte can ionize out and at least aly anodal 10 the reversible ion 16 of deviating from-embedding can occur; The reversible ion 16 of deviating from-embedding can be deviate from and embed to positive active material 14; Working first of battery is that the reversible ion of deviating from-embedding 16 embeds positive active materials 14, negative electrode active material 24 oxidations-the be dissolved as discharge process of active ion 28.
Concrete, positive active material 14 contains Li 1-xMn 2O 4, negative electrode active material 24 is Metal Zn, comprises lithium acetate in the electrolyte.Positive active material 14 can be deviate from Li +, also can embed Li +, contain Li in the electrolyte +, therefore, it is Li that battery is worked first +Be embedded into Li 1-xMn 2O 4, Metal Zn oxidation-be dissolved as Zn 2+Discharge process.
Although working first, battery is required to be discharge process, but during the battery of user in buying the present invention, can directly use as power supply equally, and not affect the performance of battery, and can discharge and recharge normally after battery is worked first, battery is very long simultaneously.
A kind of battery comprises anodal 10, negative pole 20, electrolyte, and anodal 10 comprise plus plate current-collecting body 12 and positive active material 14, and positive active material 14 can be reversible be 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 a solvent that can dissolve electrolyte and make electrolyte ionization; Electrolyte can ionize out and at least aly reduce-deposit and the active ion 28 of oxidation-dissolving at negative pole 20; Battery work first be reversiblely deviate from-embedded ion from positive active material 14 deviate from, active ion 28 is in the charging process of negative pole 20 reduction-deposition.
Concrete, positive active material 14 contains Li 1-xMn 2O 4, negative electrode active material 24 is Metal Zn, contains zinc acetate in the electrolyte, positive active material 14 can be deviate from Li +, also can embed Li +, therefore, it is Li that battery is worked first +From Li 1-xMn 2O 4In deviate from, the Zn in the electrolyte 2+The charging process of reducing-depositing at negative pole 20.
A kind of battery comprises anodal 10, negative pole 20, electrolyte, and anodal 10 comprise plus plate current-collecting body 12 and positive active material 14, and positive active material 14 can be reversible be 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 a solvent that can dissolve electrolyte and make electrolyte ionization; Electrolyte can ionize out at least a active ion 28 that reduces-deposit at negative pole 20; The ion 16 of deviating from-embedding reversible in the positive active material 14 state that reaches capacity; Battery work first be the reversible ion 16 of deviating from-embedding from anodal 10 deviate from, active ion 28 is in the charging process of negative pole 20 reduction-deposition.
As well known to those skilled in the art, the ion 16 of deviating from-embedding reversible in the positive active material 14 is in saturation condition, be that the reversible ion 16 of deviating from-embedding occupies the VOID POSITIONS in positive active material 14 structures substantially, and positive active material 14 Stability Analysis of Structures can steady operation in battery charge and discharge process.
Battery is worked first and is required to be charging process, and the namely reversible ion 16 of deviating from-embedding is deviate from from positive active material 14, and the active ion 28 in the electrolyte reduces-deposits at negative pole 20.Although the user needs it is carried out charging operations when buying this battery, just because of this, battery capacity can not be subject to any type of loss before using first, thereby has guaranteed the performance that battery used in the later stage.
Preferably, also comprise in the electrolyte ionizing out the electrolyte that the reversible ion 16 of deviating from-embedding can occur anodal 10, like this, when battery discharge, can accelerate anodal 10 with the exchange velocity of electrolyte intermediate ion, raising battery high rate charge-discharge performance.
Therefore, can reduce-deposit and the active ion 28 of oxidation-dissolving can be able to allow battery operated at negative pole 20 as long as electrolyte comprises, that is to say, in the electrolyte of this battery, only need to add active ion 28, and mandatory requirement need to not contain the ion 16 of can be reversible deviate from-embedding, and can make the battery normal operation.The bath composition of battery is simple, low cost of manufacture, and battery has widely to be used.
A kind of battery comprises anodal 10, negative pole 20, electrolyte, and anodal 10 comprise plus plate current-collecting body 12 and positive active material 14, and positive active material 14 can be reversible be 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 a solvent that can dissolve electrolyte and make electrolyte ionization; Electrolyte can ionize out at least a active ion 28 that reduces-deposit at negative pole 20; The ion 16 of deviating from-embedding reversible in the positive active material 14 is in hypersaturated state; Battery work first be the reversible ion 16 of deviating from-embedding from anodal 10 deviate from, active ion 28 reduces-is deposited as the charging process of negative electrode active material 24 at negative pole 20.
As well known to those skilled in the art, the ion 16 of deviating from-embedding reversible in the positive active material 14 is in hypersaturated state, when namely preparing positive active material 14, be on the saturated basis at positive active material 14, further positive active material 14 is carried out the embedding ion processing, to improve the capacity of positive active material 14, in order to guarantee the Stability Analysis of Structures of positive active material 14, the surface of positive active material 14 is modified or is coated by metal or metal oxide.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 3The Li that coats 1+xMn 2O 4(0＜x＜0.5), negative electrode active material 24 is Metal Zn, comprises zinc acetate in the electrolyte.Li in the positive active material 14 +Content reached hypersaturated state, therefore, it is Li that battery is worked first +From Li 1+xMn 2O 4In deviate from, the Zn in the electrolyte 2+Reduce-be deposited as the charging process of active ion sedimentary deposit 26 at negative pole 20.
