CN103682476B

CN103682476B - Battery

Info

Publication number: CN103682476B
Application number: CN201310381682.0A
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: 2012-08-28
Filing date: 2013-08-28
Publication date: 2017-06-16
Anticipated expiration: 2033-08-28
Also published as: CN107093773B; CN107093773A; CN107293811A; CN107293811B; WO2014032594A1; CN103682476A

Abstract

Present invention is disclosed a kind of battery, including housing, it is arranged at positive pole in housing, negative pole, aqueous electrolyte and barrier film, the positive pole includes composite current collector and positive active material, the composite current collector has the two sides being oppositely arranged, wherein, it is provided with positive active material at least described composite current collector one side relative with the negative pole；The battery includes n to the positive pole and negative pole, and 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, and the alternate stacked arrangement of the positive pole, negative pole is in the housing.The battery that the present invention is provided has good cycle performance and energy higher, and battery is expected to obtain extensive utilization in fields such as large-scale energy storage, peak load regulation networks.

Description

Battery

Technical field

The invention belongs to electrochemical energy storage field, and in particular to a kind of battery.

Background technology

The mankind result in the rapidly expansion in secondary cell market to the extensive utilization of new energy.In current new energy system Requirement to secondary cell is ubiquitous.Either electric automobile, wind energy, solar grid-connected or peak load regulation network, are all badly in need of one Plant cheap, reliable, the secondary cell of safety and long lifespan.The secondary cell for being developed at present is concentrated mainly on lithium ion battery, The high temperature sodium-sulphur battery, sodium nickel chlorine battery and vanadium flow battery.These batteries all have respective advantage, such as lithium ion battery and The high temperature sodium-sulphur battery long lifespan and energy density are high, and vanadium flow battery even more possesses unlimited life-span etc. in theory.But no matter Which kind of battery, all cannot simultaneously meet cheap, reliable, the requirement of safety and long lifespan.Traditional lithium ion battery is prohibitively expensive, And have potential safety hazard；The high temperature sodium-sulphur battery manufacturing technology threshold is high, and price is expensive；The multinomial technical bottleneck of vanadium flow battery is current all Fail to obtain breakthrough etc..

The research of aquo-lithium ion battery is devoted to for this Many researchers, it is desirable to which lithium ion battery is greatly reduced with this Cost and improve security, and propose some with LiMn₂O₄It is positive pole, the oxide such as LiV of vanadium₃O₈Deng being negative pole, water It is the battery of electrolyte, but the stability difference and vanadium of therefore class negative pole discharge and recharge in water have certain toxicity, so as to limit The development of such battery is made.So far, it has been suggested that the structure of aquo-lithium ion secondary cell all fail to break away to be based on The structure of lithium ion abjection-embedding principle, such as the VO having had been reported that₂/LiMn₂O₄, LiV₃O₈/LiNi_0.81Co_0.19O₂, TiP₂O₇/LiMn₂O₄, LiTi₂(PO₄)₃/LiMn₂O₄, LiV₃O₈/LiCoO₂Deng.

The content of the invention

The present invention is intended to provide a kind of simple structure, low cost, safe and reliable and cycle life battery more long.

The invention provides a kind of battery, including housing, positive pole, two negative poles, water system electricity in the housing are arranged at Solution liquid and barrier film, the positive pole include composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body With the conducting film being coated on the plus plate current-collecting body, the composite current collector has the first face and the second face that are oppositely arranged, The positive active material is arranged on first face and the second face, the positive active material can it is reversible deviate from-be embedded in Ion；The negative pole is selected from metal, alloy or carbon-based material；The aqueous electrolyte includes electrolyte, and the electrolyte is at least Active ion can be ionized out, the active ion is reduced when charging and is deposited on the negative pole formation negative electrode active material, The negative electrode active material is oxidized in being dissolved in the aqueous electrolyte in electric discharge；The barrier film keeps the water system electrolysis Liquid；The positive pole and negative pole stacking are arranged in the housing, and the positive pole is placed between described two negative poles, described two negative The positive pole is extremely shared, the barrier film is located between the positive pole and negative pole.

Present invention also offers a kind of battery, including housing, two positive poles, negative pole, water systems in the housing are arranged at Electrolyte and barrier film, the positive pole include composite current collector and positive active material, and the composite current collector includes anode collection Body and the conducting film being coated on the plus plate current-collecting body, the composite current collector have the first face and second being oppositely arranged Face, first face is relative with the negative pole, and the positive active material is provided with least described first face, and the positive pole is lived Property material can it is reversible deviate from-embedded ion；The negative pole is selected from metal, alloy or carbon-based material；The aqueous electrolyte bag Electrolyte is included, the electrolyte can at least ionize out active ion, and the active ion is reduced when charging and is deposited on institute State negative pole and form negative electrode active material, the negative electrode active material is oxidized in being dissolved in the aqueous electrolyte in electric discharge； The barrier film keeps the aqueous electrolyte；The positive pole and negative pole stacking are arranged in the housing, and the negative pole is placed in institute State between two positive poles, described two positive poles share the negative pole, the barrier film is located between the positive pole and negative pole.

Present invention also offers a kind of battery, including housing, positive pole, negative pole, water system electrolysis in the housing are arranged at Liquid and barrier film, the positive pole include composite current collector and positive active material, the composite current collector include plus plate current-collecting body and The conducting film on the plus plate current-collecting body is coated on, the composite current collector has the two sides being oppositely arranged, wherein, it is at least described Positive active material is provided with the composite current collector one side relative with the negative pole, the positive active material reversible can take off Go out-embedded ion；The battery includes n to the positive pole and negative pole, and n >=2, two adjacent positive poles are shared and are located at two positive poles Between negative pole, two adjacent negative poles share the positive pole between two negative poles；The negative pole is selected from metal, alloy or carbon Sill；The aqueous electrolyte includes electrolyte, and the electrolyte can at least ionize out active ion, the active ion It is reduced when charging and is deposited on the negative pole formation negative electrode active material, the negative electrode active material is oxidized molten in electric discharge Solution is in the aqueous electrolyte；The barrier film keeps the aqueous electrolyte；The alternate stacked arrangement of the positive pole, negative pole in In the housing, the barrier film is located between the positive pole and negative pole.

