CN104253283A

CN104253283A - Battery

Info

Publication number: CN104253283A
Application number: CN201310346594.7A
Authority: CN
Inventors: 颜竞; 刘洋; 陈璞
Original assignee: Positec Power Tools Suzhou Co Ltd
Current assignee: Positec Power Tools Suzhou Co Ltd
Priority date: 2013-06-28
Filing date: 2013-08-09
Publication date: 2014-12-31

Abstract

The invention discloses a battery, which includes an anode, a cathode and an aqueous electrolyte solution. The anode comprises a composite current collector and an anode sheet. The composite current collector comprises an anode current collector and a conductive film coating the anode current collector. The anode sheet includes an anode active substance, which can realize reversible prolapse and embedding of ions. The cathode is a metal, alloy or carbon based material. The aqueous electrolyte solution includes an electrolyte, which can at least ionize active ions. The active ions are reduced and deposited at the cathode to form a cathode active substance during charging, and the cathode active substance is oxidized and dissolved in the aqueous electrolyte solution during discharging. The battery provided by the invention has good cycle performance and high energy, and is hopeful to be widely applied in large energy storage, power grid peak shaving and other fields.

Description

Battery

Technical field

The invention belongs to electrochemical energy storage field, be specifically related to a kind of battery.

Background technology

In recent years, along with the development of science and technology, more and more outstanding to the demand of the especially renewable green energy resource of the energy, battery is just playing irreplaceable effect as the storage of energy and conversion equipment.In the large-scale pile that the battery by enormous amount forms, except the electrochemical properties that battery itself has, the consistency of battery manufacturing process becomes particularly important.

Be in battery at all multiple types, lithium secondary battery has lot of advantages compared with traditional ni-mh, NI-G secondary cell, and such as energy density is large, lightweight, can be applicable in the portable type electronic products such as notebook computer; Operating voltage is high, self discharge is low, have extended cycle life, memory-less effect, can repeatedly charge and discharge; Working temperature is wide, can use at many extreme environments; Security performance is good, produces during work without gas; Without environmental hazard, be conducive to environmental protection etc.

But, the coating method of common lithium ion cell electrode, the slurry mode of ni-mh, nickel-cadmium cell is all disposable at collection liquid surface coating active material layer, its advantage is that Making programme is relatively simple, but cannot weigh to the electrode active material layer of the binding agent including active material, conductive agent and necessity separately, sorting etc., cause battery consistency to control not good.

Therefore, prior art is real is necessary further raising.

In prior art, when usually preparing electrode, directly the slurry containing electrode active material is applied on a current collector in a certain way.Battery provided by the invention, when preparing positive pole, positive plate can be attached on composite current collector by hot pressing compound, bonding mode, so not only can simplify the technique preparing battery, enhance productivity, and the conducting film be arranged between positive plate and plus plate current-collecting body is conducive to the contact internal resistance that improves between positive plate and plus plate current-collecting body, battery has good consistency.

Negative pole is selected from metal, alloy or carbon-based material.

Concrete, negative pole is selected from Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or at least one in the metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

In the battery, preferably, battery also comprises the additive joined in negative pole and/or aqueous electrolyte, and additive is bismuth compound.Preferably, bismuth compound is selected from bismuth oxide and/or bismuth nitrate.

The using dosage of bismuth compound in negative pole is preferably as follows: when being used alone bismuth oxide, and bismuth oxide accounts for 0.1 ~ 10% of negative pole total weight.When being used alone bismuth nitrate, bismuth nitrate accounts for 0.1 ~ 10% of negative pole total weight.The mixture of bismuth oxide and bismuth nitrate can certainly be used.

Bismuth compound using dosage is in the electrolytic solution preferably as follows: when being used alone bismuth oxide, and bismuth oxide accounts for 0.01 ~ 5% of electrolyte total weight.When being used alone bismuth nitrate, bismuth nitrate accounts for 0.01 ~ 5% of electrolyte total weight.The mixture of bismuth oxide and bismuth nitrate can certainly be used.

Certainly in order to make battery performance more excellent, in negative pole and electrolyte, add bismuth compound simultaneously.

When bismuth compound adds negative pole and/or aqueous electrolyte, according to the different situations of negative pole and aqueous electrolyte morphosis, different feed postition can be selected from.Adding Way can be selected from physical method or chemical method, and physical method includes but not limited to that suspension method invests on negative pole or barrier film, vacuum is plated on negative pole or barrier film, magnetron sputtering is on negative pole or barrier film; Chemical method comprises electrochemistry, and to be plated to negative pole first-class.

In the execution mode of a negative pole, negative pole only comprises negative current collector, and negative current collector, as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.Preferably, bismuth compound adds the mode in negative pole, includes but not limited to, is added in dispersant by bismuth compound and makes dispersion liquid, by dispersion on negative current collector, finally removes dispersant.

The material of negative current collector is selected from but is not limited only to Ni metal, Ag, Pb, Sn, Fe, Al or at least one in the above-mentioned metal of Passivation Treatment, or carbon-based material, or stainless steel.Wherein, carbon-based material comprises graphite material, and the paper tinsel of such as business-like graphite compacting, the part by weight scope wherein shared by graphite is 90-100%.Stainless steel material includes but are not limited to stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.

Negative pole can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy, or at least one in oxide.The thickness range of plating/coating is 1-1000nm.Such as: plumbous or silver-colored on the negative current collector plated surface of copper, or cover one deck carbon with the form of coating.

In the execution mode of another negative pole, negative pole only comprises negative current collector, but the selection of negative current collector and active ion in electrolyte is corresponding, and namely the material of negative current collector is the simple substance of active ion, if active ion in electrolyte is Zn ²⁺, negative pole corresponds to Metal Zn.Now, negative pole is not only the deposition vehicle as active ion, also can participate in cell reaction simultaneously.Preferably, bismuth compound adds the mode in negative pole, includes but not limited to, is added in dispersant by bismuth compound and makes dispersion liquid, by dispersion on negative current collector, finally removes dispersant.

In the execution mode of another negative pole, negative pole comprises negative current collector and negative electrode active material, the selection of negative electrode active material and the corresponding of active ion in electrolyte, namely the material of negative electrode active material is the simple substance of active ion, if active ion in electrolyte is Zn ²⁺, negative electrode active material corresponds to Metal Zn.Example, negative pole comprises filtter gold and zinc paper tinsel, and filtter gold is as negative current collector, and the corresponding negative electrode active material of zinc paper tinsel, can participate in negative reaction.

In this case, bismuth compound adds the mode in negative pole, include but not limited to, bismuth compound is added in dispersant and makes dispersion liquid, by dispersion on Metal Zn negative pole, finally remove dispersant, or bismuth compound and Zn powder are mixed and made into slurry, then slurry is coated on negative current collector and makes negative pole.

Aqueous electrolyte comprises electrolyte, and electrolyte at least can ionize out active ion, and active ion is reduced when charging and is deposited on negative pole formation negative electrode active material, and negative electrode active material is oxidized when discharging to be dissolved in aqueous electrolyte.

Active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.In a preferred embodiment, active ion is Zn ²⁺.The concentration range of active ion is 0.5-15mol/L.

Preferred, also comprise a kind of electrolyte in electrolyte, this electrolyte can ionize out correspondence can there is the reversible ion deviate from-embed at positive pole.

Containing can the reversible ion deviate from-embed in electrolyte, thus positive active material and electrolyte intermediate ion exchange velocity can be improved.Concrete, positive active material is can the reversible compound deviating from-embeds lithium ion, and in electrolyte, correspondence also comprises the lithium salts that can ionize out lithium ion.The reversible ion deviate from-embed comprises lithium ion or sodium ion or magnesium ion, and the reversible ion deviate from-embed concentration range is in the electrolytic solution 0.1-10mol/L.

Active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate, formates or alkylsulfonate.

Alkylsulfonate including but not limited to aliphatic sulfonate, and is not limited on aliphatic group with functional group or substituting group.The anion of alkylsulfonate preferably meets following general formula:

R-SO ₃ ^-or Y-R '-SO ₃ ^-

In above-mentioned general formula, Y refers to substituting group, such as-F ,-OH etc.

In above-mentioned general formula, R can be branching or nonbranched fat-based; Can be the fat-based of 1 ~ 12 carbon atom, be preferably the fat-based of 1 ~ 6 carbon atom, particularly preferably methyl, ethyl and n-pro-pyl.

In above-mentioned general formula, R ' can be branching or nonbranched fat-based; Can be the fat-based of 2 ~ 12 carbon atoms, be preferably the fat-based of 2 ~ 6 carbon atoms, be more preferably non-branching, fat-based containing 2 ~ 6 carbon atoms; More preferably, substituting group and sulfonic group are not connected on same carbon atom.

Particularly preferably, alkylsulfonate is metilsulfate, and namely R is methyl.

Preferably, active ion is present in aqueous electrolyte with the form of alkylsulfonate, aqueous electrolyte containing alkyl sulfonate ion does not freeze at-20 DEG C, battery can be made to have better cryogenic property, simultaneously can also improve active ion (such as zinc ion) and deviate from the concentration of-embedded ion (as lithium ion), the increase of aqueous electrolyte intermediate ion concentration effectively can improve the high-rate charge-discharge capability of battery.Except, alkyl sulfonate ion can suppress the generation of gas in aqueous electrolyte, and effectively can reduce the self-discharge rate of battery.

In order to ensure battery capacity, the concentration of the active ion in electrolyte must reach certain limit, when alkali crossed by electrolyte, can affect the solubility of active ion in electrolyte; When electrolyte peracid, then there will be the problems such as proton embeds altogether in electrode material corrosion and charge and discharge process, therefore, the pH value range of electrolyte is 3-7.

Battery of the present invention, adds bismuth compound in negative pole or aqueous electrolyte.Due to adding of bismuth compound, pH value can be effectively suppressed to be hydrogen ion activity in the aqueous electrolyte of 3-7, the reaction activity of aqueous electrolyte and negative pole is raised, suppress the reaction between aqueous electrolyte and negative pole, thus effectively inhibit the generation of gas in battery, thus improve the security performance of battery, add the serviceability of battery simultaneously.

Certainly, in order to provide better security performance, preferably between positive pole and negative pole, barrier film is provided with in the electrolytic solution.The short circuit that the both positive and negative polarity that barrier film can avoid other unexpected factors to cause is connected and causes.

Barrier film of the present invention does not have particular/special requirement, as long as allow electrolyte to pass through and the barrier film of electronic isolation.The various barrier films that organic system lithium ion battery adopts, all go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.

The charge-discharge principle of battery provided by the invention is: during charging, deviates from the reversible ion deviate from-embed in positive active material, simultaneously oxidized with variable valency metal in positive active material, and ejected electron; Electronics arrives battery cathode via external circuit, and the active ion simultaneously in electrolyte obtains electronics at negative pole and is reduced, and is deposited on negative pole.Discharge process is the inverse process of charging.

Battery uses aqueous electrolyte, there is not the potential safety hazards such as organic electrolyte is inflammable, and aqueous electrolyte has higher ionic conductivity relative to organic electrolyte, reduces the impact of battery polarization.

Battery provided by the invention has good cycle performance, higher energy.Therefore, battery of the present invention has very large application potential in fields such as large-scale energy storage, peak load regulation networks.

[bipolar battery]

Present invention also offers a kind of battery, concrete, battery is water system bipolar battery structure.Water system bipolar battery is introduced below by concrete execution mode.

In prior art, when usually preparing electrode, directly the slurry containing electrode active material is applied on a current collector in a certain way.Electrode 10 provided by the invention, direct preparation contains the electrode slice 1 of electrode active material, then electrode slice 1, conducting film 12 and electrode current collecting body 8 are combined with each other, so not only can simplify the technique preparing electrode, enhance productivity, and the conducting film 12 be arranged between electrode slice 1 and electrode current collecting body 8 is conducive to improving the contact internal resistance between electrode slice 1 and electrode current collecting body 8, electrode 10 has good consistency.

Electrode current collecting body 8 has the first surface and second that are oppositely arranged, and preferably, the first surface of electrode current collecting body 8 and second are compounded with conducting film 12 and electrode slice 1 respectively successively.

The material of conducting film 12, at by the agency of above, just repeats no more here.

Electrode current collecting body 8 is mainly as conduction with collect the carrier of electronics, and electrode current collecting body 8 demand fulfillment surface area is large, good mechanical property, the requirement such as conduct electricity very well.The material of electrode current collecting body 8 comprises the one in carbon-based material, metal or alloy.