Preferably, also comprise in the electrolyte ionizing out the electrolyte that the reversible ion 16 of deviating from-embedding can occur anodal 10, like this, when battery charge, can accelerate anodal 10 and electrolyte intermediate ion exchange velocity, raising battery charging and discharging performance.
Because the negative pole 20 of battery comprises the negative electrode active material 24 of negative current collector 22 and participation electrochemical reaction in the second execution mode, so the first mode of operation of battery has had more selection, thus, the producer can be according to user's application scenario, select the collocation of positive pole 10, negative pole 20 and electrolyte in the battery, produce the battery with different charge and discharge modes.
The 3rd execution mode
Third embodiment of the invention has also disclosed a kind of battery, the difference of the battery that discloses with the second execution mode is: negative pole 20 only comprises negative current collector 22 in the 3rd execution mode, but negative current collector 22 is not only as the carrier of electrical conductivity and collection, also be equivalent to simultaneously negative electrode active material and can participate in negative pole 20 reactions, can oxidation in battery discharge procedure-be dissolved as active ion 28, the material that is negative current collector 22 is identical with the simple substance material of active ion 28, for example: active ion 28 is zinc ion, and corresponding negative current collector 22 is metallic zinc.
In the 3rd execution mode, negative pole 20 comprises the negative current collector 22 that participates in electrochemical reaction, and therefore, porous layer or graphene layer are to be formed at negative current collector 22 surfaces.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 that contains zinc salt.Preferably, electrolyte is the aqueous solution that contains zinc salt and lithium salts.Metallic zinc can participate in negative pole 20 reactions.
When the battery among the present invention such as need were 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 μ m.
Battery provided by the invention, has energy density high (can reach the 60%-80% of lithium ion battery), power density (is expected to reach 200% of lithium ion battery greatly, even higher), be easy to make, totally nontoxic, environmental protection, easily reclaim and with low cost (battery of same capacity is expected to reach 60% of lead-acid battery, 20% of lithium ion battery, even lower) etc. characteristics, and have good cycle performance, in embodiment, battery capacity after 4000 weeks of circulation still maintains more than 90%.Therefore, the battery among the present invention is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery as the green energy resource of a new generation very much.
Weight, the unit in the percent by volume among the present invention are well-known to those skilled in the art, and for example percent by volume refers to the weight of solute in 100 milliliters solution.Unless otherwise defined, employed all specialties are identical with the meaning that scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that better implementation method described in the literary composition and material only present a demonstration.
Below in conjunction with embodiment, be described more specifically 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 and/or change that the present invention is made all will fall into protection range of the present invention.In the present invention, if not refer in particular to, all part, percentages are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
By cyclic voltammetry (CV), make up three-electrode system and test the stability of different collectors in electrolyte.
Embodiment 1-1
Take stainless steel as work electrode, the stainless steel model is 304, and zinc electrode is to electrode and reference electrode, at stannous sulphate electrolyte 2mol/L ZnSO 4With 2mol/L Li 2SO 4In study stainless electrochemical behavior by cyclic voltammetry, voltage range is 1.0-2.4V.Stainless steel does not pass through Passivation Treatment.
Fig. 5 is the cyclic voltammetry curve of the stainless steel 304 that unpassivated is processed among the embodiment 1-1.As can be seen from the figure stainless steel anode when scanning first, locate to occur a wide oxidation peak at 1.9V (Vs.Zn), obvious O then occurred 2Separate out the peak, be accompanied by electric current and increase.In negative electrode scanning subsequently, the reduction peak of less has appearred at the 1.4V place.The oxidation peak at the 1.9V place after 1 time of circulating is hindered, and means in circulating for the first time forming oxide layer at stainless steel surfaces, and oxide layer has suppressed the further oxidation of stainless steel surfaces internal layer.But perhaps oxide layer can cause O 2Separate out.Therefore cause separating out the peak to the low potential migration and becoming increasing of oxygen.
Embodiment 1-2
Take the stainless steel of passivation as work electrode, the stainless steel model is 316, and zinc electrode is to electrode and reference electrode, at stannous sulphate electrolyte 2mol/L ZnSO 4With 2mol/L Li 2SO 4In study 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: under 50 ℃, Stainless steel 316 inserted 20% concentrated nitric acid solution, keep 0.5h, make stainless steel surfaces form passivating film, take out at last that the stainless steel water cleans and dry.
Fig. 6 is the stainless cyclic voltammetry curve of process Passivation Treatment among the embodiment 1-2.