The battery that the present invention is provided can be very good to solve the problems, such as self discharge, battery safe operation, production method simply, follow Ring function admirable and life-span are permanent, while the battery with different output discharge capacities, electricity can be set according to use demand Pond tool has been widely used.

Preferably, the housing is square.

Preferably, the positive pole, barrier film and negative pole form tabular.

Preferably, the positive pole, barrier film and negative pole winding shaping.

Preferably, the housing is cylinder barrel shaped, and the positive pole, the barrier film and the negative pole and the housing are coaxial Arrangement.

Preferably, the positive pole, the barrier film form cylinder and are arranged in the housing with the negative pole by winding.

Preferably, the material of the conducting film includes polymer and conductive filler.

Preferably, the polymer is selected from polyethylene, and polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide gathers Carbonic ester, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, in polyether sulfone, butadiene-styrene rubber or fluororesin at least one Kind.

Preferably, the conductive filler is selected from conducting polymer, carbon-based material or metal oxide.

Preferably, the material of the conducting film is selected from conducting polymer.

Preferably, the housing is set to aluminum plastic film.

Preferably, the housing is provided with fluid infusion, and the fluid infusion is used to supplement the aqueous electrolyte.

Preferably, the battery also includes the safety valve for controlling pressure in the housing.

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

Preferably, the material of the plus plate current-collecting body is selected from vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber In one kind, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or by the one kind in the above-mentioned metal of Passivation Treatment, or not Rust steel, carbon steel, Al alloys, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-Rh alloys or through transpassivation at One kind in the above-mentioned alloy of reason.

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

Preferably, the active ion include metal ion, metal be selected from Zn, Fe, Cr, Cu, Mn, Ni, Sn at least It is a kind of.

Preferably, the active ion is with least one in hydrochloride, sulfate, acetate, nitrate or formates Form is present in the aqueous electrolyte.

Present invention also offers a kind of battery, including housing, positive extraction electrode in the housing, at least one pair Polar electric pole, negative extraction electrode and aqueous electrolyte, the positive extraction electrode include plus plate current-collecting body and are arranged on the positive pole The positive active material of collector one side, the positive active material can it is reversible deviate from-embedded ion；The bipolar electrode It is arranged between the positive extraction electrode and negative extraction electrode, the bipolar electrode includes bipolar current collector and the positive pole Active material, the bipolar current collector has the first face and the second face being oppositely arranged, and the positive active material is arranged on institute State on the first face of bipolar current collector；The aqueous electrolyte includes electrolyte, and the electrolyte can at least ionize out work Property ion, the active ion charge when be reduced be deposited on the bipolar current collector the second face formed negative electrode active material Matter, the negative electrode active material is oxidized in being dissolved in the aqueous electrolyte in electric discharge；The negative extraction electrode is selected from gold Category, alloy or carbon-based material；The aqueous electrolyte is arranged between the positive extraction electrode and negative extraction electrode；It is described just to draw Go out the stacking of electrode, bipolar electrode and negative extraction electrode to be arranged in the housing.

A kind of battery safe operation of present invention offer, production method are simple, cycle performance is excellent and the life-span is permanent, together When can according to use demand set with different output voltages battery, battery tool have been widely used.

Preferably, the housing is set to square.

Preferably, the positive extraction electrode, the bipolar electrode and the negative extraction electrode form tabular.

Preferably, the battery also includes barrier film, and the barrier film keeps the aqueous electrolyte.

Preferably, it is coated with conducting film on the plus plate current-collecting body.

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

Preferably, the material of the bipolar current collector includes conductive plastics, stainless steel or by the stainless of Passivation Treatment Steel.

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

Preferably, the material of the conductive plastics includes polymer and conductive agent.

Preferably, the housing is set to aluminum plastic film.

Preferably, the housing is provided with fluid infusion, and the fluid infusion is used to supplement the electrolyte.

Preferably, the material of the negative extraction electrode is selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or through transpassivation At least one in the metal for the treatment of, or at least one in the alloy containing above-mentioned metal, or graphite foil, graphite flake, At least one in carbon cloth, carbon felt, carbon fiber, or copper is tin plating, or brass.

Present invention also offers a kind of battery, including housing, positive pole, barrier film, negative pole and water system in the housing Electrolyte, the positive pole includes plus plate current-collecting body and participates in the positive active material of electrochemical reaction, the positive active material Including can it is reversible deviate from-compound of embedded ion；The negative pole is selected from metal, alloy or carbon-based material；The water system electricity Solution liquid includes electrolyte, and the electrolyte can at least ionize out active ion, and it is heavy that the active ion is reduced when charging Product forms negative electrode active material in the negative pole, and the negative electrode active material is oxidized in electric discharge and is dissolved in the water system electrolysis In liquid；The stacking of the positive pole, the barrier film and the negative pole is arranged in the housing, and the barrier film is located at the positive pole and institute State between negative pole.

The battery that the present invention is provided, battery structure is simple, safe operation, low production cost, with considerable service life, It is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery.

Preferably, the housing is square.

Preferably, the positive pole, barrier film and negative pole form tabular.

Preferably, the positive pole, barrier film and negative pole winding shaping.

Preferably, the housing is aluminum plastic film.