Carbon-based material is selected from the one in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In a particular embodiment, plus plate current-collecting body is graphite, and as the paper tinsel that business-like graphite is suppressed, the part by weight scope wherein shared by graphite is 90-100%.

Metal is wire netting or metal forming, and metal comprises Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.

The main purpose of metal being carried out Passivation Treatment makes metallic surface form one deck passivating film, thus in battery charge and discharge process, can play stable collection and the effect of conduction electron, and can not participate in electrode reaction, ensures battery performance.

Alloy comprises stainless steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned metal of Passivation Treatment.

Stainless steel comprises stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.

Same, stainless steel is carried out Passivation Treatment be also can be stable play and collect and the effect of conduction electron, and electrode reaction can not be participated in, guarantee battery performance.In a specific embodiment, the stainless detailed process of passivation is: at 50 DEG C, stainless steel is inserted half an hour in the nitric acid of 20%, makes stainless steel surfaces form one deck passivating film.Stainless steel after passivation uses as electrode current collecting body.

The chemical property of thickness to electrode 10 of electrode current collecting body 8 has certain influence, and the thickness of electrode current collecting body 8 is too thin, can affect the mechanical strength of electrode current collecting body 8; The thickness of electrode current collecting body 8 is too thick, can increase the weight of electrode 10, thus affects the energy density of electrode 10, and in the present invention, have high energy density to make battery and export, preferably, the thickness of electrode current collecting body 8 is 10 μm-100 μm.

Example, electrode current collecting body 8 adopts stainless steel, can carry out punching process to stainless steel, and preferably, pore size scope is 500 μm of-5mm; Also sand paper can be adopted to polish to stainless steel, make stainless steel surfaces roughening; Suitable weak acid can also be selected to carry out microcorrosion to stainless steel, and object increases stainless specific area under the prerequisite not destroying stainless steel machinery performance.Treated electrode current collecting body 8 has larger specific area, is conducive to the Compound Degree improving electrode current collecting body 8 and conducting film 12, reduces the contact internal resistance between electrode slice 1 and electrode current collecting body 8.

Concrete, by hot pressing mixed binding by electrode slice 1, conducting film 12 and electrode current collecting body 8, hot pressing compound is heated polymerizable thing under the glass transition temperature by polymer in higher than conducting film 12, polymeric material in conducting film 12 is made to soften and reach the state being bonded to collector, apply certain pressure simultaneously, pressure size is not particularly limited, main purpose be make electrode slice 1, combine between conducting film 12 and electrode current collecting body 8 tightr.Concrete, the temperature T of hot pressing compound meets the following conditions: T _g<T<T _m, wherein T _gthe glass transition temperature of polymer in conducting film, T _mit is the fusing point of polymer in conducting film.

The preparation process of electrode can be completed by a step hot pressing compound, concrete, is placed in by conducting film 12 between electrode slice 1 and electrode current collecting body 8, directly electrode slice 1, conducting film 12 and electrode current collecting body 8 is combined with each other by hot pressing compound.

The preparation process of electrode also can be completed by two step hot pressing compounds, and namely hot pressing superpacket draws together first step hot pressing compound and second step hot pressing compound.First step hot pressing compound can be attached on electrode current collecting body 8 by conducting film 12, or is attached on electrode slice 1 by conducting film 12.Corresponding, second step hot pressing compound is attached on conducting film 12 by electrode slice 1, or be attached on conducting film 12 by electrode current collecting body 8.

Preferably, first step hot pressing compound is attached on electrode current collecting body 8 by conducting film 12, preferred, is attached to respectively by two panels conducting film 12 on the first surface of electrode current collecting body 8 and second.

Electrode current collecting body 8 is placed between two panels conducting film 12, preferably, the area of conducting film 12 is at least equal with the area of electrode current collecting body 8, like this, in first step hot pressing recombination process, main component is that the conducting film 12 of polymer has certain ductility, and the conducting film 12 after calendering covers on the first surface of electrode current collecting body 8 and second completely, then conducting film 12, electrode current collecting body 8 and conducting film 12 is combined with each other.Preferentially conducting film 12 is attached on electrode current collecting body 8; electrode current collecting body 8 and conducting film 12 can be combined with each other more closely; and the part that the rear conducting film 12 of calendering exceeds electrode current collecting body 8 is also sealed into one completely in first step hot pressing recombination process; conducting film 12 pairs of electrode current collecting bodies 8 are played a protective role; electrolyte is avoided to produce corrosion to electrode current collecting body 8 and cause self discharge; the more important thing is, conducting film 12 better can play the effect of the contact internal resistance reduced between electrode slice 1 and electrode current collecting body 8.

In second step hot pressing compound, two panels is cut out the hot pressing of sizable electrode slice 1 and to be compound on conducting film 12, finally make electrode slice 1, conducting film 12, electrode current collecting body 8 be combined with each other, obtain electrode.

In a particular embodiment, also comprise binder polymer in electrode slice active material layer, the weight proportion that binder polymer accounts for active material layer is 0.5-10%.Because binder polymer proportion is less, can not there is significant change in binder polymer in hot pressing recombination process, and therefore the form of electrode slice and performance can not be affected.Preferably, the temperature of hot pressing compound is lower than the decomposition temperature of binder polymer in electrode slice.

By hot pressing compound, conducting film is compounded between electrode slice and electrode current collecting body, conducting film not only can peel resistance between modified electrode sheet and electrode current collecting body, improve the stability of electrode, and the resistance between electrode slice and electrode current collecting body is reduced, make the battery containing this electrode have high Energy transmission.

Electrode of the present invention can be constructed by hot pressing alternatively and be compounded to form positive pole containing positive plate, conducting film and plus plate current-collecting body, or the negative pole containing negative plate, conducting film and negative current collector, or the bipolar electrode containing positive plate, conducting film, collector and negative plate.

The solution of the present invention is set forth further below by specific embodiment.

Summary of the invention

The present invention aims to provide a kind of battery with good cycle performance and higher energy.

The invention provides a kind of battery, comprise positive pole, negative pole and aqueous electrolyte, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

Present invention also offers a kind of battery, comprise positive pole, two negative poles and aqueous electrolyte, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion, described composite current collector has the first surface and second that are oppositely arranged, and described positive plate is arranged on described first surface and second; Described two negative poles share described positive pole, and described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

Present invention also offers a kind of battery, comprise two positive poles, negative pole and aqueous electrolytes, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion, described composite current collector has the first surface and second that are oppositely arranged, described first surface is relative with described negative pole, and at least described first surface is provided with described positive plate; Described two positive poles share described negative pole, and described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

Present invention also offers a kind of battery, comprise positive pole, negative pole and aqueous electrolyte, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion, described composite current collector has the two sides be oppositely arranged, wherein, the one side that at least described composite current collector is relative with described negative pole is provided with positive plate; Described negative pole is selected from metal, alloy or carbon-based material; Described battery n to described positive pole and negative pole, n >=2, two adjacent positive poles share the negative pole between two positive poles, and two adjacent negative poles share the positive pole between two negative poles; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

Preferably, described battery also comprises the additive joined in described negative pole and/or aqueous electrolyte, and described additive is bismuth oxide and/or bismuth nitrate.

Preferably, described negative pole is selected from Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or at least one in the described metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

Present invention also offers a kind of battery, comprise positive extraction electrode, at least one bipolar electrode, negative extraction electrode and aqueous electrolyte, described positive extraction electrode comprises composite current collector and is arranged on the positive plate of described composite current collector one side, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion; Described bipolar electrode is arranged between described positive extraction electrode and negative extraction electrode, described bipolar electrode comprises bipolar current collector and described positive plate, described bipolar current collector has the first surface and second that are oppositely arranged, and described positive plate is arranged on the first surface of described bipolar current collector; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced second the formation negative electrode active material being deposited on described bipolar current collector when charging, described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte; Described negative extraction electrode is selected from metal, alloy or carbon-based material; Described aqueous electrolyte is arranged between described positive extraction electrode and negative extraction electrode.

Preferably, described battery also comprises the additive joined in described negative extraction electrode and/or aqueous electrolyte, and described additive is bismuth oxide and/or bismuth nitrate.

Preferably, the peripheral part of described bipolar current collector is provided with the sealing for sealing described aqueous electrolyte.

Preferably, the material of described bipolar current collector comprises conductive plastics, stainless steel or the stainless steel through Passivation Treatment.

Preferably, the material of described conductive plastics is selected from conducting polymer.

Preferably, the material of described conductive plastics comprises polymer and conductive agent.

Preferably, material selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al of described negative extraction electrode or at least one in the described metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

Preferably, described positive plate also comprises the carrier of electrochemicaUy inert, and described positive active material is formed on the carrier.

Preferably, described carriers electron insulate and has loose structure.

Preferably, the range of aperture size of described carrier is 50-200 order.

Preferably, described carrier can conduction electron.

Preferably, the material of described carrier is selected from least one in polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polyamide, polyurethanes, polyacrylonitrile.

Preferably, described carrier is nonwoven fabrics.

Preferably, the thickness of described carrier is less than 1mm.

Preferably, described carrier has the first surface and second that are oppositely arranged, and the first surface of described carrier and second are all formed with described positive active material.

Preferably, described positive active material is formed on the carrier by slurry.

Preferably, described positive active material has spinel structure, layer structure or olivine structural.

Preferably, described conducting film comprises thermoplastic polymer.

Preferably, described conducting film is attached on described plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.

Preferably, described positive plate is attached on described conducting film by hot pressing compound, bonding mode.

Preferably, the material of described plus plate current-collecting body is selected from the one in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned alloy of Passivation Treatment.

Preferably, described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.

Preferably, described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate, formates or alkylsulfonate.

Preferably, described alkylsulfonate is metilsulfate.

Preferably, described aqueous electrolyte also comprise with described positive active material can reversible deviate from-the corresponding ion of embedded ion.

Preferably, described battery also comprises barrier film, and described barrier film keeps described aqueous electrolyte.

Battery provided by the invention has cheap price, good cycle performance and higher energy.Therefore, battery of the present invention is expected to obtain in fields such as large-scale energy storage, peak load regulation networks use widely.

Present invention also offers a kind of battery pack, comprise several batteries as above.

Present invention also offers a kind of uninterrupted power supply, comprise battery as above.

Present invention also offers a kind of vehicle, comprise battery as above as motor driven power supply.

Present invention also offers a kind of electrode slice, the carrier that described electrode slice comprises electrochemicaUy inert and the active material layer be formed on described carrier, described carriers electron insulate and has loose structure.

Preferably, the range of aperture size of described carrier is 50-200 order.

Preferably, the thickness of described carrier is less than 1mm.

Preferably, the thickness range of described electrode slice is 0.3-1.5mm.

Preferably, described carrier has the first surface and second that are oppositely arranged, and the first surface of described carrier and second are all formed with described active material layer.

Described in a kind of electrode, electrode comprises electrode slice as above.

Preferably, described electrode also comprises the electrode current collecting body with conducting film, and described electrode slice is attached on described conducting film.

A preparation method for electrode slice, described preparation method comprises the following steps: prepare slurry, is formed on the carrier of electrochemicaUy inert by described slurry, forms active material layer, and described carriers electron insulate and has loose structure, drying and moulding.

Preferably, described slurry comprises electrode active material, binding agent and conductive agent, and described electrode active material participates in electrochemical reaction.

Preferably, described electrode active material accounts for the percentage by weight of described active material layer is 60-99%.

Preferably, in described active material layer, the surface density of electrode active material is 200-2000g/m ².

Preferably, the temperature range of described drying is 50-130 DEG C.

A kind of preparation method of electrode, described preparation method comprises the following steps: electrode slice, conducting film and electrode current collecting body are combined, described conducting film is between described electrode slice and electrode current collecting body, the carrier that described electrode slice comprises electrochemicaUy inert and the active material layer be formed on described carrier, described carriers electron insulate and has loose structure, and described conducting film comprises polymer.

Preferably, by described electrode slice, conducting film and electrode current collecting body by hot pressing mixed binding, the temperature T of described hot pressing compound meets the following conditions: T _g<T<T _m, wherein T _gthe glass transition temperature of polymer in described conducting film, T _mit is the fusing point of polymer in described conducting film.

Preferably, described hot pressing compound comprises first step hot pressing compound and second step hot pressing compound, described first step hot pressing compound is attached on described electrode current collecting body by described conducting film, and described second step hot pressing compound is attached on described conducting film by described electrode slice.

Preferably, the area of described conducting film is at least equal with the area of described electrode current collecting body.

Preferably, described carrier is nonwoven fabrics.

Preferably, the range of aperture size of described carrier is 50-200 order.