Experimental result is presented at solution such as the dense HNO that contains oxidant 3After the passivation, it is more stable that stainless steel becomes, and O in the solution 2Separate out the peak favorable reproducibility, at different cycle period O 2Separate out not significantly difference of peak shape.On the other hand, O 2Evolution or deposition potential moves to high potential a little, and does not occur separating out of obvious oxygen before 2.0V.This result is extremely important to the water system battery, because highly stable in the battery operated voltage range of water system through the stainless steel of transpassivation.
Embodiment 1-3
Take the stainless steel of passivation as work electrode, the stainless steel model is 316P, and zinc electrode is to electrode and reference electrode, at nitrate electrolyte 3mol/L Zn (NO 3) 2With 6mol/L LiNO 3In study 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 the Stainless steel 316 P CV curve in nitrate electrolyte through Passivation Treatment.
Embodiment 1-4
Take aluminium alloy as work electrode, zinc electrode is to electrode and reference electrode, at acetate electrolyte 1.5mol/L Zn (Ac) 2With the electrochemical behavior of studying aluminium alloy among the 3mol/L LiAc 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/L ZnSO 4With 2mol/L Li 2SO 4In study the electrochemical behavior of aluminium alloy by cyclic voltammetry, voltage range is 1.0-2.4V, aluminium alloy is in 2.4V lower surface generation passivation.
Fig. 8 and Fig. 9 are respectively the CV curve of aluminium alloy in acetate and stannous sulphate electrolyte among embodiment 1-4 and the 1-5.In Fig. 8, significant oxidation peak has appearred during first anode scanning, and fluctuation appears in electric current slightly, non-faradic currents or other processes that this phenomenon may produce owing to oxidation or the ionic adsorption of aluminum alloy surface.Aluminium alloy surface when 2.4V is formed passivating film by electrochemical oxidation, after for the first time anode scanning, at 1.0-2.1V all without any the peak, and O 2Evolution or deposition potential moves to high potential, analyses the oxygen electric current and diminishes.Show through the aluminium alloy behind the electrochemical passivation highly stable in the battery operated voltage range of water system.
Embodiment 1-6
Take graphite foil as work electrode, zinc electrode is to electrode and reference electrode, at hydrochloride electrolyte 4mol/L ZnCl 2With the electrochemical behavior of studying graphite foil among the 3mol/L LiCl by cyclic voltammetry.
Embodiment 1-7
The stainless steel of processing take unpassivated is as work electrode, and zinc electrode is to electrode and reference electrode, at hydrochloride electrolyte 4mol/L ZnCl 2With the stainless electrochemical behavior of studying the unpassivated processing among the 3mol/L LiCl by cyclic voltammetry.
Figure 10 and Figure 11 are respectively the CV curve of embodiment 1-6 and 1-7.Can find out that by the CV curve graphite foil is relatively stable in solution of chlorate, except the separating out of oxygen occurs under high potential, obvious oxidation or reduction peak do not appear under whole electrochemical window, this phenomenon has been proved carbon-based material and has been adapted in the solution of chlorate as collector, and the stainless steel that unpassivated is processed not too is suitable for solution of chlorate.
By the Tafel curve, make up three-electrode system and test the corrosion rate of different collectors 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) 2In 3mol/L LiAc, study the corrosion behavior of aluminium foil by the Tafel curve.
Embodiment 2-2
As work electrode, its excess-three electrode composition and test condition are with embodiment 2-1 with the stainless steel 304 rod.
Embodiment 2-3
As work electrode, its excess-three electrode composition and test condition are with embodiment 2-1 with graphite rod.
Embodiment 2-4
As work electrode, its excess-three electrode composition and test condition are with embodiment 2-1 with aluminium alloy.
Embodiment 2-5
With the stainless steel 304 of passivation as work electrode, its excess-three electrode form and test condition with embodiment 2-1.Concrete stainless steel is processed by chemical passivation.
Embodiment 2-6
Take the aluminium alloy of passivation as work electrode, its excess-three electrode form and test condition with embodiment 2-1.Aluminium alloy is processed by electrochemical passivation, aluminium alloy is discharged and recharged charge and discharge cycles 1 time.
Embodiment 2-7
With the aluminium alloy of passivation as work electrode, its excess-three electrode form and test condition with embodiment 2-1.Concrete aluminium alloy is processed by electrochemical passivation, aluminium alloy is discharged and recharged electrochemical passivation charge and discharge cycles 50 times.
Corrosion current can obtain from Tafel curve and formula 1.Based on area, density and the possible corrosion mechanism (quantity of electron transfer in corrosion process) of work electrode, obtain the corrosion rate of several different plus plate current-collecting bodies as shown in table 1, wherein.R is corrosion resistance, I CorrBe corrosion current.