Present invention also offers battery, including housing, positive pole, barrier film, negative pole and the water system electrolysis in the housing Liquid, the positive pole includes plus plate current-collecting body and participates in the positive active material of electrochemical reaction, and the positive active material includes Can it is reversible deviate from-compound of embedded ion；The negative pole is selected from metal, alloy or carbon-based material；The aqueous electrolyte Including electrolyte, the electrolyte can at least ionize out active ion, and the active ion is reduced when charging and is deposited on The negative pole forms negative electrode active material, and the negative electrode active material is oxidized in electric discharge and is dissolved in the aqueous electrolyte In；The stacking of the positive pole, the barrier film and the negative pole is arranged in the housing, and the barrier film is located at the positive pole and described Between negative pole.

The battery that the present invention is provided, safety non-toxic high with energy density, environmental protection is easily reclaimed and with low cost, this hair Battery in bright is highly suitable as the energy storage system and lead-acid battery in large-scale energy storage field as the green energy resource of a new generation Substitute.

Preferably, the housing is set to cylinder barrel shaped, and the positive pole, barrier film and the negative pole and the housing are coaxial Arrangement.

Preferably, the positive pole, barrier film and negative pole form cylinder and are arranged in the housing by winding.

Preferably, the negative pole and the barrier film are cylinder barrel shaped, and the plus plate current-collecting body is cylinder, the positive pole Active material is arranged between the barrier film and the plus plate current-collecting body.

Preferably, the battery also includes retainer ring, and the retainer ring fixes the plus plate current-collecting body, the barrier film, institute State negative pole and the housing；The material of the retainer ring is polyvinyl chloride, and the retainer ring is two, is respectively arranged at described The two ends of housing.

Preferably, the retainer ring includes upper strata ring and lower floor's ring, and the upper strata ring and lower floor's ring are formed in one, The upper strata ring fixes the plus plate current-collecting body and the barrier film, and lower floor's ring fixes the barrier film and the negative pole.

Preferably, the external diameter of the upper strata ring is identical with the internal diameter of the negative pole, the internal diameter of the upper strata ring with it is described just The diameter of pole collector is identical；The external diameter of lower floor's ring is identical with the internal diameter of the barrier film, the internal diameter of lower floor's ring and institute The diameter for stating plus plate current-collecting body is identical.

Preferably, the housing is aluminum plastic film.

Brief description of the drawings

Fig. 1 is the integrally-built generalized section of battery that implementation method one is provided；

Fig. 2 is the structural representation of composite current collector in Fig. 1；

Fig. 3 is the structural representation of battery core in Fig. 1, wherein, show diagrammatically battery unit；

Fig. 4 is the integrally-built generalized section of battery that implementation method two is provided；

Fig. 5 is the integrally-built generalized section of battery that implementation method two is provided, wherein, composite current collector is oppositely arranged Two sides on be provided with positive active material；

Fig. 6 is the integrally-built generalized section of battery that implementation method three is provided, wherein, battery include the two pairs of positive poles and Negative pole；

Fig. 7 is the generalized section of the battery core that implementation method three is provided, wherein, positioned at outermost positive pole composite current collector Positive active material is provided with the two sides being oppositely arranged；

Fig. 8 is the integrally-built generalized section of battery that implementation method three is provided, wherein, the logarithm of positive pole and negative pole is big In 2；

Fig. 9 is the integrally-built generalized section of battery that implementation method four is provided；

Figure 10 is the structural representation of bipolar electrode in Fig. 9；

Figure 11 is the schematic diagram of battery structure in Fig. 9, wherein, show diagrammatically battery unit；

Figure 12 is the charging principle schematic diagram of the battery that implementation method four is provided；

Figure 13 is the integrally-built generalized section of battery that implementation method five is provided；

Figure 14 is battery structure schematic diagram in Figure 13, wherein, show diagrammatically battery unit；

Figure 15 is the integrally-built generalized section of battery that implementation method six is provided；

Figure 16 is the integrally-built generalized section of battery that implementation method seven is provided；

Figure 17 is the structural representation of the battery that implementation method eight is provided；

Figure 18 is the structural representation of the battery that implementation method eight is provided, and barrier film is folded with Z-shaped；

Figure 19 is the deployed condition schematic diagram of battery in Figure 18；

Figure 20 is the structural representation of the battery that implementation method eight is provided, wherein, battery winding shaping；

Figure 21 is that the structure of battery in implementation method nine splits schematic diagram；

Figure 22 is the structural representation of retainer ring in middle battery in Figure 21；

Figure 23 is the battery charging and discharging cycle performance figure that embodiment 1 is provided.

Wherein：

1. battery 2, the negative pole of 72. positive pole 4,74,160.

The positive active material of 6,78. aqueous electrolyte, 8. composite current collector 10,82.

The barrier film of 12,80,152. plus plate current-collecting body, 14. conducting film 16,76,156.

The lid of 20. battery unit, 22,70. housing 24,84.

The face of 26,86. seal cap, 28,88. safety valve 81. first

The battery of 82. second 30,40,50. battery of face 100.

The bipolar current collector of 52. 54. positive extraction electrode of bipolar electrode 56.

The negative extraction electrode in 61. first face, 62. second face 58.

The plane of 60. 64,68. battery unit of sealing 90.

The curved portions of 110,120,130. 140,150. battery of battery 92.

The 94. positive poles winding clearing end 96. negative pole winding retainer ring of clearing end 154.

The lower floor's ring of 158. positive active material, 162. upper strata ring 164.

Specific embodiment

The battery that the present invention is provided has energy density higher, the cycle performance of stabilization, in such as mobile phone, notebook computer Deng portable type electronic product, electric automobile, the field such as electric tool has considerable application prospect.

【Battery with internal parallel structure】

A kind of battery, battery has internal parallel structure.Below in conjunction with the accompanying drawings and specific embodiment has to illustrate The battery of internal parallel structure.