Preferably, the thickness range of described conducting film is 10 μm of-2mm.

Preferably, in described conducting film, polymer is selected from thermoplastic polymer.

Preferably, before the described electrode current collecting body of use, described electrode current collecting body is through transpassivation, punching, polishing or weak acid corrosion treatment.

Preferably, the thickness range of described electrode current collecting body is 10 μm-100 μm.

Preferably, the material of described electrode current collecting body is selected from the one of carbon-based material, metal or alloy, and wherein, described carbon-based material is selected from the one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber; Wherein, described metal is selected from Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment; Wherein, described alloy is selected from stainless steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned alloy of Passivation Treatment.

Preferably, the thickness of described carrier is less than 1mm.

The invention provides that electrode slice is easy to processing, thickness is homogeneous and be easy to sorting, consistency of performance is good, and the battery applying this electrode slice has cheap price, good cycle performance and higher energy.Therefore, battery of the present invention is expected to obtain in fields such as large-scale energy storage, peak load regulation networks use widely.

Accompanying drawing explanation

Fig. 1 is the cell integrated structural profile schematic diagram that execution mode one provides;

Fig. 2 is the structural representation of the bipolar electrode that execution mode one provides;

Fig. 3 is the generalized section of the cell integrated structure that execution mode one provides, and wherein, show diagrammatically battery unit;

Fig. 4 is that execution mode one provides battery charging principle schematic diagram;

Fig. 5 is the generalized section of the cell integrated structure that execution mode two provides;

Fig. 6 is the generalized section of the cell integrated structure that execution mode two provides, and wherein, show diagrammatically battery unit;

Fig. 7 is the generalized section of the cell integrated structure that execution mode three provides;

Fig. 8 is the generalized section of the cell integrated structure that execution mode four provides;

Fig. 9 is the generalized section of the cell integrated structure that execution mode five provides;

Figure 10 is the generalized section of the cell integrated structure that execution mode five provides, and wherein, show diagrammatically battery unit;

Figure 11 is the generalized section of the cell integrated structure that execution mode six provides;

Figure 12 is the generalized section of the cell integrated structure that execution mode seven provides, and wherein, positive pole and negative pole are two;

Figure 13 is the generalized section of the cell integrated structure that execution mode seven provides, and wherein, the number of positive pole and negative pole is greater than two;

Figure 14 is the structural representation of electrode slice provided by the invention, wherein, the first surface of carrier and second is all formed with active material layer;

Figure 15 is the cross-sectional view of electrode provided by the invention;

Figure 16 is the cross-sectional view of electrode provided by the invention, wherein electrode current collecting body has conducting film;

Figure 17 is the internal resistance of cell that provides of embodiment 1 and comparative example 1 and the relation curve of discharge and recharge time;

Figure 18 is the battery discharge curve that embodiment 3 and comparative example 2 provide;

Figure 19 is the discharge capacity of the cell that provides of embodiment 4 and cycle-index relation curve;

Figure 20 is the discharge capacity of the cell that provides of embodiment 5 and cycle-index relation curve.

Wherein:

Embodiment

A kind of battery, battery can be applied to as the portable type electronic product such as mobile phone, notebook computer, electric automobile, electric tool etc.

[battery]

Battery positive pole, negative pole and aqueous electrolyte, aqueous electrolyte is between positive pole and negative pole.

Positive pole comprises composite current collector and positive plate, and composite current collector comprises plus plate current-collecting body and is coated on conducting film on plus plate current-collecting body, and positive plate comprises positive active material, positive active material can reversible deviate from-embedded ion.

Positive active material participates in electrochemical reaction, and the weight percentage ranges that positive active material accounts for positive plate is 60-99%.In order to make just have higher capacity, in positive plate, the surface density scope of positive active material is 200-2000g/m ².

Concrete, positive active material has spinel structure, layer structure or olivine structural.

Concrete, lithium ion, sodium ion or magnesium ion can deviate from-embedded to positive active material reversiblely.

Positive active material can be meet general formula Li _1+xmn _ym _zo _kcan the reversible compound deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, Ni.Preferably, positive active material contains LiMn ₂o ₄.Preferred, positive active material contains the LiMn through overdoping or coating modification ₂o ₄.

Positive active material can be meet general formula Li _1+xm _ym ' _zm " _co _2+ncan the reversible compound deviating from-embed the layer structure of lithium ion, wherein,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material contains LiCoO ₂.

Positive active material can be meet general formula Li _xm _1-ym ' _y(XO ₄) _ncan the reversible compound deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO ₄.

In current Lithium Battery Industry, nearly all positive active material all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn ₂o ₄can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li _1+xmn _ym _zo _kbe as the criterion, comprise the LiMn through various modification widely ₂o ₄positive active material.Same, LiFePO ₄and LiCoO ₂also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively _xm _1-ym ' _y(XO ₄) _nand Li _1+xm _ym ' _zm " _co _2+npositive active material.

Positive active material be lithium ion deviate from-inlaid scheme time, can select as LiMn ₂o ₄, LiFePO ₄, LiCoO ₂, LiM _xpO ₄, LiM _xsiO _ycompounds such as (wherein M are a kind of variable valency metal).

In addition, the compound N aVPO of sodium ion can be deviate from-embed ₄f, can deviate from-embed the compound Mg M of magnesium ion _xo _y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive active material of battery of the present invention, therefore, the present invention is not limited to lithium ion battery.

In a particular embodiment, when preparing positive plate, also can add binding agent in positive active material, binding agent is conducive to positive active material is bonded together uniformly, thus is processed to form positive plate.The weight percentage ranges that binding agent accounts for positive plate is 0.5-10%.Concrete, binding agent is selected from but is not limited only to polymer, and polymer is selected from least one in polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC), sodium carboxymethylcellulose derivative (CMC derivation), butadiene-styrene rubber (SBR), butadiene-styrene rubber derivative (SBR derivation).Butadiene-styrene rubber derivative has hydrophilic butadiene-styrene rubber (PSBR100) as what obtained by chemical modification.

In a particular embodiment, when preparing positive plate, also can add conductive agent in positive active material, conductive agent mainly play improve positive active material in positive plate lead electronic capability, the weight percentage ranges that conductive agent accounts for positive plate is 0.5-30%.Conductive agent comprises at least one be selected from conducting polymer, carbon nano-tube, activated carbon, Graphene, carbon black, graphite, carbon fiber, conductivity ceramics.Carbon black includes but are not limited to acetylene black, section's qin carbon black (Ketjen black, KB) and super-p carbon black.Conductive agent can also comprise metal oxide.Metal oxide includes but are not limited to lead oxide and tin oxide.

In the present invention, positive plate be should be to the understanding of positive plate and comprise necessary positive active material, and do not comprise plus plate current-collecting body.In prior art, when usually preparing positive pole, directly the slurry containing active material is applied on a current collector in a certain way, dry aft-loaded airfoil and become positive pole.The positive pole prepared under this technique, the weight of whole positive pole can only be weighed when carrying out sorting, and consider the inhomogeneities of each areal weight distribution of collector itself, this sorting can not be accurate to the weight measuring active material in each positive pole, cause the inconsistent of each positive electrode capacity thus, finally cause the inconsistent of whole Battery pack and affect chemical property and rate of finished products.In the present invention, positive plate can depart from plus plate current-collecting body and prepare separately shaping, in the process preparing positive plate, is conducive to weighing sorting separately to positive active material, has increased substantially battery consistency and has made battery be easy to assembling.

In a particular embodiment, positive plate also comprises the carrier of electrochemicaUy inert, positive active material is formed on carrier, carrier has the first surface and second that are oppositely arranged, do not limit, the first surface of carrier or second are formed with positive active material, or the first surface of carrier and second are all formed with positive active material.

The preparation method of positive plate is not particularly limited, and in a particular embodiment, the first slurry of preparation containing positive active material, be then formed on carrier by slurry, positive active material is formed on carrier by slurry.

Carrier mainly plays a part to carry positive active material, the electrochemicaUy inert of carrier own, according to as well known to those skilled in the art, electrochemicaUy inert and carrier do not participate in any electrochemical reaction, stable is present in positive plate, only exists as the matrix carrying active material layer.

In a concrete execution mode, carriers electron insulate and has loose structure, concrete, the range of aperture size of carrier is 50 order-200 orders, like this, under ensureing that carrier has certain mechanical performance prerequisite, not only being conducive to positive active material is attached on carrier, improve the resistance to peeling force of positive active material and carrier, ensure the work that positive plate is stable, and facilitate the transmission of positive active material intermediate ion.

In another particular embodiment of the invention, carrier can conduction electron, and the material of carrier includes but are not limited to electroconductive resin or metal.

The thickness of carrier is not particularly limited, but in order to ensure that positive plate has high energy density, therefore needs the thickness controlling positive plate, concrete, the thickness range of positive plate is 0.3-1.5mm, and as the carrier of one of positive plate composition, preferably, the thickness of carrier is less than 1mm.

Concrete, from manufacture craft, carrier can be nonwoven fabrics, and nonwoven fabrics, not through textile process, forms by means of only physical means is bonding.The composition of nonwoven fabrics is not specifically limited, as long as can meet the conditions such as electrochemicaUy inert.Non-woven weight is very light, stable performance, easily sizing and cost is low.In the present invention, by nonwoven fabrics and positive active material connected applications in positive plate, make positive plate weight lighter and there is stable chemical property.

From composition, the material of carrier is selected from least one in polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), polyamide (PA), polyurethanes (PU), polyacrylonitrile (PAN).These materials can be stable be present in positive plate and do not participate in electrochemical reaction, and be that the energy density that battery is high exports saving in weight.

In the prior art preparing positive pole, the slurry containing graphite on a current collector, such as, in lithium ion battery, is coated on Copper Foil and makes negative pole by the normally direct slurry coating by containing active material; In lead-acid battery, lead plaster is coated on grid and makes negative pole.The electrode prepared under this technique, the weight of whole electrode can only be weighed when carrying out sorting, and consider the inhomogeneities of each areal weight distribution of collector itself, this sorting can not be accurate to the weight measuring active material in each electrode, cause the inconsistent of each positive electrode capacity thus, finally cause the inconsistent of whole Battery pack and affect chemical property and rate of finished products.Positive plate provided by the invention, positive active material, binding agent and the ratio of conductive agent are accurately consistent, and the carrier of electrochemicaUy inert is also the material selecting consistency very high, and thus obtained positive plate weight consistency is very high.

Composite current collector comprises plus plate current-collecting body and be coated on plus plate current-collecting body upper conductive film, and plus plate current-collecting body is mainly as conduction and the carrier collecting electronics, and plus plate current-collecting body demand fulfillment surface area greatly, good mechanical property, the requirement such as conduct electricity very well.The material of plus plate current-collecting body comprises the one in carbon-based material, metal or alloy.

Metal comprises Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.In a particular embodiment, plus plate current-collecting body is nickel foam.Composite current collector containing nickel foam, is not easily corroded in aqueous electrolyte, thus makes the cathode performance containing this composite current collector more stable.

The main purpose of metal being carried out Passivation Treatment makes metallic surface form one deck passivating film, thus in battery charge and discharge process, can play stable collection and the effect of conduction electron, and can not participate in positive pole reaction, ensures battery performance.

Alloy comprises stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned metal of Passivation Treatment.

Same, stainless steel is carried out Passivation Treatment be also can be stable play and collect and the effect of conduction electron, and electrode reaction can not be participated in, guarantee battery performance.In a specific embodiment, the stainless detailed process of passivation is: at 50 DEG C, stainless steel is inserted half an hour in the nitric acid of 20%, makes stainless steel surfaces form one deck passivating film.Stainless steel after passivation uses as collector.

The chemical property of thickness to positive pole of plus plate current-collecting body has certain influence, and the thickness of plus plate current-collecting body is too thin, can affect the mechanical strength of plus plate current-collecting body; The thickness of plus plate current-collecting body is too thick, can increase the weight of positive pole, thus affects the energy density of positive pole, and in the present invention, have high energy density to make battery and export, preferably, the thickness of plus plate current-collecting body is 10 μm-100 μm.

Preferably, before use plus plate current-collecting body, plus plate current-collecting body is through transpassivation, punching, polishing or weak acid corrosion treatment, treated plus plate current-collecting body has larger specific area, be conducive to the Compound Degree improving plus plate current-collecting body and conducting film, thus reduce the contact internal resistance between positive plate and composite current collector.