Formula 1: i = nFA k 0 { - c O exp [ - α nF RT ( E - E 0 ) ] + c R exp [ ( 1 - α ) nF RT ( E - E 0 ) ) ] }
Table 1
Figure BDA00001720206200192
Figure BDA00001720206200201
As can be seen from Table 1: the corrosion rate of aluminium foil is the highest, and stainless steel and the aluminium alloy corrosion rate in acetate solution is little 10 times than aluminium foil.Respectively through the stainless steel after chemical passivation and the electrochemical passivation processing and corrosion rate decline 6-12 times of aluminium alloy.And the corrosion rate behind the further electrochemical oxidation of aluminium alloy also can further descend, and 50 post-etching speed of electrochemicial oxidation circulation descend 150 times.This result and CV result coincide, and CV result shows that analysing the oxygen curve after the circulation for several times dies down.
Further, study the chemical property of battery by specific embodiment.
Embodiment 3-1
With LiMn 2O 4Be positive active material, positive active material, conductive agent acetylene black (AB), binding agent Kynoar (PVDF) mixed and are dissolved in the 1-METHYLPYRROLIDONE (NMP) making anode sizing agent according to 83: 10: 7 part by weight.Plus plate current-collecting body is graphite foil, and anode sizing agent evenly is coated on the plus plate current-collecting body, and 110 ℃ of lower dryings were made positive pole in 24 hours in air.The battery cathode collector is stainless steel.Electrolyte is to contain the aqueous solution that concentration is 4mol/L zinc chloride and 3mol/L lithium chloride, by titration 0.1mol/L lithium hydroxide in electrolyte the pH value of electrolyte is adjusted to 4.Barrier film is the glass felt-cloth.Positive pole, negative pole are assembled into battery, and the centre separates with barrier film, injects electrolyte.Treat that battery pack leaves standstill after installing began with 4C multiplying power charging and discharging in 12 hours subsequently.The charging/discharging voltage interval is 1.4-2.15V.
The voltage of the battery that Figure 12 provides for embodiment of the invention 3-1 and the relation curve of discharge capacity, the enclosed pasture efficient of battery is about 97%, and showing simultaneously in the good and cyclic process of the chemical property of battery does not almost have side reaction to occur yet.
The discharge capacity of the battery that Figure 13 provides for embodiment of the invention 3-1 and the relation curve of cycle-index, as can be seen from the figure, the 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%, shows that the cycle performance of battery is very good.
Embodiment 3-2
Battery positive electrode active material is Li among the embodiment 3-6 1.08Co 0.03Al 0.03Mn 1.94O 4, all the other battery formations are 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 that adopts doping vario-property to process 2O 4The cycle life of the battery of positive active material further obtains to improve.
Embodiment 3-3
With Li 1.05Mn 1.89Co 0.03Al 0.03O 4Be positive active material, positive active material, binding agent PVDF, super-p carbon black mixed and are dissolved in the 1-METHYLPYRROLIDONE (NMP) making anode sizing agent according to 83: 10: 7 part by weight, plus plate current-collecting body is the graphite cake of thickness 1mm.The 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 provides of embodiment 3-3 and the relation curve of cycle-index, from figure, can clearly find out, 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 enclosed pasture efficient of the battery that provides of embodiment 3-3 and the relation curve of cycle-index, and as can be seen from the figure behind the circulating battery 4000 times, enclosed pasture efficient shows that still near 100% the charge-discharge performance of the battery among the present invention is highly stable.
Embodiment 3-4
With LiMn 2O 4Be positive active material, positive active material, polyfluortetraethylene of binding element (PTFE), super-p carbon black mixed and are dissolved in the 1-METHYLPYRROLIDONE (NMP) making anode sizing agent according to 83: 10: 7 ratio.Plus plate current-collecting body is the stainless (steel) wire of thickness 30 μ m, and stainless steel evenly is coated on anode sizing agent on the plus plate current-collecting body without passivation, and 110 ℃ of lower dryings were made positive pole in 24 hours in air.The battery cathode collector is thickness 10 μ m Copper Foils.Electrolyte is to contain the aqueous solution that concentration is 1mol/L lithium acetate and 1.5mol/L zinc acetate, by titration 0.1mol/L lithium hydroxide and 0.1mol/LHAc in electrolyte the pH value of electrolyte is adjusted to 4.Barrier film is the glass felt-cloth.Positive pole, negative pole are assembled into battery, and the centre separates with barrier film, injects electrolyte.Treat that battery pack leaves standstill after installing began with 0.5C multiplying power charging and discharging in 12 hours subsequently.The charging/discharging voltage interval is 1.5-2.1V.
Figure 17 is the discharge capacity of the battery that provides of embodiment 3-4 and the relation curve of cycle-index.Can clearly see from figure: battery first discharge capacity is, the discharge capacity that circulates after 250 times does not almost have difference with discharge capacity first, shows that the cycle performance of battery is highly stable, and battery provided by the invention has excellent chemical property.