Implementation method one

Refer to shown in Fig. 1, a kind of battery 1, including housing 22, it is arranged at 2, two negative poles 4, water of positive pole in housing 22 It is electrolyte 6 and barrier film 16.Positive pole 2 and the stacking of negative pole 4 are arranged in 22 in housing, and positive pole 2 is placed between two negative poles 4, two Negative pole 4 shares positive pole 2, and barrier film 16 is located between positive pole 2 and negative pole 4, and barrier film 16 keeps aqueous electrolyte 6.

Housing 22 may be configured as the composite membrane of metal, plastics or metal and plastics, such as steel, aluminium, acrylonitrile-butadiene-benzene Ethylene copolymer (ABS), polypropylene (PP), nylon or aluminum plastic film etc..Preferably, housing 22 is set to aluminum plastic film, so that Housing is relatively thin, while reducing battery weight, also increases the space of inside battery.Aluminum plastic film includes one layer of aluminium flake and is arranged at The plastic sheet of aluminium flake side.Preferably, aluminum plastic film includes one layer of aluminium flake and is arranged at the ground floor plastic sheet and the of aluminium flake both sides Two layers of plastic sheet.

Housing 22 could be arranged to square.

Specifically, the order stacking arrangement according to negative pole 4, barrier film 16, positive pole 2, barrier film 16 and negative pole 4 forms tabular, It is placed in housing 22, as shown in Figure 1.So as to battery 1 may be designed as rectangular cell, such as cuboid or square.The battery structure Simply, convenient manufacture, cost are simple.

In addition, the order stacking arrangement according to negative pole 4, barrier film 16, positive pole 2, barrier film 16 and negative pole 4 forms tabular, so Winding shaping afterwards, so as to form tabular battery core.Preferably, positive pole 2, barrier film 16 and negative pole 4 are disposed as strip.According to electricity Pond design needs to be wound into the different number of turns.

Housing may be arranged as cylinder barrel shaped (not shown).

Specifically, the order stacking arrangement according to negative pole 4, barrier film 16, positive pole 2, barrier film 16 and negative pole 4 forms tabular, Then it is arranged in housing by winding the cylindrical battery core of formation, positive pole 2, barrier film 16, negative pole 4 and housing arranged in co-axial alignment.So as to, Battery may be designed as cylindrical battery, and battery structure is simple, convenient manufacture.

Specific in implementation method one, battery also includes the lid 24 being connected with housing 22, and the extension of positive pole 2 passes lid 24, the end that the extension of positive pole 2 passes lid 24 is provided with seal cap 26.Seal cap 26 needs steady with preferable electric conductivity and chemistry It is qualitative.In addition, seal cap 26 can also prevent the hole that aqueous electrolyte is passed from positive pole 2 from evaporating, so as to reduce aqueous electrolyte 6 Consumption.Positive pole 2 is connected with external circuit.

Negative pole 4 also extends and passes lid 24, so as to be connected with external circuit.Equally, negative pole 4 extends the end for passing lid 24 It is provided with seal cap (not shown).

In addition, battery 1 is in charging process, and especially during the fast later stage close to charging, due to the decomposition of aqueous electrolyte 6, Hydrogen, carrier of oxygen can be produced, the pressure in battery container can also rise, when pressure rises to certain value, battery container 22 can occur Deformation.Therefore, battery 1 also includes the safety valve 28 for controlling pressure in housing 22.When the pressure in the housing 22 of battery is arrived When being pressed up to default valve opening, safety valve 28 is opened, and pressure is discharged, and prevents housing 22 from deforming, so as to improve the life-span of battery 1 And security.

In addition, when the pressure in housing 22 reaches default valve closing and presses, safety valve 28 is closed, and prevents internal gas outside Leakage.Meanwhile, it is also prevented from extraneous air and is had undesirable effect into housing 22 is interior.And the hydrogen for being also prevented from separating out meets naked light When produce tempering, so as to ignite the internal gas of housing 22.

The fluid infusion (not shown) for supplementing aqueous electrolyte 6 is also provided with housing 22.So, when water system is electrolysed When liquid is consumed, electrolyte can be injected by fluid infusion.

Preferably, fluid infusion is to install the mounting hole (not shown) at safety valve 28.

Positive pole 2 is arranged between two negative poles 4, and aqueous electrolyte 6 is provided between positive pole 2 and negative pole 4, and positive pole 2 includes Composite current collector 8 and positive active material 10, composite current collector 8 have the first face 81 and the second face 82 being oppositely arranged, positive pole Active material 10 is arranged on the first face 81 and the second face 82, as shown in Figure 2.

The production method of positive pole 2 is not particularly limited, and positive active material 10 can be attached to by way of coating On composite current collector 8, for example, positive active material 10 is made slurry, is then coated on composite current collector 8 by slurry method； Positive active material 10 can also be attached on composite current collector 8 by way of stacking, for example, will be molded by predefined size Composite current collector 8 and positive active material 10 suppressed, make between positive active material 10 and composite current collector 8 make electrical contact with Well, positive pole 2 is formed.The coating density range of positive active material 10 is 100-1000g/m²。

Specifically, positive active material 10 has spinel structure, layer structure or olivine structural.

Specifically, positive active material 10 can it is reversible deviate from-be embedded in lithium ion, sodium ion or magnesium ion.