Plus plate current-collecting body is coated with the conducting film that one deck can conduct electricity, the selection of conducting film must to meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, do not occur swelling, high voltage can not oxidized, be easy to be processed into densification, the waterproof and film of conduction.On the one hand, conducting film can play a protective role to plus plate current-collecting body, avoids aqueous electrolyte to the corrosion of plus plate current-collecting body.On the other hand, be conducive to reducing the contact internal resistance between positive plate and plus plate current-collecting body, improve the energy of battery.

In order to effectively play the effect of conducting film, the thickness of conducting film needs effective control.The too thin easy breakage of conducting film thickness, caliper uniformity is also bad, and aqueous electrolyte easily penetrates; Conducting film is too thick, affects conductive capability.Preferably, the thickness of conducting film is 10 μm of-2mm, and conducting film effectively can not only play the effect of protection plus plate current-collecting body, and is conducive to reducing the contact internal resistance between positive plate and plus plate current-collecting body, improves the energy of battery.

Plus plate current-collecting body has the first surface and second that are oppositely arranged, and preferably, the first surface of plus plate current-collecting body and second are all coated with conducting film.

Conducting film comprises the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50-95%, and preferably, polymer is selected from thermoplastic polymer.In order to enable conducting film conduct electricity, there is the form that two kinds feasible: (1) polymer is conducting polymer; (2) conducting film also comprises conductive filler.

Conducting polymer choice requirement, namely can not as the ionic conduction of charge transfer medium for having electric conductivity but electrochemicaUy inert.Concrete, conducting polymer includes but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and any mixture thereof.Conducting polymer inherently has conductivity, but can also adulterate to conducting polymer or modification to improve its conductive capability further.Consider from the stable use electric conductivity and battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.

Same, the choice requirement of conductive filler be surface area little, be difficult to oxidation, degree of crystallinity high, there is conductivity but electrochemicaUy inert, namely can not as the ionic conduction of charge transfer medium.

The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler mass percent scope is in the conductive film 5-50%.The average grain diameter of conductive filler is not particularly limited, usual scope at 100nm to 100 μm.

Preferably, conductive filler is carbon-based material, and form or the mechanical performance of carbon-based material do not specially require, example, and carbon-based material is selected from the one in graphite, carbon nano-tube or amorphous carbon.Amorphous carbon includes but are not limited to active carbon and carbon black.The preferred carbon black of carbon-based material and graphite, it has large potential window, thus stablizes the both positive and negative polarity electromotive force of relative broad range and have high conductivity.Metal oxide includes but are not limited to lead oxide, tin oxide.

When comprising conductive filler in conducting film, the polymer in conducting film preferably comprises the non-conductive polymer played in conjunction with conductive filler effect, and non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.

Concrete, thermoplastic polymer includes but are not limited to polyolefin as polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, polyolefin, polyamide and Kynoar is preferably.These polymer are easily melted by heat, therefore easily and plus plate current-collecting body and positive plate be combined with each other.In addition, these polymer have large potential window, thus make positive stabilizer pole be also battery output density saving in weight.

Concrete, the slurry that can contain thermoplastic polymer by preparation is also coated with and cure pastes forms conducting film.Certainly, what conductive filler can be extra is contained in slurry, concrete, by polymer and conductive filler with certain complex method as dispersion compound, level compound carry out processing the conducting film obtaining and have electric conductivity.Preferably, by polymer monomer and conductive filler mixing, because polymer monomer is Small molecular, conductive filler can be good at being dispersed in polymer monomer, then under the effect of initator, polymer monomer is polymerized, prepares conducting film.

Conducting film is attached on plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.

Hot pressing compound is heated polymerizable thing under the glass transition temperature by polymer in higher than conducting film, polymeric material in conducting film is softened and reaches the state being bonded to plus plate current-collecting body, apply certain pressure simultaneously, pressure size is not particularly limited, main purpose be make to combine between conducting film and plus plate current-collecting body tightr.

In the execution mode vacuumized, conducting film can be made into the sack of pre-sizing, three edge sealings, then the plus plate current-collecting body cut out be placed in conducting film bag, by the mode vacuumizing, seal, conducting film is coated on plus plate current-collecting body closely.

In the execution mode of spraying, the slurry of preparation containing thermoplastic polymer, then uniformly sprays on plus plate current-collecting body by slurry, after slurry cooling, solidification, namely plus plate current-collecting body is coated with one deck conducting film.

Execution mode one

Refer to shown in Fig. 1 and Fig. 2, battery 20 comprises positive extraction electrode 22, at least one bipolar electrode 24, negative extraction electrode 26 and aqueous electrolyte 28.Positive extraction electrode 22, bipolar electrode 24 and the stacked setting of negative extraction electrode 26, positive extraction electrode 22 and negative extraction electrode 26 lay respectively at the superiors and orlop, and bipolar electrode 24 and aqueous electrolyte 28 are arranged between positive extraction electrode 22 and negative extraction electrode 26.Specific in Fig. 1, battery 20 comprises two bipolar electrodes 24.

Positive extraction electrode 22 comprises plus plate current-collecting body 30 and is arranged on the positive plate 23 of plus plate current-collecting body 30 one side, and positive plate 23 comprises positive active material 50, positive active material 50 can reversible deviate from-embedded ion.Specific in execution mode one, positive plate 23 also comprises the carrier 2 of electrochemicaUy inert, and positive active material 50 is formed on carrier.

Foregoing describes plus plate current-collecting body 30, positive active material 50 and carrier 2, just no longer repeat here to introduce.

Fig. 2 is the summary section of the bipolar electrode 24 forming battery 20, bipolar electrode 24 comprises bipolar current collector 32 and positive plate 23, bipolar current collector 32 has the first surface 321 and the second face 322 that are oppositely arranged, and positive plate 23 is arranged on the first surface 321 of bipolar current collector 32.The first surface 321 of bipolar current collector 32 is contrary with the second face 322 polarity, and first surface 321 is equivalent to positive pole, and the second face 322 is equivalent to negative pole.

Positive plate 23 is attached in bipolar current collector 32 by certain mode, and as stacked, compacting, bonding or hot pressing compound etc., in positive plate 23, carrier 2 and positive active material 50 have been introduced in detail above, just repeat no more here.

The material of bipolar current collector 32 can be conductive plastics, and preferably, the thickness range of bipolar current collector 32 is 50 to 100 μm.

The material of conductive plastics is selected from conducting polymer, concrete, and conducting polymer includes but are not limited at least one in polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, poly quinoline or polyparaphenylene.Conducting polymer inherently has conductivity, but can also adulterate to conducting polymer or modification to improve its conductive capability further.

Conductive plastics can also be compound conductive plastics, composite conductive plastic take polymer as main matrix, and it is formulated to mix conductive agent wherein, here, whether polymer itself conducts electricity is not particularly limited, and the conductive capability of compound conductive plastics mainly realizes by conductive agent.Concrete, conductive plastics comprises polymer and conductive agent, and polymer includes but are not limited to polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.Concrete, polymer can be the polytetrafluoroethylene in fluororesin, can also be copolymer, as the copolymer of polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).

Conductive agent comprises carbon-based material, metal or metal oxide.The mass percent scope of conductive agent in conductive plastics is 10-90%.

Carbon-based material is selected from the one in graphite, carbon nano-tube or amorphous carbon.Amorphous carbon includes but are not limited to active carbon and carbon black.

The form of metal is not limit, and can be metal powder, sheet metal, metal strand, metallic fiber.Metal oxide includes but are not limited to lead oxide, tin oxide.

Concrete, by polymer and conductive agent with certain complex method as dispersion compound, level compound carry out processing the plastics with electric conductivity obtained.

The material of bipolar current collector 32 can also be stainless steel or the stainless steel through Passivation Treatment, stainless mechanical performance is better than conductive plastics, therefore, when using stainless steel as bipolar current collector 32, the thickness of bipolar current collector 32 can be thinner, concrete, the thickness range of bipolar current collector 32 is 20-100 μm.

The method of passivation for stainless steel process does not limit, and can be physical method passivation, chemical method passivation or electrochemical method passivation.The object of passivation is the compatibility in order to improve bipolar current collector 32 and aqueous electrolyte 28, thus reduces the generation of side reaction, makes battery have stable cycle performance.

In the present invention, mechanical property requirements for the bipolar current collector 32 forming bipolar electrode 24 is not high, namely the conductive plastics of lighter in weight or the stainless steel of thinner thickness can be adopted as bipolar current collector 32, battery 20 overall weight is reduced, and therefore the energy density of battery 20 is significantly improved.

Negative extraction electrode 26 is selected from metal, alloy or carbon-based material.

Concrete, negative extraction electrode 26 is selected from Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or at least one in the metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

Negative extraction electrode 26 can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy, or at least one in oxide.The thickness range of plating/coating is 1-1000nm.Such as: plumbous or silver-colored on negative extraction electrode 26 plated surface of copper, or cover one deck carbon with the form of coating.The thickness range of plus plate current-collecting body 30 and negative extraction electrode 26 is 1-10mm.

Negative extraction electrode 26 is with the negative pole introduced above, namely negative extraction electrode 26 only can not participate in electrode reaction as the matrix of electron collection and conduction, or negative extraction electrode 26 comprises negative current collector and negative electrode active material, if negative extraction electrode 26 is filtter gold and zinc paper tinsel, zinc paper tinsel is consistent with negative electrode active material.

Aqueous electrolyte 28 is arranged between positive extraction electrode 22 and negative extraction electrode 26, positive extraction electrode 22, bipolar electrode 24 and the stacked setting of negative extraction electrode 26, when bipolar electrode in battery 20 24 is one, between positive extraction electrode 22 and adjacent bipolar electrode 24, between bipolar electrode 24 and adjacent negative extraction electrode 26, be provided with aqueous electrolyte 28.When more than one of bipolar electrode 24 in battery 20, between positive extraction electrode 22 and adjacent bipolar electrode 24, between adjacent bipolar electrode 24, between bipolar electrode 24 and adjacent negative extraction electrode 26, be provided with aqueous electrolyte 28.

Aqueous electrolyte 28 comprises electrolyte, electrolyte at least can ionize out active ion, active ion is reduced second the formation negative electrode active material being deposited on bipolar current collector 32 when charging, negative electrode active material is oxidized when discharging to be dissolved in aqueous electrolyte 28, and active ion is present in water system electrolysis 28 liquid with at least one form in hydrochloride, sulfate, acetate, nitrate, formates or alkylsulfonate.

Aqueous electrolyte 28 and active ion, at by the agency of above, just repeat no more here.

In battery 20, preferably, battery 20 also comprises the additive joined in negative extraction electrode 26 and/or aqueous electrolyte 28, and additive is bismuth oxide and/or bismuth nitrate.Same, the addition manner of additive, at by the agency of above, just repeats no more here.

Battery 20 in execution mode one also comprises barrier film 34, barrier film 34 is arranged between positive extraction electrode 22 and adjacent bipolar electrode 24, between bipolar electrode 24 and adjacent negative extraction electrode 26, in execution mode one, battery 20 comprises two bipolar electrodes 24, therefore, between adjacent bipolar electrode 24, barrier film 34 is also provided with.On the one hand, barrier film 34 is for keeping aqueous electrolyte 28, and barrier film 34 prevents battery 20 short circuit on the other hand.

Barrier film 34 can use porous septum, bonded fabric or glass fibre.Porous septum includes but are not limited to polyethylene (PE), polypropylene (PP), the one in polyimides, or the lamination barrier film of PE-PP, PP-PE-PP.Bonded fabric includes but are not limited to artificial silk, acetate fiber, nylon.The impregnation amount of aqueous electrolyte 28 in barrier film 34 within the scope of the hold facility of barrier film 34, also can exceed hold in range, because battery 20 is provided with sealing 36, can prevent aqueous electrolyte 28 from leaking.

The peripheral part of bipolar current collector 32 is provided with the sealing 36 for sealing aqueous electrolyte 28, be not particularly limited, sealing 36 can adopt sealing ring, the shape of sealing ring is preferably rectangle, as long as the selection of sealing ring can realize excellent sealing effectiveness under the environment for use of battery 20.

Be not particularly limited, the material of sealing 36 is rubber, and rubber is selected from but is not limited only to the one in silicon class rubber, fluorine class rubber, olefin rubber, nitrile rubber, wherein, olefin rubber includes but are not limited to butadiene-styrene rubber (SBR), neoprene (CR).The rubber resin of these sealings has good sealing (fluid tight), resistance to acids and bases, resistance to chemical reagents, durability, weatherability and thermal endurance, and can keep for a long time under the environment for use of battery 20 these excellences performance and can not deterioration, therefore can effectively prevent aqueous electrolyte 28 from oozing out from battery 20, thus prevent battery 20 short circuit that causes due to the leakage of aqueous electrolyte 28, ensure the stable circulation performance of battery 20.