Embodiment 4-1
With LiMn 2O 4Be positive active material, ratio according to 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 again positive active material and conductive carbon black, stirred 2 hours, and added at last the SBR stirring and obtained anode sizing agent in 10 minutes.Plus plate current-collecting body is the graphite foil of thickness 0.1mm, anode sizing agent evenly is coated on the plus plate current-collecting body, and thickness 0.3mm, positive plate was made in 120 degree oven dry in 12 hours.The battery cathode collector is the graphite foil of thickness 0.1mm.(coconut husk is fired, specific area 1500m with the activated carbon powder 2/ g), and conductive carbon black, PVDF mixes with 90: 5: 5 ratio, adds NMP it is dissolved, and evenly is coated on the negative current collector graphite foil and makes porous layer, and thickness is 0.1mm.Electrolyte is to contain the aqueous solution that concentration is 4mol/L zinc chloride and 3mol/L lithium chloride, and barrier film is the nonwoven fabrics barrier film.With positive plate, negative plate is assembled into battery, and the centre separates with barrier film.Inject electrolyte, the electrolyte major part is stored in the porous layer, the Zn in the charge and discharge process in the electrolyte 2+/ Zn reduces at negative pole-deposits and oxidation-solubilizing reaction, and especially the interface between porous layer inside and porous layer and negative current collector is reduced-deposited and oxidation-solubilizing reaction.Figure 18 is the structural representation that negative pole currect collecting of the present invention surface is formed with porous layer.In the charge and discharge process, zinc is in negative pole deposition/dissolving.Micron-sized hole can effectively adsorb a large amount of electrolyte and zinc deposition basic point is provided in the activated carbon.Figure 19 is the partial enlarged drawing of porous layer among Figure 18, can obviously see the active ion sedimentary deposit 26 that is deposited on porous layer inside.Treat that battery pack leaves standstill after installing began with 1C multiplying power charging and discharging in 12 hours subsequently.The 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, so cycling).Figure 20 is the LiMn of embodiment of the invention 4-1 2O 4/ Zn battery first charge-discharge voltage-capacity curve figure.
Embodiment 4-2
The mode identical with embodiment 4-1 made battery, and different is zinc-plated as the battery cathode collector with Copper Foil.Relative graphite foil, the Copper Foil electric conductivity is better, and mechanical strength is higher, and is also thinner.Adopt Copper Foil to be conducive to improve the negative discharge performance of battery, also can reduce the battery volume simultaneously, improve the volume energy density of battery.But simple Copper Foil can not be as the negative pole of ion-exchange battery, because at copper foil surface, the efficient of zinc deposition is very low.Therefore, can plate one deck tin at copper foil surface, to improve deposition efficiency.
Because negative current collector itself can not affect the performance of battery greatly, with charging and discharging curve and execution mode one basic simlarity of battery that this execution mode is done.
Embodiment 4-3
The mode identical with embodiment 4-1 made battery, and different is as the battery porous layer with commercially available activated carbon fiber cloth.Microstructure and the activated carbon of this activity carbon cloth are similar, and thickness (not compression) is about 0.5mm, and compression is rear 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.Structure with this battery that forms is identical with battery structure shown in Figure 15, and just the material of porous layer comprises activated carbon fiber cloth.Clearly, the battery that top method is made simple in structure can be carried out suitability for industrialized production at faster speed.The same with the porous layer that is comprised of activated carbon of mentioning in execution mode one and the execution mode two, activated carbon fiber cloth also can provide enough large negative pole specific area.
Embodiment 5-1
With LiMn 2O 4Be positive active material, mix at 8: 1: 1 according to positive active material, active carbon black, bonding agent PVDF weight ratio, be cut into the disk of diameter 12mm, thickness 0.1-0.2mm, be compressed on the 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 the positive and negative electrode, barrier film are filter paper.Electrolyte is to contain the lithium sulfate of 4mol/L lithium ion and 2mol/L zinc ion and the mixed aqueous solution of zinc sulfate, and the pH that adds the LiOH adjusting electrolyte of 0.1mol/L by titration is 5.
Battery is discharged and recharged, and 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
Among the embodiment 5-2, plus plate current-collecting body is the alloy foil of thickness 50 μ m, and negative pole is the metallic zinc paper tinsel of thickness 50 μ m, and electrolyte is 1.5mol/L Zn (Ac) 2With 2mol/L LiAc, barrier film is the glass felt-cloth, and all the other batteries compositions and method of testing are with embodiment 5-1.
Figure 21 and Figure 22 are respectively the CV curve chart of the battery that embodiment 5-1 and 5-2 provide.As can be seen from the figure, each time anode and negative electrode scanning be all to should having two significant oxidation peak (1.95V and 1.85V) and two reduction peak (1.85V and 1.7V), and this is consistent with lithium ion deviating from organic bath/embed mechanism.Except these two obvious oxidation-reduction pairs, less oxidation peak has also appearred after the circulation primary, and peak current appears at 1.6V, and the cause of this oxidation peak may be deviating from-embedding of proton.This result has further verified the stable fine of battery of the present invention, and has excellent charge-discharge performance.
In addition, the battery among the embodiment 5-2 still near 90%, shows that the efficiency for charge-discharge of battery is very high in the enclosed pasture efficient of circulation after 600 times.