Positive active material 10 can meet formula Li_1+xMn_yM_zO_kCan it is reversible deviate from-point that is embedded in lithium ion is brilliant The compound of stone structure, wherein, -1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M be selected from Na, Li, Co, Mg, At least one in Ti, Cr, V, Zn, Zr, Si, Al, Ni.Preferably, positive active material contains LiMn₂O₄.It is furthermore preferred that just Pole active material contains the LiMn through overdoping or coating modification₂O₄。

Positive active material 10 can meet formula Li_1+xM_yM′_zM″_cO_2+nCan it is reversible deviate from-be embedded in lithium ion The compound of layer structure, wherein, -1<X≤0.5,0≤y≤1,0≤z≤1,0≤c≤1, -0.2≤n≤0.2, M, M ', M " Be respectively selected from Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al at least one of.Preferably, positive active material contains LiCoO₂。

Positive active material 10 can meet formula Li_xM_1-yM′_y(XO₄)_nCan it is reversible deviate from-be embedded in lithium ion The compound of olivine structural, wherein, 0<X≤2,0≤y≤0.6,1≤n≤1.5, M be selected from Fe, Mn, V or Co, M ' be selected from Mg, At least one of Ti, Cr, V or Al, X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO₄。

In current Lithium Battery Industry, nearly all positive active material all can be through modifications such as overdoping, claddings.But mix Miscellaneous, the means such as coating modification cause the chemical general formula of material to express complicated, such as LiMn₂O₄Can not represent makes extensively at present The formula of " LiMn2O4 ", and should be with formula Li_1+xMn_yM_zO_kIt is defined, widely including by various modified LiMn₂O₄ Positive active material.Likewise, LiFePO₄And LiCoO₂Also should be construed broadly to include by various doping, cladding etc. Modified, formula corresponds with Li_xM_1-yM′_y(XO₄)_nAnd Li_1+xM_yM′_zM″_cO_2+nPositive active material.

When positive active material 10 is lithium ion abjection-inlaid scheme, can be from such as LiMn₂O₄、LiFePO₄、 LiCoO₂、LiM_xPO₄、LiM_xSiO_yCompounds such as a kind of (wherein M are variable valency metal).

Additionally, the compound N aVPO of sodium ion can be deviate from-is embedded in₄F, can deviate from-be embedded in the compound Mg M of magnesium ion_xO_y (wherein M is a kind of metal, 0.5<x<3,2<y<6)-the change of embedded ion or functional group can and with similar functions, be deviate from Compound can serve as the positive active material of battery of the present invention, therefore, the invention is not limited in lithium ion battery.

In a particular embodiment, when positive pole is prepared, binding agent can be also added in anode sizing agent, binding agent is favourable Uniformly it is bonded together in positive active material 10 is made.Binding agent weight percentage ranges of solid content in anode sizing agent are 0.5-10%.Specifically, binding agent is selected from but is not limited only to polymer, polymer is selected from polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride Alkene (PVDF), sodium carboxymethylcellulose (CMC), sodium carboxymethylcellulose derivative (CMC derivation), butadiene-styrene rubber (SBR), at least one in butadiene-styrene rubber derivative (SBR derivation).Butadiene-styrene rubber derivative is as passed through chemical modification Obtain with hydrophilic butadiene-styrene rubber (PSBR100).

In a particular embodiment, when positive pole is prepared, conductive agent can be also added in anode sizing agent, conductive agent is main That plays raising positive active material 10 leads electronic capability, and conductive agent weight percentage ranges of solid content in anode sizing agent are 0.5-30%.Conductive agent includes being selected from conducting polymer, CNT, activated carbon, Graphene, carbon black, graphite, carbon fiber, conduction At least one in ceramics.Carbon black includes but are not limited to acetylene black, section's qin carbon black (Ketjen black, KB) and super- P carbon blacks.Conductive agent can also include metal oxide.Metal oxide includes but are not limited to lead oxide and tin oxide.

Fig. 2 is the generalized schematic of composite current collector 8, and composite current collector 8 includes plus plate current-collecting body 12 and is coated on positive pole Conducting film 14 on collector 12.

The conducting film 14 being coated on plus plate current-collecting body 12 must is fulfilled in aqueous electrolyte can be with stable existence, insoluble In electrolyte, there is no swelling, high voltage and can not be oxidized, be easily processed into fine and close, waterproof and conductive film.One side Face, conducting film can play a protective role to plus plate current-collecting body, it is to avoid corrosion of the aqueous electrolyte to plus plate current-collecting body.The opposing party Face, advantageously reduces the contact internal resistance between positive active material and plus plate current-collecting body, improves the energy of battery.

In order to effectively play the effect of conducting film 14, the thickness of conducting film 14 needs effective control.Conducting film 14 is thick The too thin easy breakage of degree, caliper uniformity is also bad, and aqueous electrolyte 6 is penetrated readily through；Conducting film 14 is too thick, and influence is led Electric energy power.Preferably, the thickness of conducting film 14 is 10 μm of -2mm, and conducting film 14 can not only effectively play protection anode collection The effect of body 12, and advantageously reduce the contact internal resistance between positive active material 10 and plus plate current-collecting body 12.

Plus plate current-collecting body 12 has the first face and the second face being oppositely arranged, it is preferred that the first face of plus plate current-collecting body 12 Conducting film 14 is coated with the second face.

Conducting film 14 can be bonded by binding agent, hot pressing is compound or method that is vacuumizing is coated on plus plate current-collecting body 12 On, example, plus plate current-collecting body 12 is placed between two panels conducting film 14, it is compound by heating, make the clad anode of conducting film 14 Collector 12, and ensure that conducting film 14 is more intact than the part sealing that plus plate current-collecting body 12 has more.

Conducting film 14 includes the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50-95%, excellent Choosing, polymer is selected from thermoplastic polymer.In order that conducting film can be conductive, there are two kinds of feasible forms：(1) polymer is Conducting polymer；(2) conducting film also includes conductive filler.

Conducting polymer choice requirement be conductive energy but electrochemicaUy inert, i.e., will not be used as charge transfer medium Ionic conduction.Specifically, conducting polymer include but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, Polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and its any mixture.Conducting polymer inherently has It is conductive, it is also possible to being doped to conducting polymer or being modified further to improve its conductive capability.From electric conductivity Used with the stabilization in battery and considered, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.