In addition, as long as effectively can realize action effect of the present invention, the various rubber as having acid resistance and sealing all can be used as the material of sealing 36 of the present invention.

Be not particularly limited, when sealing 36 adopts sealing ring, the area of barrier film 34 is less than the encirclement area of sealing ring, and the height of sealing ring is not less than the thickness sum of barrier film 34 and positive plate 23, when assembled battery, be placed in the circle of sealing ring by the barrier film 34 being soaked with aqueous electrolyte 28, barrier film 34 does not participate in sealing, can avoid the leakage of the aqueous electrolyte 28 that may cause because adopting porous septum like this.Certainly, the area of barrier film 34 also can be greater than the encirclement area of the sealing 36 being arranged on bipolar electrode 24 peripheral part, as long as barrier film 34 is finally one-body molded with sealing 36, aqueous electrolyte 28 can not be caused to reveal just.

Refer to shown in Fig. 3, bipolar electrode 24 is arranged between positive extraction electrode 22 and negative extraction electrode 26 stackedly, electronics is only derived from positive extraction electrode 22 and negative extraction electrode 26 or is imported, battery 20 is equivalent to 3 battery unit 38 internal series-connections, positive pole, negative pole, aqueous electrolyte and barrier film is had in each battery unit 38, aqueous electrolyte 28 is sealed by sealing 36, avoid the short circuit between the battery unit 38 that causes due to the leakage of aqueous electrolyte 28, thus ensure the normal work of battery 20.

Such as, one of them battery unit 38 comprises the second face 322 of plus plate current-collecting body 30, positive plate 23, barrier film 34, aqueous electrolyte 28, sealing 36 and the bipolar current collector 32 as negative pole.Sealing 36 for sealing the aqueous electrolyte 28 in each battery unit 38, to avoid the short circuit causing battery 20 because of the leakage of aqueous electrolyte 28.Battery 20 shown in Fig. 3 only comprises two bipolar electrodes 24, but in fact the number of bipolar electrode 24 in battery 20 can be set according to user demand easily, thus preparation has the battery of different output voltage and has the battery of high output voltage, battery tool provided by the invention has been widely used.

Battery preparation technique in the present invention is simple, battery can be prepared by stacked mode, concrete, negative extraction electrode places rectangular seal stackedly, the peripheral part of sealing ring and negative extraction electrode is fitted, and in the circle of sealing ring, then places the barrier film being soaked with aqueous electrolyte, then stack gradually bipolar electrode and positive extraction electrode, electrode active material in positive extraction electrode and bipolar electrode is placed towards negative extraction electrode simultaneously, and aqueous electrolyte is sealed by sealing ring.The number of bipolar electrode determines the output voltage that battery is last, and therefore, can arrange the number of bipolar electrode according to user demand, battery tool has been widely used.

In order to prevent from the impact of outside, ecological deterioration, with encapsulating material or shell by the battery 20 entirety sealing after stacked good sealing, thus complete the making of battery 20.The material of encapsulating material or shell is preferably by the coated metal material such as polymer, and metal as coated in polypropylene screen, metal includes but are not limited to aluminium, stainless steel, nickel or copper.

Please refer to shown in Fig. 4, the charge-discharge principle of water system bipolar battery 20 provided by the invention is: in a battery unit 38, during charging, in positive plate 23 can reversible deviate from-positive active material 50 of embedded ion in deviate from this ion, active ion simultaneously in aqueous electrolyte 28 obtains electronics in the second face 322 of bipolar current collector 32 and is reduced, and be deposited on the second face 322, form negative electrode active material.In the battery unit 38 containing negative extraction electrode 26, active ion obtains electronics and is reduced on negative extraction electrode 26, is deposited on negative extraction electrode 26.Discharge process is then the inverse process of charging.

In the present invention, the bipolar electrode 24 forming battery 20 only arranges positive plate 23 at the first surface 321 of bipolar current collector 32, second face 322 of bipolar current collector 32 is then equivalent to negative pole, matrix is provided for active ion obtains electron reduction-deposition, active ion is present in aqueous electrolyte 28, at the first surface 321 of bipolar current collector 32 and the second face 322, all electrode active material is set relative in prior art, battery 20 structure in the present invention is compacter, and battery 20 has excellent energy density and power density.In addition, the battery 20 in the present invention adopts aqueous electrolyte 28, environmental protection safer relative to the lithium ion battery of current business-like employing organic system electrolyte.

Battery 20 in the present invention, be equivalent to the series connection of several battery units 38 and formed, each battery unit 38 is well sealed by sealing 36, thus prevents the short circuit that causes due to the leakage of aqueous electrolyte 28.In addition, even if battery of the present invention does not arrange special leakage-proof part or insulating element, also can prevent the short circuit between battery unit 38, thus the bipolar battery with excellent ionic conductance, charge-discharge performance is provided.In addition, can arrange the bipolar electrode 24 of varying number according to user demand, thus preparation has the battery 20 of different output voltage, battery 20 purposes widely.

Execution mode two

Refer to shown in Fig. 5, execution mode two provides a kind of battery 100 and comprises positive extraction electrode 40, at least one bipolar electrode 24, negative extraction electrode 26 and aqueous electrolyte 28.What bipolar electrode 24 was stacked is arranged between positive extraction electrode 40 and negative extraction electrode 26, and positive extraction electrode 40 and negative extraction electrode 26 lay respectively at the superiors and orlop.

With the difference of execution mode one be: positive extraction electrode 40 comprises composite current collector and is arranged on the positive plate 23 of composite current collector 30 one side, the conducting film 12 that composite current collector comprises plus plate current-collecting body 30 and is coated on plus plate current-collecting body 30.

Conducting film 12 can by vacuumizing, the method for hot pressing compound or spraying is coated on the one or both sides of plus plate current-collecting body 30, and then in conjunction with positive plate 23 on composite current collector, the thickness of conducting film 12 is 0.01-0.2mm.Specific in Fig. 5, the two sides of plus plate current-collecting body 30 is all coated with conducting film 12.

The material of conducting film 12 is also introduced in detail above, just repeats no more here.

On the one hand, conducting film 12 can reduce the contact resistance between plus plate current-collecting body 30 and positive plate 23; On the other hand, be coated on the conducting film 12 in plus plate current-collecting body 30 one side, avoid plus plate current-collecting body 30 directly to contact with aqueous electrolyte 28, avoid the etching problem that aqueous electrolyte 28 pairs of plus plate current-collecting bodies 30 are potential, ensure the stability of plus plate current-collecting body 30, improve the self discharge problem that battery 100 is possible, thus make battery 100 have stable cycle performance.

Refer to shown in Fig. 6, battery unit 38 is sealed by sealing 36, and sealing 36 is arranged on the peripheral part of bipolar current collector 32, for sealing aqueous electrolyte 28.

In execution mode two, all the other formations of battery 100 and assembling mode are with execution mode one, repeat no longer one by one here.

The battery 100 provided in execution mode two, adopt the plus plate current-collecting body 30 that conducting film 12 is coated, stop the etching problem that aqueous electrolyte 28 pairs of plus plate current-collecting bodies 30 are potential, make battery 100 except there is the features such as high output voltage, safety, environmental protection, further increase the stable circulation performance of battery 100.

Execution mode three

Refer to shown in Fig. 7, execution mode three provides a kind of battery 200, comprises positive extraction electrode 22, at least one bipolar electrode 24, negative extraction electrode 26 and aqueous electrolyte 28.What bipolar electrode 24 was stacked is arranged between positive extraction electrode 22 and negative extraction electrode 26, and positive extraction electrode 22 and negative extraction electrode 26 lay respectively at the superiors and orlop.That battery 200 does not comprise barrier film with the difference of execution mode one.

Same, battery unit (not shown) is sealed by sealing 36, and sealing 36 is arranged on the peripheral part of bipolar current collector 32, for sealing aqueous electrolyte 28.Example, sealing 36 can adopt sealing ring, the height of sealing ring is greater than the thickness of positive plate 23, by having the sealing ring of certain altitude, make to keep certain distance between positive extraction electrode 22 and adjacent bipolar electrode 24 and between bipolar electrode 24 and adjacent negative extraction electrode 26, to avoid battery 200 short circuit.Sealing 36 is provided with equally when more than one of the number of bipolar electrode 24 in battery 200, between adjacent bipolar electrode 24.

When preparing the battery in execution mode three, can first the positive extraction electrode 22 prepared by predetermined dimension, bipolar electrode 24 and negative extraction electrode 26 be carried out arranging and sealing.Concrete, positive plate 23 on positive extraction electrode 22 and bipolar electrode 24 arranges towards negative extraction electrode 26 simultaneously, sealing 36 can adopt the elastomeric material having and exceed positive plate 23 thickness as sealing ring, sealing ring is arranged on the peripheral part of bipolar current collector 32, the mode finally by injection injects aqueous electrolyte 28; Sealing 36 can also adopt thermoplastic rubber material, when tentatively sealing, only thermoplastic rubber material can be set at the peripheral part on bipolar current collector 32 3 limit, retain openings at one side, after positive extraction electrode 22, bipolar electrode 24 and negative extraction electrode 26 are arranged, make Cure of Rubber shaping by heating or heat pressurization, then by the aqueous electrolyte 28 that scheduled volume is injected at unencapsulated place, finally more all battery units are sealed completely.

In execution mode three, all the other formations of battery 200 and assembling mode are with execution mode one, repeat no longer one by one here.

Battery 200 in execution mode three does not adopt barrier film, and battery 200 can not only give work that is normal, that continue, and due to weight lighter, therefore battery 200 has more excellent energy density and specific power.In addition, when preparing battery 200, sealing 36 can be formed easily, preventing the short circuit caused due to the leakage of aqueous electrolyte 28.Even if battery 200 does not arrange special leakage-proof part, can prevent the short circuit between battery unit, battery 200 has excellent cycle performance and cycle life.

Execution mode four

Refer to shown in Fig. 8, execution mode four provides a kind of battery 300, comprises positive extraction electrode 40, at least one bipolar electrode 24, negative extraction electrode 26 and aqueous electrolyte 28.What bipolar electrode 24 was stacked is arranged between positive extraction electrode 40 and negative extraction electrode 26, and positive extraction electrode 40 and negative extraction electrode 26 lay respectively at the superiors and orlop.

That battery 200 does not comprise barrier film with the difference of execution mode two.

Battery 300 in execution mode four, the conducting film 12 be formed on plus plate current-collecting body 30 has completely cut off plus plate current-collecting body 30 and the contact of aqueous electrolyte 28, improves the stable of plus plate current-collecting body 30, thus ensures that battery 300 has stable cycle performance.Do not use battery 300 weight of barrier film lighter, be convenient to while user carries, provide excellent performance.

Battery in the present invention, collector in bipolar electrode can adopt the stainless steel of conductive plastics or thinner thickness, while guarantee normal battery operation, the weight of battery is lighter, makes the battery in the present invention have obvious advantage in energy density and volume; Secondly, battery adopts aqueous electrolyte, and aqueous electrolyte has relatively higher ionic conductance, improves the high rate performance of battery; Battery use safety, environmental protection and manufacture craft are simple, and in preparation process, can have the battery of different output voltage according to user demand preparation, battery use is extensive, has commercial application prospect.

Battery containing bipolar electrode is provided in the present invention, only in the one side of bipolar electrode in conjunction with positive plate, in bipolar electrode, second of bipolar current collector do not have negative electrode active material before battery first charge-discharge, active ion is present in aqueous electrolyte, when charging to battery, be deposited on bipolar current collector first surface, battery has excellent cycle performance.Meanwhile, what battery adopted is aqueous electrolyte, and relative to the lithium ion battery adopting organic system electrolyte, the battery in the present invention is safer, environmental protection.In addition, can prepare by the number arranging bipolar electrode the battery having different output voltage, have high output voltage, battery use is extensive and preparation technology is simple, and battery has commercial applications potentiality.

[there is the battery of internal parallel structure]

Present invention also offers a kind of battery, concrete, battery has internal parallel structure.The battery with internal parallel structure is set forth further below by concrete execution mode.

Execution mode five

Refer to shown in Fig. 9, a kind of battery 400, comprise positive pole 42, two negative poles 44 and aqueous electrolyte 28, positive pole 42 is arranged between two negative poles 44, and two negative poles 44 share positive pole 42, are provided with aqueous electrolyte 28 between negative pole 44 and positive pole 42.