Embodiment 5-3
Among the embodiment 5-3, plus plate current-collecting body is the stainless steel 304 through transpassivation, and the thickness of stainless steel 304 is 50 μ m, and electrolyte is 2mol/L ZnSO 4With 2mol/L Li 2SO 4, barrier film is the glass felt-cloth, and all the other batteries form with embodiment 5-1, and the charging/discharging voltage interval is 1.4-2.1V.The concrete stainless method of passivation is: under 50 ℃, stainless steel inserted 20% red fuming nitric acid (RFNA) and reach half an hour, make stainless steel surfaces form one deck passivating film.
Figure 23 is the CV curve of battery among the embodiment 5-3.
Embodiment 5-4
Among the embodiment 5-4, plus plate current-collecting body is the stainless steel 304 through transpassivation, and electrolyte is 3mol/LZn (NO 3) 2With 6mol/L LiNO 3, all the other batteries form with embodiment 5-1, and the charging/discharging voltage interval is 1.4-2.2V.The concrete stainless method of passivation is with embodiment 5-3.
Figure 24 is the CV curve of battery among the embodiment 5-4.
Embodiment 5-5
The mode identical with embodiment 5-1 made battery, difference is that 304 type stainless steels of the process Passivation Treatment take thickness as 1mm replace graphite foil as plus plate current-collecting body, concrete Passivation Treatment process is: under 50 ℃, stainless steel inserted 20% nitric acid and reach half an hour, make stainless steel surfaces form one deck passivating film.Electrolyte is to contain the aqueous solution that concentration is 1.5mol/L zinc acetate and 3mol/L lithium acetate.Battery cathode is metallic zinc.Treat that battery pack left standstill 12 hours after installing, and began with the 1mA constant current battery to be carried out charging and discharging subsequently.The charging/discharging voltage interval is 1.4-2.2V.
Embodiment 5-6
The mode identical with embodiment 5-1 made battery, and difference is that 316 type stainless steels with Passivation Treatment replace 304 type stainless steels as plus plate current-collecting body, and concrete Passivation Treatment process is with embodiment 5-5.Treat that battery pack left standstill 12 hours after installing, begin subsequently respectively with the constant current of 1mA and 3mA battery to be carried out charging and discharging.The charging/discharging voltage interval is 1.4-2.2V.
Figure 25 is the CV curve of battery among the embodiment 5-6.
Embodiment 5-7
The mode identical with embodiment 5-6 made battery, and difference is that electrolyte is to contain the aqueous solution that concentration is 3mol/L zinc sulfate and 3mol/L lithium sulfate.Treat that battery pack left standstill 12 hours after installing, begin subsequently respectively with the constant current of 1mA, 2mA, 3mA battery to be carried out charging and discharging.The charging/discharging voltage interval is 1.4-2.2V.
Embodiment 5-8
The mode identical with embodiment 5-7 made battery, and difference is that metallic aluminium with Passivation Treatment is as plus plate current-collecting body.Process to the metallic aluminium Passivation Treatment is: treat that battery pack left standstill 12 hours after installing, begin subsequently with the 1mA constant current battery to be carried out charging and discharging, voltage all is charged to 2.4V during charging, and namely the charging/discharging voltage interval is 1.4-2.4V, makes the metallic aluminium surface form one deck passivating film.
The capability retention test
By embodiment 5-1 is discharged and recharged operation to the battery among the 5-8, to detect the cycle performance of battery.
Table 2 discharges and recharges under the 1mA constant current to the battery among the 5-8 for embodiment 5-1, and 80 times battery performance circulates:
Table 2
Figure BDA00001720206200251
As can be seen from Table 2, through the stainless steel of Passivation Treatment the battery performance during as plus plate current-collecting body from capability retention and efficiency for charge-discharge two aspects all than more excellent.
To the constant current charge-discharge test of embodiment 5-6 with 3mA, circulating, capability retention is 94% after 80 times, efficiency for charge-discharge is 98%, and battery performance is better than with 1mA constant current charge-discharge test result, illustrates that the battery among the present invention has excellent battery performance under large electric current.
Embodiment 5-7 with the test of the constant current charge-discharge of 2mA, 3mA, circulate that capability retention is respectively 92% and 72% after 80 times, and efficiency for charge-discharge is battery that 99%, embodiment 5-7 provides with battery performance the best of 2mA constant current charge-discharge.
Embodiment 5-9
With LiMn 2O 4Be positive active material, mix at 8: 1: 1 according to positive active material, active carbon black, bonding agent PVDF weight ratio, be coated on the stainless steel collector of passivation, make positive pole.The passivation for stainless steel method is with embodiment 5-3.Negative pole is the metallic zinc paper tinsel of thickness 50 μ m, and metallic zinc doubles as negative electrode active material and negative current collector.Barrier film is the glass felt-cloth.Electrolyte is the mixed aqueous solution that contains 2mol/L lithium acetate, 1.5mol/L zinc acetate and 1mol/L zinc sulfate, and regulating electrolyte pH is 5.
Battery is discharged and recharged, and 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 show, battery near 100%, shows that the battery of employing mixed electrolyte salt has stable charge-discharge performance in the enclosed pasture efficient of circulation 200 times.