Likewise, the choice requirement of conductive filler for surface area is small, be difficult to aoxidize, crystallinity is high, conductive but electricity Chemical inertness, i.e., will not be used as the ionic conduction of charge transfer medium.

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

Preferably, conductive filler is carbon-based material, and the form or mechanical performance of carbon-based material are not specially required, example , carbon-based material is selected from the one kind in graphite, CNT or amorphous carbon.Amorphous carbon include but are not limited to activated carbon and Carbon black.The preferred carbon black of carbon-based material and graphite, it has big potential window, so as to the positive and negative electrode potential stabilization to relative broad range simultaneously With electric conductivity high.Metal oxide includes but are not limited to lead oxide, tin oxide.

When conductive filler is included in conducting film, the polymer in conducting film is preferably comprised and played with reference to conductive filler effect Non-conductive polymer, non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, it is non- Conducting polymer is thermoplastic polymer.

Specifically, thermoplastic polymer includes but are not limited to polyolefin such as polyethylene, polypropylene, polybutene, polychlorostyrene second Alkene, polystyrene, polyamide, makrolon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, polyether sulfone, butylbenzene rubber One or more in glue or Kynoar.Wherein, preferably polyolefin, polyamide and Kynoar.These polymer Melted easily by heat, therefore be easily combined with each other with plus plate current-collecting body and positive plate.Additionally, these polymer have greatly Potential window, so that positive stabilizer pole and be battery output density saving weight.

Specifically, can be by preparing slurry containing thermoplastic polymer and being coated with and cure pastes form conduction Film.Certainly, what conductive filler can be extra is contained in slurry, specifically, polymer and conductive filler are combined with certain Mode is combined the conducting film for being processed and obtaining conductive energy as disperseed compound, level.Preferably, by polymer monomer and Conductive filler mixes, and because polymer monomer is small molecule, conductive filler can be good at being dispersed in polymer monomer, then Polymer monomer is polymerized in the presence of initiator, prepare conducting film.

The carrier that plus plate current-collecting body 12 conducts and collects primarily as electronics, is not involved in electrochemical reaction, i.e., in battery 1 In operating voltage range, what plus plate current-collecting body 12 can be stablized is present in aqueous electrolyte 6, so that it is steady to ensure that battery 1 has Fixed cycle performance.Plus plate current-collecting body 12 needs to meet big surface area, good mechanical property, conducts electricity very well etc. and requiring.Positive pole collection The material of fluid 12 includes the one kind in carbon-based material, metal or alloy.

Carbon-based material is selected from the one kind in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In tool In the implementation method of body, plus plate current-collecting body is graphite, such as the paper tinsel of commercialized graphite compacting, the wherein part by weight shared by graphite Scope is 90-100%.

Metal includes Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or by the above-mentioned metal of Passivation Treatment Kind.In a particular embodiment, plus plate current-collecting body 12 is nickel foam.Composite current collector containing nickel foam, in water system electrolysis It is difficult to be corroded in liquid 6, so that the performance of positive pole 2 containing this composite current collector 8 is more stablized.

It is metallic surface is formed one layer of passivating film by the main purpose that metal is passivated treatment, so as to be filled in battery In discharge process, collection and the conduction electronics of stabilization can be played a part of, without participating in positive pole reaction, it is ensured that battery performance.

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

Stainless steel includes stainless (steel) wire, stainless steel foil, and the model of stainless steel includes but are not limited to stainless steel 304 or not One kind in rust steel 316 or Stainless steel 316 L.

Likewise, by stainless steel be passivated treatment be also can stablize play collect and conduction electronics work With without participating in electrode reaction, it is ensured that battery performance.In a specific embodiment, the detailed process of passivation stainless steel is： At 50 DEG C, stainless steel is inserted half an hour in 20% nitric acid, stainless steel surfaces is formed one layer of passivating film.It is stainless after passivation Steel is used as collector.

The thickness of plus plate current-collecting body 12 has certain influence on the chemical property of positive pole 2, and the thickness of plus plate current-collecting body 12 is too It is thin, the mechanical strength of plus plate current-collecting body 12 can be influenceed；The thickness of plus plate current-collecting body 12 is too thick, can increase the weight of positive pole 2, so that The energy density of positive pole 2 is influenceed, in the present invention, in order that there is battery energy density high to export, it is preferred that anode collection The thickness of body 12 is 10 μm -100 μm.

Preferably, before using plus plate current-collecting body 12, plus plate current-collecting body 12 is rotten through transpassivation, punching, polishing or weak acid Erosion is processed, and treated plus plate current-collecting body 12 has larger specific surface area, is conducive to improving plus plate current-collecting body 12 and conduction The Compound Degree of film 14, so as to reduce the contact internal resistance between positive active material 10 and composite current collector 8.

In the present invention, positive pole 2 uses composite current collector 8, i.e., in the Surface coating conducting film 14 of plus plate current-collecting body 12, lead Electrolemma 14 is using polymer or composition polymer with superior electrical conductivity energy, on the one hand, conducting film 14 can be improved further Plus plate current-collecting body 12 leads electronic capability, so as to improve the big high rate performance of battery；On the other hand, it is coated on plus plate current-collecting body 12 Conducting film 14, it is to avoid plus plate current-collecting body 12 and the directly contact of aqueous electrolyte 6, solve aqueous electrolyte 6 to positive pole collection The potential etching problem of fluid 12, it is ensured that the stability of plus plate current-collecting body 12, solves the problems, such as the possible self discharge of battery 1, so that Make battery 1 that there is the cycle performance of stabilization.

Negative pole 4 is selected from metal, alloy or carbon-based material, and the thickness range of negative current collector is 20 to 500 μm.