Positive pole 42 comprises composite current collector and positive plate 23, and composite current collector comprises plus plate current-collecting body 30 and is coated on the conducting film 12 on plus plate current-collecting body 30, and positive plate 23 comprises positive active material 50, positive active material can reversible deviate from-embedded ion.

Composite current collector has the first surface and second that are oppositely arranged, and positive plate 23 is arranged on first surface and second.

Specific in execution mode five, positive plate 23 comprises the carrier of electrochemicaUy inert, and positive active material 50 is formed on carrier, and positive active material 50 and carrier, at by the agency of above, just repeat no more here.

Preferably, the first surface on plus plate current-collecting body 30 and second are coated with conducting film 12 simultaneously, as shown in Figure 9.Then, positive plate 23 is attached on the conducting film 12 of composite current collector more in a certain way, as hot pressing compound, bonding, stacked or compacting.

Conducting film 12 can by vacuumizing, the method for hot pressing compound or spraying is coated on plus plate current-collecting body 30, example, plus plate current-collecting body 30 is placed between two panels conducting film 12, by heating compound, make conducting film 12 clad anode collector 30, and ensureing that the part sealing that conducting film 12 has more than plus plate current-collecting body 30 is intact, the thickness being coated on the conducting film 12 of plus plate current-collecting body 30 one side is 10-200 μm.

Conducting film, at preceding detailed description, just repeats no more here.

Negative pole 44 is selected from metal, alloy or carbon-based material.

Concrete, negative pole 44 is selected from Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or at least one in the metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

Aqueous electrolyte 28 comprises electrolyte, electrolyte at least can ionize out active ion, active ion is reduced when charging and is deposited on negative pole 44 and forms negative electrode active material, negative electrode active material is oxidized when discharging to be dissolved in aqueous electrolyte 28, and active ion is present in aqueous electrolyte 28 with at least one form in hydrochloride, sulfate, acetate, nitrate, formates or alkylsulfonate.

In execution mode five, with the difference of battery 20, battery 400 is mainly that battery 400 has internal parallel structure.Therefore, battery basic composition is just repeated no more here.

Battery 400 in execution mode five also comprises barrier film 34, and barrier film 34 is arranged between positive pole 42 and negative pole 44, and on the one hand, barrier film 34 prevents battery 400 short circuit; On the other hand, barrier film 34 can keep aqueous electrolyte 28, concrete, after negative pole 44, barrier film 34, positive pole 42, barrier film 34 and negative pole 44 are arranged, put it into package casing, encapsulate after injecting a certain amount of aqueous electrolyte 28, barrier film 34 is immersed in aqueous electrolyte 28, namely absorb aqueous electrolyte 28 in barrier film 34, ensure that the ionic conduction path between positive pole 42 and negative pole 44; In addition, also first barrier film 34 can be immersed in aqueous electrolyte 28, and then the barrier film 34 absorbing aqueous electrolyte 28 is placed between positive pole 42 and negative pole 44.

Barrier film 34 can use porous septum, bonded fabric or glass fibre.Porous septum includes but are not limited to polyethylene (PE), polypropylene (PP), the one in polyimides, or the lamination barrier film of PE-PP, PP-PE-PP.Bonded fabric includes but are not limited to artificial silk, acetate fiber, nylon.The impregnation amount of aqueous electrolyte 28 in barrier film within the scope of the hold facility of barrier film, also can exceed hold in range, because battery 400 is provided with package casing, can prevent aqueous electrolyte 28 from leaking.

In order to prevent from the impact of outside, ecological deterioration, with encapsulating material or shell by the battery 400 entirety sealing after stacked good sealing, thus complete the making of battery 400.The material of encapsulating material or shell is preferably by the coated metal material such as polymer, and metal as coated in polypropylene screen, metal includes but are not limited to aluminium, stainless steel, nickel or copper.

Refer to shown in Figure 10, positive pole 42 is arranged between negative pole 44 stackedly, negative pole 44 shares positive pole 42, electronics is derived from plus plate current-collecting body 30 and negative pole 44 or is imported, battery 400 is equivalent to 2 battery unit 46 internal parallels, in each battery unit 46, have positive pole 42, negative pole 44, aqueous electrolyte 28 and barrier film 34, barrier film 34 keeps aqueous electrolyte 28.In battery structure provided by the invention, owing to being in parallel between battery unit 46, aqueous electrolyte 28 can shuttle back and forth and can not cause battery unit 46 short circuit, the work that battery 400 can be normal, stable in any battery unit 46.

Relative in prior art with the battery that formed of individual battery cells parallel connection, a positive pole 42 is only adopted to form the battery 400 with parallel-connection structure in the present invention cleverly, two negative poles 44 share a positive pole 42, make use of the first surface of plus plate current-collecting body 30 and second fully, and positive plate 23 is set simultaneously on first surface and second, not only save positive electrode, and make battery 400 structure compacter, alleviate the weight of battery 400, the battery 400 therefore in the present invention has excellent energy density and power density.Finally, the battery 400 in the present invention adopts aqueous electrolyte 28, environmental protection safer relative to the lithium ion battery of current business-like employing organic system electrolyte.

Battery preparation technique in the present invention is simple, can prepare battery by stacked mode, concrete, by negative pole 44, the barrier film 34 being soaked with aqueous electrolyte 28, positive pole 42 and negative pole 44 stationary arrangement successively, then encapsulates it.Battery 400 is equivalent to 2 battery unit 46 parallel connections and is formed, seal member need not be set especially between battery unit 46 and battery unit 46, the battery 400 with this internal parallel structure can be normal, stable work, there is excellent charge-discharge performance, and battery 400 can export higher capacity, battery 400 is widely used.

Execution mode six

Refer to shown in Figure 11, execution mode six provides a kind of battery 500, comprises two positive poles 42, negative pole 44 and aqueous electrolyte 28, and negative pole 44 is arranged between two positive poles 42, two positive poles 42 share negative pole 44, are provided with aqueous electrolyte 28 between negative pole 44 and positive pole 42.

In execution mode six positive pole, negative pole and aqueous electrolyte selection and preparation with execution mode five, repeat no longer one by one here.

Battery in execution mode five, six is all be equivalent to two battery units in parallel, difference is, battery 400 in execution mode five is that two negative poles 44 share a positive pole 42, and the battery 500 in execution mode six is the shared negative poles 44 of two positive poles 42, therefore, battery provided by the invention has to be selected flexibly, when reality manufactures battery, can in conjunction with factors such as the weight of manufacture craft, both positive and negative polarity, material costs, select the battery making structure as shown in execution mode five or six, make the final battery obtained have more cost and performance advantage.

Battery in the present invention has internal parallel structure, and compared to parallel-connection structure battery of the prior art, the battery in the present invention more saves material and compact conformation, light, makes the battery in the present invention have obvious advantage in energy density and volume; Secondly, battery adopts aqueous electrolyte, and aqueous electrolyte has relatively higher ionic conductance, improves the high rate performance of battery; Battery use safety, environmental protection and manufacture craft are simple, and in preparation process, can have the battery of different output capacity according to user demand preparation, battery use is extensive, has commercial application prospect.

Execution mode seven

Present invention also offers a kind of battery 600, comprise positive pole 42, negative pole 44 and aqueous electrolyte 28.

Positive pole 42 comprises composite current collector and positive plate 23, the conducting film 12 that composite current collector comprises plus plate current-collecting body 30 and is coated on plus plate current-collecting body 30, positive plate 23 comprises positive active material 50, composite current collector has the two sides be oppositely arranged, wherein, the one side that at least composite current collector is relative with negative pole 44 is provided with positive plate 23, positive active material 50 can reversible deviate from-embedded ion.Positive pole 42, at by the agency of above, just repeats no more here.

Battery n is to positive pole and negative pole, and n >=2, positive pole, negative pole are arranged alternately, and two adjacent positive poles 42 share the negative pole 44 between two positive poles 42, and two adjacent negative poles 44 share the positive pole 42 between two negative poles 44.Specific in Figure 12, battery 600 comprises two pairs of positive poles 42 and negative pole 44.

Specific in execution mode seven, positive plate 23 also comprises the carrier of electrochemicaUy inert.Positive active material 50 is formed on carrier.

Negative pole and aqueous electrolyte, at also by the agency of above, just repeat no more here.

Concrete, refer to shown in Figure 12, composite current collector has the first surface and second that are oppositely arranged, when positive pole 42 is between two negative poles 44, the first surface that composite current collector is oppositely arranged is all relative with negative pole with second, and the two sides that therefore composite current collector is oppositely arranged all needs to arrange positive plate 23; And for being positioned at outermost positive pole 42, composite current collector only has one side relative with negative pole 44, therefore the one side that at least composite current collector is relative with negative pole 44 arranges positive plate 23, composite current collector and the opposing one side of negative pole 44 are not particularly limited, and can arrange positive plate 23 according to actual fabrication process selectivity.

Battery 600 shown in Figure 12 is containing two pairs of positive poles 42 and negative pole 44, be equivalent to 3 battery unit (not shown) in parallel, but when actual fabrication battery, battery structure provided by the invention can be easy to increase positive pole or negative pole or positive pole and negative pole according to user demand, such as superpose negative pole at the outermost positive pole place of battery 600 or superpose negative pole and positive pole successively, or superpose positive pole at the outermost negative pole place of battery 600 or superpose positive pole and negative pole successively, positive pole and the negative pole of superposition are alternately arranged.The number of positive pole and negative pole is determined according to user demand.As shown in figure 13, although output voltage no change that battery is total, battery has higher capacity, and battery structure is flexible, of many uses, has commercial application prospect.

In the battery system containing neutral aqueous electrolyte, be difficult to find and meet existing certain mechanical performance, excellent electric conductivity simultaneously, again can in neutral aqueous electrolyte the plus plate current-collecting body of stable existence, therefore the commercialization process of water system battery is stagnated always.Battery provided by the invention just in time can address this problem; the positive pole of battery comprises plus plate current-collecting body, conducting film and positive plate; conducting film is formed on plus plate current-collecting body; conducting film can improve the electric conductivity of plus plate current-collecting body on the one hand; the more important thing is and plus plate current-collecting body is played a protective role; isolated neutral aqueous electrolyte is to the corrosion of plus plate current-collecting body; make collection that plus plate current-collecting body can be stable in discharge process and derive electronics; thus ensureing that battery has stable cycle performance, battery provided by the invention has good Commercial Prospect.

Present invention also offers a kind of battery pack, battery pack is containing several above-mentioned batteries, concrete, carrys out production battery pack by series, parallel or its two or more battery that is connected.The capacity of battery pack and voltage freely can be adjusted by the series connection of battery and/or parallel way.Vehicle and transportation means can be used as the power supply of train according to battery provided by the invention or the battery pack that built by battery, and be used as can fix/can install power supply as uninterrupted power supply.

[electrode slice]

A kind of electrode slice, electrode slice is easy to processing, thickness is homogeneous and be easy to sorting, and consistency of performance is good, and the battery applying this electrode slice has cheap price, good cycle performance and higher energy.

Refer to shown in Figure 14, a kind of electrode slice 1, the carrier 2 comprising electrochemicaUy inert and the active material layer 4 be formed on carrier 2.Electrode slice 1 can be applied to the negative or positive electrode of battery, and in order to make battery have higher energy density, preferably, the thickness range of electrode slice 1 is 0.3-1.5mm, and in a particular embodiment, the thickness of electrode slice 1 is 0.4mm.

Active material layer 4 is formed on carrier 2, and carrier 2 has the first surface and second that are oppositely arranged, is not particularly limited, and active material layer 4 can be formed on first surface or second, also can be formed on first surface and second simultaneously.

In the present invention, electrode slice 1 be should be to the understanding of electrode slice 1 and comprise necessary active material layer 4, and do not comprise collector.In prior art, when usually preparing electrode, directly the slurry containing active material is applied on a current collector in a certain way, dry aft-loaded airfoil and become electrode.The electrode prepared under this technique, the weight of whole electrode can only be weighed when carrying out sorting, and consider the inhomogeneities of each areal weight distribution of collector itself, this sorting can not be accurate to the weight measuring active material in each electrode, cause the inconsistent of each electrode capacity thus, finally cause the inconsistent of whole Battery pack and affect chemical property and rate of finished products.In the present invention, electrode slice 1 departs from collector and prepares separately shaping, in the process preparing electrode slice 1, is conducive to weighing separately sorting to active material layer 4, increased substantially battery consistency and made battery be easy to assembling.

In a particular embodiment, active material layer 4 comprises electrode active material, binding agent and conductive agent, and electrode active material participates in electrochemical reaction.Electrode slice 1 provided by the invention, according to the difference of electrode active material, can be applied to dissimilar battery, and example, battery variety comprises Ni-MH battery, lead-acid battery, lithium ion battery etc.