Embodiment 6-1
With LiMn 2O 4Be positive active material, positive active material, super-p carbon black, bonding agent PVDF are mixed according to part by weight at 83: 10: 7, as dispersant, make anode sizing agent with NMP, evenly be coated on the plus plate current-collecting body graphite foil of thickness 80 μ m, subsequent drying, compacting obtain positive pole.Negative pole is the metallic zinc paper tinsel of thickness 50 μ m, and metallic zinc is negative electrode active material, simultaneously the double negative current collector of doing also.Barrier film is the glass felt-cloth.Electrolyte is the deionized water solution that contains 3mol/L lithium chloride and 4mol/L zinc chloride, and the pH that regulates electrolyte by the LiOH solution that drips 0.1mol/L in electrolyte is 4.Under the room temperature, battery is discharged and recharged with the 4C multiplying power at voltage range 1.5-2.1V.
Figure 27 is battery first charge-discharge among the embodiment 6-1 and the relation curve of 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 battery capacity of 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 enclosed pasture efficient and cycle-index, as can be seen from the figure battery in the enclosed pasture efficient of circulation after 1000 times more than 80%.
Embodiment 6-2
With LiMn 2O 4Be positive active material, positive active material, super-p carbon black, bonding agent PVDF are mixed according to part by weight at 83: 10: 7, as dispersant, make anode sizing agent with NMP, evenly be coated on the plus plate current-collecting body graphite foil of thickness 80 μ m, subsequent drying, compacting obtain positive pole.Negative pole is the metallic zinc paper tinsel of thickness 50 μ m, and metallic zinc is negative electrode active material, simultaneously the double negative current collector of doing also.Barrier film is non-woven fibre cloth.Electrolyte is the aqueous solution that contains 3mol/L lithium chloride and 4mol/L zinc chloride, and the pH that regulates electrolyte by the LiOH solution that drips 0.1mol/L in electrolyte is 4.Under the room temperature, battery is discharged and recharged with the 1C multiplying power 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 enclosed pasture efficient and cycle-index, and battery is in the enclosed pasture efficient of circulation after 30 times nearly 90%.
Embodiment 6-3
With LiMn 2O 4Be positive active material, positive active material, super-p carbon black, bonding agent CMC-SBR are mixed according to part by weight at 83: 10: 7, with NMP as dispersant, make anode sizing agent, evenly be coated on the plus plate current-collecting body stainless steel foil of thickness 50 μ m, stainless steel is without passivation, and subsequent drying, compacting obtain positive pole.Negative pole is the metallic zinc paper tinsel of thickness 40 μ m, and metallic zinc is negative electrode active material, simultaneously the double negative current collector of doing also.Barrier film is the glass felt-cloth.Electrolyte is the aqueous solution that contains 1mol/L lithium acetate and 1.5mol/L zinc acetate, and the pH that regulates electrolyte by LiOH and the 0.1mol/L HAc solution of dropping 0.1mol/L in electrolyte is 4.Under the room temperature, battery is discharged and recharged with the 0.5C multiplying power at voltage range 1.5-2.1V.
The battery experimental result shows among the embodiment 6-3, and the discharge capacitance that circulating battery is 320 times and enclosed pasture efficient show that all near 100% battery has very excellent cycle performance and life-span.
Embodiment 6-4
In embodiment 6-4, battery placed under 55 ℃ discharge and recharge, with research 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 still has good discharge capacitance under 55 ℃ of high temperature, and circulating battery does not almost have obvious capacity attenuation 160 times.
Embodiment 6-5
With LiMn 2O 4Be positive active material, positive active material, super-p carbon black, bonding agent PVDF are mixed according to part by weight at 83: 10: 7, with NMP as dispersant, make anode sizing agent, evenly be coated on the plus plate current-collecting body stainless (steel) wire of thickness 30 μ m, stainless steel is without passivation, and subsequent drying, compacting obtain positive pole.Negative pole is the metallic zinc paper tinsel of thickness 10 μ m, and metallic zinc is negative electrode active material, simultaneously the double negative current collector of doing also.Barrier film is the glass felt-cloth.Electrolyte is the aqueous solution that contains 1mol/L lithium acetate and 1.5mol/L zinc acetate, and the pH that regulates electrolyte by LiOH and the 0.1mol/L HAc solution of dropping 0.1mol/L in electrolyte is 4.Under the room temperature, battery is discharged and recharged with the 0.5C multiplying power 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, 30 discharge capacities of circulating battery are not decay almost, shows that battery charging and discharging stability provided by the invention is good.