Specifically, negative pole 4 be selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or by the metal of Passivation Treatment extremely Few one kind, or at least one in the alloy containing above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber At least one, or copper is tin plating, or brass.

In an implementation method for negative pole 4, negative pole 4 only includes negative current collector, and negative current collector conducts as electronics Carrier with collecting, is not involved in electrochemical reaction.The material of negative current collector be selected from but be not limited only to Ni metal, Ag, Pb, Sn, Fe, Al or by least one in the above-mentioned metal of Passivation Treatment, or carbon-based material, or stainless steel.Wherein, carbon substrate Material includes graphite material, such as the paper tinsel that commercialized graphite is suppressed, 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 4 is also selected from the metal containing hydrogen-evolution overpotential plating/coating high, so as to reduce the hair of negative pole side reaction It is raw.Plating/coating is selected from least one of the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy, or oxide.Plating/coating Thickness range be 1-1000nm.For example：Lead or silver on the negative current collector plated surface of copper, or covered in the form of coating One layer of carbon.

In the implementation method of another negative pole 4, negative pole 4 is only including negative current collector, but the selection of negative current collector With in electrolyte active ion it is corresponding, i.e., the material of negative current collector for active ion simple substance, such as in electrolyte activity from Son is Zn²⁺, negative pole 4 corresponds to metal Zn.Now, negative pole 4 functions not only as the deposition vehicle of active ion, while can also join With cell reaction.

In the implementation method of another negative pole 4, negative pole 4 includes negative current collector and negative electrode active material, negative electrode active The selection of material with electrolyte active ion it is corresponding, i.e., the material of negative electrode active material for active ion simple substance, such as electricity Active ion is Zn in solution liquid²⁺, negative electrode active material corresponds to metal Zn.Example, negative pole 4 includes filtter gold and zinc paper tinsel, yellow Copper Foil may participate in negative pole 4 and react as negative current collector, zinc paper tinsel correspondence negative electrode active material.

Aqueous electrolyte 6 includes electrolyte, and electrolyte can at least ionize out active ion, active ion quilt when charging Reduction is deposited on negative pole 4 and forms negative electrode active material (not shown), and negative electrode active material is oxidized in electric discharge and is dissolved in water system In electrolyte 6.

Active ion includes metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.Preferred Implementation method in, active ion is Zn²⁺.The concentration range of active ion is 0.5-15mol/L.

It is furthermore preferred that also including a kind of electrolyte in aqueous electrolyte 6, this electrolyte can ionize out correspondence in positive pole The ion of reversible abjection-insertion can occur.

In aqueous electrolyte 6 containing can it is reversible deviate from-ion that be embedded in, such that it is able to improve positive active material 10 and The intermediate ion exchange velocity of aqueous electrolyte 6.Specifically, positive active material 10 for can it is reversible deviate from-be embedded in the change of lithium ion Compound, it is corresponding in electrolyte also to include that the lithium salts of lithium ion is ionized out.The ion of reversible abjection-insertion includes lithium ion Or sodium ion or magnesium ion, the concentration range of the ion of reversible abjection-insertion in aqueous electrolyte is 0.1-10mol/L.

Active ion is present in water at least one form in hydrochloride, sulfate, acetate, nitrate or formates In being electrolyte.

In order to ensure battery capacity, the concentration of the active ion in aqueous electrolyte 6 must reach certain limit, work as water system When electrolyte crosses alkali, the solubility of active ion in electrolyte can be influenceed；When aqueous electrolyte peracid, then electrode material occurs The problems such as proton is embedded in altogether in material corrosion and charge and discharge process, therefore, the pH value range of aqueous electrolyte is 3-7.

Barrier film 16 is arranged between positive pole 2 and negative pole 4, on the one hand, barrier film 16 prevents the short circuit of battery 1；On the other hand, barrier film 16 can keep aqueous electrolyte 6, specifically, by negative pole 4, barrier film 16, positive pole 2, barrier film 16 and the stacked arrangement of negative pole 4 it is good after, Housing 22 is placed on, a certain amount of post package of aqueous electrolyte 6 is injected, barrier film 16 is immersed in aqueous electrolyte 6, i.e. barrier film Aqueous electrolyte 6 is absorbed in 16, it is ensured that the ionic conduction path between positive pole 2 and negative pole 4；In addition, it is also possible to first Barrier film 16 is immersed in aqueous electrolyte 6, the barrier film 16 that aqueous electrolyte 6 then will be absorbed again is placed on positive pole 2 and bears Between pole 4.

Barrier film 16 can use porous septum, bonded fabric or glass fibre.Porous septum includes but are not limited to poly- second The lamination barrier film of alkene (PE), polypropylene (PP), the one kind in polyimides, or PE-PP, PP-PE-PP.Bonded fabric include but It is not limited only to artificial silk, acetate fiber, nylon.Impregnation amount of the aqueous electrolyte in barrier film can be in the holding capacity model of barrier film In enclosing, it is also possible to more than hold in range, because battery 1 is provided with housing, can prevent aqueous electrolyte 6 from leaking.

Refer to shown in Fig. 1 and Fig. 3, be arranged between negative pole 4 to the stacking of positive pole 2, negative pole 4 shares positive pole 2, and electronics is from just Pole collector 12 and negative pole 4 are derived or imported, battery 1 equivalent to 2 internal parallels of battery unit 20, in each battery unit 20 In have positive pole 2, negative pole 4, aqueous electrolyte 6 and a barrier film 16, barrier film 16 keeps aqueous electrolyte 6.In the electricity that the present invention is provided In pool structure, due to be between battery unit 20 it is in parallel, aqueous electrolyte 6 can be shuttled in any battery unit 20 without The short circuit of battery unit 20, the work that battery 1 can normally, stable can be caused.