In a specific embodiment, electrode slice 1 is applied to positive pole, and electrode active material is positive active material.Positive active material participates in electrochemical reaction, and the weight percentage ranges that positive active material accounts for active material layer is 60-99%.In order to make just have higher capacity, in active material layer, the surface density scope of positive active material is 200-2000g/m ².Concrete, positive active material can reversible deviate from-embedded ion.Concrete, lithium ion, sodium ion or magnesium ion can deviate from-embedded to positive active material reversiblely.Concrete, positive active material, at by the agency of above, is not just repeating here.

Carrier 2 mainly plays a part to carry active material layer 4, the electrochemicaUy inert of carrier 2 own, according to as well known to those skilled in the art, electrochemicaUy inert and carrier 2 do not participate in any electrochemical reaction, stable is present in electrode slice 1, only exists as the matrix carrying active material layer 4.In addition, carrier 2 electronic isolation and there is loose structure, concrete, the range of aperture size of carrier 2 is 50 order-200 orders, like this, under guarantee carrier 2 has certain mechanical performance prerequisite, not only being conducive to active material layer 4 is attached on carrier 2, improve the resistance to peeling force of active material layer 4 and carrier 2, ensure the work that electrode slice 1 is stable, and facilitate the transmission of electrode active material intermediate ion.

The thickness of carrier 2 is not particularly limited, but in order to ensure that electrode slice 1 has high energy density, therefore needs the thickness of control electrode sheet 1, and as the carrier 2 of one of electrode slice 1 composition, preferably, the thickness of carrier 2 is less than 1mm.

Concrete, from manufacture craft, carrier 2 can be nonwoven fabrics, and nonwoven fabrics, not through textile process, forms by means of only physical means is bonding.The composition of nonwoven fabrics is not specifically limited, as long as can meet the conditions such as electrochemicaUy inert.Non-woven weight is very light, stable performance, easily sizing and cost is low.In the present invention, by nonwoven fabrics and active material layer connected applications in electrode slice, make electrode slice 1 weight lighter and there is stable chemical property.

From composition, the material of carrier 2 is selected from least one in polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene (PE), polypropylene (PP), polyamide (PA), polyurethanes (PU), polyacrylonitrile (PAN).These materials can be stable be present in electrode slice 1 and do not participate in electrochemical reaction, and be that the high energy density of battery exports saving in weight.

In the prior art preparing electrode, the slurry containing graphite on a current collector, such as, in lithium ion battery, is coated on Copper Foil and makes negative pole by the normally direct slurry coating by containing active material; In lead-acid battery, lead plaster is coated on grid and makes negative pole.The electrode prepared under this technique, the weight of whole electrode can only be weighed when carrying out sorting, and consider the inhomogeneities of each areal weight distribution of collector itself, this sorting can not be accurate to the weight measuring active material in each electrode, cause the inconsistent of each electrode capacity thus, finally cause the inconsistent of whole Battery pack and affect chemical property and rate of finished products.Electrode slice 1 provided by the invention, in active material layer 4, electrode active material, binding agent and the ratio of conductive agent are accurately consistent, and the carrier 2 of electrochemicaUy inert is also the material selecting consistency very high, and thus obtained electrode slice 1 weight consistency is very high.

[preparation method of electrode slice]

A preparation method for electrode slice 1, preparation method comprises the following steps:

Prepare slurry: be formed in by slurry on the carrier 2 of electrochemicaUy inert, form active material layer 4, carrier 2 electronic isolation and have loose structure, final drying is shaping.

Concrete, slurry comprises electrode active material, binding agent and conductive agent, and electrode active material participates in electrochemical reaction.The weight percentage ranges that electrode active material accounts for active material layer is 60-99%, and in active material layer, the surface density scope of electrode active material is 100-3000g/m ², in order to make battery have high Energy transmission, preferably, in active material layer, the surface density scope of electrode active material is 200-2000g/m ².

When preparing slurry, adopt dispersant that electrode active material, binding agent and conductive agent are mixed uniformly, dispersant includes but are not limited to water.

After being mixed by slurry, be formed on carrier 2, the mode of formation is not particularly limited, and comprises scraper for coating, silk screen printing or slurry.

In a particular embodiment, by tensile pulp machine, slurry is coated on carrier 2.General, tensile pulp machine inside has the slurry tank of collecting slurry, and carrier is guided by deflector roll and enters slurry tank inside, and carrier immerses in slurry, and the viscosity of slurry is 3000-100000mPa.s, and when carrier 2 pulls out from slurry tank, slurry sticks on carrier 2.The thickness of slurry can control, and as scraper, scraper wipes slurry unnecessary on carrier off according to predetermined thickness, thus realizes the thickness controlling carrier 2 spreading mass, and makes the slurry on carrier 2 surface more even.

The carrier 2 being stained with slurry is carried out drying process, usually, the evaporation under normal pressure or low pressure and ambient temperature or high temperature, by removal of solvents in pulp layer, the speed of removal of solvents is preferably and keeps substantially constant along pulp surface.Preferably, carry out drying process at being 50-130 DEG C in normal pressure, temperature, the electrode slice 1 of such drying and moulding has more homogeneous thickness.Finally, according to design requirement, electrode slice 1 is cut into target sizes.

In a particular embodiment, by positive active material LiMn ₂o ₄, conductive agent super-p, binding agent CMC and SBR mix according to being predefined in water, mixing all with after, be coated on nylon wire by the slurry of acquisition, drying at 70 DEG C, acquisition positive plate, finally rolls predetermined thickness by positive plate.

Preparation method provided by the invention, carrier 2 that is homogeneous with weight, electrochemicaUy inert is substrate, coats on carrier 2 by electrode active material, binding agent and conductive agent etc., makes separately the electrode slice 1 not having collector.Preparation method's technique is simple, and in the process preparing electrode slice 1, be conducive to weighing sorting separately to active material layer 4, electrode slice 1 thickness of preparation is homogeneous, and stable performance, the electrode containing electrode slice 1 has good consistency.Increase substantially battery consistency and made battery be easy to assembling.

[electrode]

Refer to shown in Figure 15, a kind of electrode 6, comprise electrode current collecting body 8 and electrode slice 1, the carrier 2 that electrode slice 1 comprises electrochemicaUy inert and the active material layer 4 be formed on carrier 2, carrier 2 electronic isolation and there is loose structure.

Refer to shown in Figure 16, electrode current collecting body 8 has conducting film 12, and conducting film 12 is formed in the surface of electrode current collecting body 8 in a certain way, and electrode slice 1 to be attached on conducting film 12 thus to form electrode 10.Specific in Figure 16; the two sides that electrode current collecting body 8 is oppositely arranged all is formed with conducting film 12; conducting film 12 not only can reduce the contact internal resistance between electrode slice 1 and electrode current collecting body 8; and the impact being subject to electrolyte can be avoided by guard electrode collector 8, thus ensure that electrode 10 has stable chemical property.

[preparation method of electrode]

A preparation method for electrode 10, preparation method comprises the following steps:

Electrode slice 1, conducting film 12 and electrode current collecting body 8 are combined, conducting film 12 is between electrode slice 1 and electrode current collecting body 8, the carrier 2 that electrode slice 1 comprises electrochemicaUy inert and the active material layer 4 be formed on carrier 2, carrier 2 electronic isolation and have loose structure, conducting film 12 comprises polymer.

In obtained electrode 10, conducting film 12 is between electrode slice 1 and electrode current collecting body 8.Electrode current collecting body 8 has the first surface and second that are oppositely arranged.Be not particularly limited, can only hot pressing composite conductive film 12 on first surface or second; Also can at first surface and second composite conductive film of hot pressing simultaneously 12.Preferably, the first surface of electrode current collecting body 8 and second are compounded with conducting film 12 and electrode slice 1 by hot pressing all successively.

Electrode 10 provided by the invention, electrode 10 can be positive pole, negative pole or bipolar electrode, according to the difference of active material layer in electrode slice, can be applied to dissimilar battery, and example, battery variety comprises Ni-MH battery, lead-acid battery, lithium ion battery etc.

In electrode slice 1, active material layer 4 is formed on carrier 2, and carrier 2 has the first surface and second that are oppositely arranged, is not particularly limited, and active material layer 4 can be formed on first surface or second, also can be formed on first surface and second simultaneously.In addition, carrier 2 electronic isolation and there is loose structure, like this, under guarantee carrier 2 has certain mechanical performance prerequisite, not only being conducive to active material layer 4 is attached on carrier 2, improve the resistance to peeling force of active material layer 4 and carrier 2, ensure the work that electrode slice 1 is stable, and facilitate the transmission of electrode active material intermediate ion.

In electrode slice 1, active material layer 4 and carrier 2 are introduced in detail above, just repeat no more here, will be introduced conducting film 12 and electrode current collecting body 8 respectively below.

The conducting film 12 that one deck can conduct electricity is set between electrode slice 1 and electrode current collecting body 8, the selection of conducting film 12 must to meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, do not occur swelling, high voltage can not oxidized, be easy to be processed into densification, the waterproof and film of conduction.On the one hand, conducting film 12 pairs of electrode current collecting bodies 8 can play a protective role, and avoid aqueous electrolyte to the corrosion of collector.On the other hand, be conducive to reducing the contact internal resistance between electrode slice 1 and electrode current collecting body 8, improve the energy of battery.

In order to effectively play the effect of conducting film 12, the thickness of conducting film 12 needs effective control.The too thin easy breakage of conducting film 12 thickness, caliper uniformity is also bad, and electrolyte easily penetrates; Conducting film 12 is too thick, affects conductive capability.Preferably, the thickness of conducting film 12 is 10 μm of-2mm, and conducting film 12 effectively can not only play the effect of guard electrode collector 8, and is conducive to reducing the contact internal resistance between electrode slice 1 and electrode current collecting body 8, improves the energy of battery.

Embodiment 1

Prepare positive pole: by LiMn2O4 LMO, conductive agent super-P, binding agent SBR and CMC mixes in water according to mass ratio 90:5:2.5:2.5, forms uniform anode sizing agent, and in water, solids content is 60-70%.Nylon wire is immersed in anode sizing agent completely, then the nylon wire being stained with anode sizing agent is taken out, dry at 60 DEG C, form active material layer, carried out compressing tablet subsequently, be cut into 6 × 6cm size, make positive plate, positive plate thickness is 0.4mm, and positive active material surface density is 750g/m ².

Conducting film is the composite material containing polyethylene and conductive black.Conducting film thickness is 50 μm.

Plus plate current-collecting body is the punching carbon steel of 50 μm.

Plus plate current-collecting body is placed in the middle of two panels conducting film, conducting film size is slightly larger than plus plate current-collecting body, at 115-140 DEG C, by aerostatic press, conducting film and plus plate current-collecting body is combined with each other, pressure is 0.5MPa, and it is intact to ensure that conducting film has more part sealing than punching carbon steel.

Again the composite current collector prepared is placed between two panels positive plate, repeats above-mentioned steps and obtain positive pole.Each walks compound tense, and the compressing time of aerostatic press is 10s.

Barrier film is AGM fibreglass diaphragm, and negative pole is the zinc paper tinsel of thick 50 μm, and barrier film is suitable with positive pole with negative pole size.

Electrolyte is the ZnSO of 2mol/L ₄with the Li of 1mol/L ₂sO ₄mixed aqueous solution.

After battery pack installs into, inject electrolyte.Static 3 hours, charge-discharge test can be started.

Charge-discharge test:

Carry out constant current charge-discharge with 0.2C to battery, voltage range is 1.4-2.1V, discharge and recharge cabinet (holding up sky).

Embodiment 2

In example 2, conducting film thickness is 100 μm, and all the other compositions of battery and preparation method are with embodiment 1.

Comparative example 1

In comparative example 1, the making of positive pole is not adopt hot compound, and just simple physical superposes positive plate, conducting film and plus plate current-collecting body.All the other compositions of battery and preparation method are with embodiment 1.

Figure 17 example to give in embodiment 1 and comparative example 1 battery in first time charge and discharge process the internal resistance of cell to the graph of relation of time.In Fig. 1-■-expression comparative example 1 in battery charging process;-● the battery discharge procedure in-expression comparative example 1;-▲-represents the battery charging process in embodiment 1; Battery discharge procedure in-▼-expression embodiment 1.