Embodiment 7-1
With LiMn 2O 4Be positive active material, with positive active material, super-p carbon black, bonding agent PVDF according to part by weight 8: 1: mix, as dispersant, make anode sizing agent with NMP, evenly be coated on the plus plate current-collecting body graphite foil of thickness 80 μ m, subsequent drying, compacting obtain positive pole.Negative current collector is the graphite foil of thickness 50 μ m, and metallic zinc is plated on the graphite foil as negative electrode active material.Barrier film is the glass felt-cloth.Electrolyte is the aqueous solution that contains 2mol/L lithium acetate and 1.5mol/L zinc acetate, and the pH that regulates electrolyte by the LiOH solution that drips 0.1mol/L in electrolyte is 4.Under the room temperature, battery is discharged and recharged with the 0.5C multiplying power at voltage range 1.5-2.1V.
Embodiment 7-2
The mode identical with embodiment 7-1 made 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 made battery, and difference is that Copper Foil replaces graphite foil as negative current collector.
The battery that embodiment 7-1 provides to 7-3, battery have good cycle performance.
Although the 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 is modified and/or flexible or to adopt the replacement scheme that is equal to be obvious, the essence that all can not break away from spirit of the present invention, the term that occurs among the present invention is used for elaboration and the understanding to technical solution of the present invention, can not be construed as limiting the invention.

Claims (18)

1. a battery comprises 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, and described positive active material can be reversible be deviate from-embedded ion;
Described negative pole comprises negative current collector at least;
Described electrolyte comprises at least a solvent that can dissolve electrolyte and make described electrolyte ionization; Described electrolyte can ionize out at least a charge and discharge process at described negative pole and reduce-deposit and the active ion of oxidation-dissolving;
It is characterized in that: 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.
2. battery according to claim 1, it is characterized in that: the thickness range of described porous layer or graphene layer is 0.05-1mm.
3. 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%.
4. battery according to claim 1, it is characterized in that: the volume range that described nanoscale hole accounts for described porous layer is 10-99%.
5. battery according to claim 1, it is characterized in that: the scope of the average diameter of described nanoscale hole is 1-150nm.
6. battery according to claim 1, it is characterized in that: the material of described porous layer is selected from carbon-based material.
7. battery according to claim 6 is characterized in that: described carbon-based material is selected from least a in section's qin carbon black, activated carbon, carbon nano-tube, carbon fiber, the graphite.
8. battery according to claim 6, it is characterized in that: described carbon-based material is the mixture of activated carbon powder and binding agent, the weight percentage ranges that described activated carbon powder accounts for described porous layer is 20-99%.
9. battery according to claim 1, it is characterized in that: described negative pole also comprises the negative electrode active material that is formed at described negative pole currect collecting surface, described negative electrode active material can oxidation in described battery discharge procedure-be dissolved as described active ion.
10. battery according to claim 1 is characterized in that: the material of described negative current collector is selected from metal Ni, Cu, Ag, Pb, Sn, Fe, Al or a kind of through in the above-mentioned metal of Passivation Treatment.
11. battery according to claim 1, it is characterized in that: the metal that the material of described negative current collector is selected from carbon-based material, stainless steel, silicon or has plating/coating, described plating/coating contain in simple substance, alloy or the oxide of C, Sn, In, Ag, Pb, Co, Zn at least a.
12. battery according to claim 11 is characterized in that: the thickness range of described plating/coating is between 1-1000nm.
13. battery according to claim 1 is characterized in that: described active ion comprises metal ion, and described metal is selected from least a among Zn, Fe, Cr, Cu, Mn, the Ni.
14. battery according to claim 13 is characterized in that: described metal ion is present in the described electrolyte with at least a form in chlorate, sulfate, nitrate, acetate, formates, the phosphate.
15. battery according to claim 1 is characterized in that: lithium ion, sodium ion, zinc ion or magnesium ion can be reversible deviate from-embed to described positive active material.
16. battery according to claim 1 is characterized in that: the material of described plus plate current-collecting body is selected from graphite, stainless steel, aluminium alloy, through stainless steel or the aluminium alloy of transpassivation.
17. a battery comprises positive pole, negative pole, electrolyte,
Described positive pole comprises positive active material, and described positive active material can be reversible be deviate from-embedded ion;
Described negative pole comprises the negative electrode active material that participates in electrochemical reaction;
Described electrolyte comprises at least a solvent that can dissolve electrolyte and make described electrolyte ionization;
Described electrolyte can ionize out at least a charge and discharge process described negative pole reduce-deposit and the active ion of oxidation-dissolving or/and the ion of can be reversible deviate from-embedding at described positive pole at least a charge and discharge process, described negative electrode active material can oxidation in discharge process-be dissolved as described active ion;
It is characterized in that: described negative pole also comprises porous layer or the graphene layer that is formed at described negative electrode active material surface, and described porous layer has micron or sub-micron or nanoscale hole.
18. a battery comprises 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, and described positive active material is can be reversible to deviate from-compound of embedded ion;
Described negative pole is the electrochemistry inertia conductive electrode that does not participate in electrochemical reaction;
Described electrolyte is the aqueous solution, contains at least in charge and discharge process at described negative pole to reduce-deposit and the metal ion of oxidation-dissolving;
It is characterized in that: described negative pole comprises negative current collector and is formed at the porous layer with micron hole of described negative pole currect collecting surface.
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