As can be seen from the figure, in embodiment 1, internal resistance of cell curve plateau lower than curve plateau in comparative example 1, will illustrate that the discharge and recharge internal resistance of battery in embodiment 1 will be starkly lower than battery in comparative example 1.Meanwhile, along with battery charging and discharging cycle-index increases, in embodiment 1, the internal resistance of cell has almost no change, and in comparative example 1, the internal resistance of cell progressively increases.Experimental result shows: the positive pole prepared by hot pressing complex method, can obviously improve positive pole internal resistance, makes the battery containing positive pole have excellence, stable cycle performance.In addition, in embodiment 2, battery performance is better than battery in embodiment 1, illustrates that conducting film thickness has certain influence to battery performance, and thickness is that the cycle performance of battery of the conducting film of 100 μm is better.

Embodiment 3

Prepare positive pole: by LiMn2O4 LMO, conductive agent super-P, binding agent SBR and CMC mixes in water according to mass ratio 90:5:2.5:2.5, forms uniform anode sizing agent, and in water, solids content is 60-70%.Nylon wire is immersed in anode sizing agent completely, then the nylon wire being stained with anode sizing agent is taken out, dry at 60 DEG C, form active material layer, carried out compressing tablet subsequently, be cut into 8 × 10cm size, make positive plate, positive plate thickness is 0.4mm, and positive active material surface density is 750g/m ².Plus plate current-collecting body is 50 μm of thick perforation 304 stainless steels.Be superimposed together obtained positive plate and sizable plus plate current-collecting body formation positive pole.

Barrier film is AGM glass fibre, and negative pole is the zine plate of thick 50 μm, and barrier film is suitable with positive pole with negative pole size.5 positive poles and 6 negative poles are staggered, separate between positive pole and negative pole with barrier film, form a battery, theoretical capacity is about 6Ah.

Electrolyte is the ZnSO of 2mol/L ₄with the Li of 1mol/L ₂sO ₄mixed aqueous solution, regulates electrolyte pH to be 4.After battery pack installs into, inject 170 milliliters of electrolyte, static 3 hours, can charge-discharge test be started.Carry out constant current charge-discharge with 0.2C to battery, voltage range is 1.4-2.1V.

Comparative example 2

In comparative example 2, positive plate directly on plus plate current-collecting body stainless steel, carries out continuous slurry coating, is then die-cut into required size, and all the other formations of battery and manufacture method are with embodiment 3.

The discharge curve of the battery that Figure 18 provides for embodiment 3 and comparative example 2.As can be seen from the figure, in embodiment 3, the discharge capacity of battery is higher than the battery in comparative example 2.Showing relative to directly forming positive active material on a current collector, containing the battery preparing separately positive plate, there is higher discharge capacity.

Table 1 lists the capacity of the positive plate of 5 batches prepared by two kinds of methods by providing in embodiment 3 and comparative example 2, the positive plate capacitance tolerance (difference between heap(ed) capacity and minimum capacity) obtained by embodiment 3 is as can be seen from the table less, and positive plate has excellent Capacity uniformity.This result shows that electrode slice provided by the invention improves the effect having highly significant to battery consistency.

Table 1

Embodiment 4

Prepare positive pole: by LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC mixes in water according to mass ratio 86.5:10:2.5:1, forms uniform anode sizing agent.Nylon wire is immersed in anode sizing agent completely, then the nylon wire being stained with anode sizing agent is taken out, dry at 60 DEG C, form positive active material, carried out compressing tablet subsequently, be cut into 6 × 6cm size, make positive plate, positive plate thickness is 0.4mm, and positive active material surface density is 750g/m ².

In composite current collector, conducting film is the composite material containing polyethylene and conductive black.Conducting film thickness is 100 μm.

Plus plate current-collecting body is the punching carbon steel of 50 μm.

Again the composite current collector prepared and positive plate are fitted, repeat above-mentioned hot pressing composite steps and obtain positive pole.Each walks compound tense, and the compressing time of aerostatic press is 10s.

Negative pole comprises negative current collector and negative electrode active material, and negative current collector is the filtter gold of thick 10 μm, and negative electrode active material is the zinc paper tinsel of thickness 50 μm.

Electrolyte is the zine methqne-sulfonate of 2mol/L and the pyrovinic acid lithium mixed aqueous solution of 3mol/L, regulates electrolyte pH to be 3.5.

Barrier film is AGM fibreglass diaphragm, and barrier film is suitable with positive pole with negative pole size.

After battery pack installs into, inject electrolyte, static a moment can start charge-discharge test.

Charge-discharge test

Carry out constant current charge-discharge with 0.2C to battery, voltage range is 1.4-2.1V.

Figure 19 is discharge capacity of the cell and cycle-index relation curve in embodiment 4.As can be seen from the figure, battery has stable cycle performance.

Embodiment 5

Prepare positive pole: by LiMn2O4 LMO, conductive agent graphite, binding agent SBR and CMC mixes in water according to mass ratio 86.5:10:2.5:1, forms uniform anode sizing agent.Nylon wire is immersed in anode sizing agent completely, then the nylon wire being stained with anode sizing agent is taken out, dry at 60 DEG C, form positive active material, carried out compressing tablet subsequently, be cut into 8 × 10cm size, make positive plate, positive plate thickness is 0.4mm, and positive active material surface density is 750g/m ².Plus plate current-collecting body is 50 μm of thick punching carbon steels.

Plus plate current-collecting body is the punching carbon steel of 50 μm.

Be superimposed together obtained positive plate and sizable composite current collector formation positive pole, and the two sides of composite current collector is all superimposed with positive plate.

Negative pole comprises negative current collector and negative electrode active material, and negative current collector is the filtter gold of thick 10 μm, and negative electrode active material is the zinc paper tinsel of thickness 50 μm, and the two sides of filtter gold is all superimposed with zinc paper tinsel.

Barrier film is AGM glass fibre, and barrier film is suitable with positive pole with negative pole size.

6 positive poles and 7 negative poles are staggered, separate between positive pole and negative pole with barrier film, form a battery, theoretical capacity is about 6Ah.

Electrolyte is the ZnSO of 2mol/L ₄with the Li of 1mol/L ₂sO ₄mixed aqueous solution, regulates electrolyte pH to be 3.5.After battery pack installs into, inject 170mL electrolyte, static 3 hours, can charge-discharge test be started.0.2C constant current charge and 2.05 or 2.1V constant voltage charge, 0.2C constant-current discharge, voltage range is 1.4-2.1V.

Figure 20 is discharge capacity of the cell and cycle-index relation curve in embodiment 5.As can be seen from the figure, the discharge capacity of battery is highly stable, and battery charging and discharging circulates the discharge capacity 6Ah nearly of 40 times, does not almost decay, illustrates that battery has stable cycle performance.

Although inventor has done more detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, to those skilled in the art, above-described embodiment to be modified and/or flexible or adopt equivalent replacement scheme to be obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.

Claims

1. a battery, comprise positive pole, negative pole and aqueous electrolyte, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

2. a battery, comprise positive pole, two negative poles and aqueous electrolyte, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion, described composite current collector has the first surface and second that are oppositely arranged, and described positive plate is arranged on described first surface and second; Described two negative poles share described positive pole, and described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

3. a battery, comprise two positive poles, negative pole and aqueous electrolytes, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion, described composite current collector has the first surface and second that are oppositely arranged, described first surface is relative with described negative pole, and at least described first surface is provided with described positive plate; Described two positive poles share described negative pole, and described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

4. a battery, comprise positive pole, negative pole and aqueous electrolyte, described positive pole comprises composite current collector and positive plate, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion, described composite current collector has the two sides be oppositely arranged, wherein, the one side that at least described composite current collector is relative with described negative pole is provided with described positive plate; Described negative pole is selected from metal, alloy or carbon-based material; Described battery n to described positive pole and negative pole, n >=2, described positive pole, negative pole are arranged alternately, and two adjacent positive poles share the negative pole between two positive poles, and two adjacent negative poles share the positive pole between two negative poles; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced when charging and is deposited on described negative pole formation negative electrode active material, and described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte.

5. according to the battery in claim 1-4 described in any one, it is characterized in that: described battery also comprises the additive joined in described negative pole and/or aqueous electrolyte, described additive is bismuth oxide and/or bismuth nitrate.

6. according to the battery in claim 1-4 described in any one, it is characterized in that: described negative pole is selected from Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or at least one in the described metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

7. a battery, comprise positive extraction electrode, at least one bipolar electrode, negative extraction electrode and aqueous electrolyte, described positive extraction electrode comprises composite current collector and is arranged on the positive plate of described composite current collector one side, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described positive plate comprises positive active material, described positive active material can reversible deviate from-embedded ion; Described bipolar electrode is arranged between described positive extraction electrode and negative extraction electrode, described bipolar electrode comprises bipolar current collector and described positive plate, described bipolar current collector has the first surface and second that are oppositely arranged, and described positive plate is arranged on the first surface of described bipolar current collector; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced second the formation negative electrode active material being deposited on described bipolar current collector when charging, described negative electrode active material is oxidized when discharging to be dissolved in described aqueous electrolyte; Described negative extraction electrode is selected from metal, alloy or carbon-based material; Described aqueous electrolyte is arranged between described positive extraction electrode and negative extraction electrode.

8. battery according to claim 7, is characterized in that: described battery also comprises the additive joined in described negative extraction electrode and/or aqueous electrolyte, and described additive is bismuth oxide and/or bismuth nitrate.

9. battery according to claim 7, is characterized in that: the peripheral part of described bipolar current collector is provided with the sealing for sealing described aqueous electrolyte.

10. battery according to claim 7, is characterized in that: the material of described bipolar current collector comprises conductive plastics, stainless steel or the stainless steel through Passivation Treatment.

11. batteries according to claim 10, is characterized in that: the material of described conductive plastics is selected from conducting polymer.

12. batteries according to claim 10, is characterized in that: the material of described conductive plastics comprises polymer and conductive agent.

13. batteries according to claim 7, it is characterized in that: material selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al of described negative extraction electrode or at least one in the described metal of Passivation Treatment, or containing at least one in the alloy of above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, at least one in carbon fiber, or copper is zinc-plated, or brass.

14., according to the battery in claim 1-13 described in any one, is characterized in that: described positive plate also comprises the carrier of electrochemicaUy inert, and described positive active material is formed on the carrier.

15. batteries according to claim 14, is characterized in that: described carriers electron insulate and has loose structure.

16. batteries according to claim 15, is characterized in that: the range of aperture size of described carrier is 50-200 order.

17. batteries according to claim 14, is characterized in that: described carrier can conduction electron.

18. batteries according to claim 14, is characterized in that: the material of described carrier is selected from least one in polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polyamide, polyurethanes, polyacrylonitrile.

19. batteries according to claim 14, is characterized in that: described carrier is nonwoven fabrics.

20. batteries according to claim 14, is characterized in that: the thickness of described carrier is less than 1mm.

21. batteries according to claim 14, is characterized in that: described carrier has the first surface and second that are oppositely arranged, and the first surface of described carrier and second are all formed with described positive active material.

22. batteries according to claim 14, is characterized in that: described positive active material is formed on the carrier by slurry.

23., according to the battery in claim 1-13 described in any one, is characterized in that: described positive active material has spinel structure, layer structure or olivine structural.

24., according to the battery in claim 1-13 described in any one, is characterized in that: described conducting film comprises thermoplastic polymer.

25., according to the battery in claim 1-13 described in any one, is characterized in that: described conducting film is attached on described plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.

26., according to the battery in claim 1-13 described in any one, is characterized in that: described positive plate is attached on described composite current collector by hot pressing compound or bonding mode.

27. according to the battery in claim 1-13 described in any one, it is characterized in that: the material of described plus plate current-collecting body is selected from the one in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned alloy of Passivation Treatment.

28., according to the battery in claim 1-13 described in any one, is characterized in that: described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.

29., according to the battery in claim 1-13 described in any one, is characterized in that: described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate, formates or alkylsulfonate.

30., according to the battery in claim 29 described in any one, is characterized in that: described alkylsulfonate is metilsulfate.

31., according to the battery in claim 1-13 described in any one, is characterized in that: described aqueous electrolyte also comprise with described positive active material can reversible deviate from-the corresponding ion of embedded ion.

32., according to the battery in claim 1-13 described in any one, is characterized in that: described battery also comprises barrier film, and described barrier film keeps described aqueous electrolyte.

33. 1 kinds of battery pack, comprise several as the battery in claim 1-32 as described in any one.

34. 1 kinds of uninterrupted power supplys, comprise as the battery in claim 1-32 as described in any one.

35. 1 kinds of vehicles, comprise if the battery in claim 1-32 as described in any one is as motor driven power supply.