The charge-discharge principle of battery that the present invention is provided is：In a battery unit 20, during charging, reversible can take off Go out-positive active material 10 of embedded ion in deviate from the ion, while active ion in aqueous electrolyte 6 is in negative pole 4 It is reduced to electronics, and is deposited on negative pole 4, forms negative electrode active material.Discharge process is then the inverse process for charging.

In the present invention, positive pole 2 uses composite current collector 8, is coated on the conducting film 14 on plus plate current-collecting body 12 equivalent to guarantor Cuticula, can effectively prevent corrosion of the aqueous electrolyte 6 to plus plate current-collecting body 12, improve the influence of the self discharge of battery 1.Except this Outside, relative in the prior art with the individual battery cells battery that is constituted of parallel connection, it is of the invention in cleverly only with one just Pole 2 constitutes the battery 1 with parallel-connection structure, and two negative poles 4 share a positive poles 2, sufficiently make use of the of composite current collector 8 Simultaneously 81 and second face 82, and positive active material 10 is set simultaneously on the first face 81 and the second face 82, not only save just Pole material, and make the structure of battery 1 compacter, alleviates the weight of battery 1, thus battery 1 in the present invention have it is excellent Energy density and power density.In addition, the battery 1 in the present invention uses aqueous electrolyte 6, relative to commercialization at present Use organic system electrolyte lithium ion battery it is more safe and environment-friendly.

Battery preparation technique in the present invention is simple, battery can be prepared by way of stacking, specifically, negative pole, leaching Barrier film, positive pole and the negative pole for having aqueous electrolyte stack gradually arrangement and are placed in housing, and then it is packaged.Battery 1 equivalent to 2 formation in parallel of battery unit 20, without especially setting seal member between battery unit 20 and battery unit 20, Battery 1 with this internal parallel structure can normally, stabilization work, with excellent charge-discharge performance, and battery 1 Capacity higher can be exported, battery 1 is widely used.

Implementation method two

Refer to shown in Fig. 4, implementation method two provides a kind of battery 30, including housing 22, is arranged in housing 22 Two positive poles 2, negative pole 4, aqueous electrolyte 6 and barrier films.Positive pole 2 and the stacking of negative pole 4 are arranged in housing 22, and negative pole 4 is arranged on Between two positive poles 2, two positive poles 2 share negative pole 4, and barrier film is provided between negative pole 4 and positive pole 2, and barrier film keeps water system electrolysis Liquid.

Positive pole 2 includes composite current collector 8 and positive active material 10, and composite current collector 8 includes plus plate current-collecting body 12 and bag Overlay on the conducting film 14 on plus plate current-collecting body.Composite current collector 8 has the first face 81 and the second face 82 being oppositely arranged, the first face 81 is relative with negative pole 4, and positive active material 10 is arranged on the first face 81, certainly, is not particularly limited, positive-active Material 10 can also be arranged on the second face 82 simultaneously, as shown in Figure 5.Negative pole 4 is selected from metal, alloy or carbon-based material；Water system Electrolyte includes electrolyte, and electrolyte can at least ionize out active ion, active ion be reduced when charging be deposited on it is negative Pole 4 forms negative electrode active material (not shown), and negative electrode active material is oxidized in being dissolved in aqueous electrolyte 6 in electric discharge.

Positive active material 10, composite current collector 8, negative pole and aqueous electrolyte 6 by the agency of in implementation method one, this In be just not repeated.

Likewise, the one side of conducting film 14 can further improve the conductive capability of plus plate current-collecting body 12, another side is conductive The mainly isolation contact with aqueous electrolyte 6 of plus plate current-collecting body 12 of film 14, so as to avoid aqueous electrolyte 6 to plus plate current-collecting body 12 Corrosion, it is ensured that the stability of plus plate current-collecting body 12.

Housing 22 can set squarely or cylinder barrel shaped, corresponding, and battery 30 may be designed as rectangular cell or cylinder Battery.

Specifically, the stacking arrangement of positive pole 2, barrier film 16, negative pole 4, barrier film 16 and positive pole 2 forms tabular, housing 22 is placed in In, as shown in Figure 4.So as to battery 30 may be designed as rectangular cell, such as cuboid or square.The battery structure is simple, convenient Manufacture, cost are simple.

In addition, the stacking arrangement of positive pole 2, barrier film 16, negative pole 4, barrier film 16 and positive pole 2 forms tabular, then winding shaping, So as to form tabular battery core.Preferably, positive pole 2, barrier film 16 and negative pole 4 are disposed as strip.According to battery design needs It is wound into the different number of turns.

Housing 22 may be arranged as cylinder barrel shaped.

Specifically, the stacking arrangement of positive pole 2, barrier film 16, negative pole 4, barrier film 16 and positive pole 2 forms tabular, then by volume It is arranged in housing 22 around cylindrical battery core is formed, positive pole 2, barrier film 16, negative pole 4 and the arranged in co-axial alignment of housing 22.So as to battery can Cylindrical battery is designed as, battery structure is simple, convenient manufacture.

Remaining composition of battery 30 is no longer repeated one by one here with implementation method one in implementation method two.

Battery in implementation method one, two is all comparable to two battery units in parallel, and difference is, in implementation method one Battery 1 is that two negative poles 4 share a positive pole 2, and the battery 30 in implementation method two is the shared negative pole 4 of two positive poles 2, Therefore, the battery that the present invention is provided has flexible selection, in actually manufacture battery, can combine manufacture craft, both positive and negative polarity The factor such as weight, material cost, selection makes the battery of the structure as shown in implementation method one or two, makes the electricity for finally obtaining Pond has more cost and performance advantage.

Battery in the present invention, positive pole uses composite current collector, i.e., using the plus plate current-collecting body with conducting film cladding, lead Electrolemma prevents corrosion of the aqueous electrolyte to plus plate current-collecting body as the diaphragm of plus plate current-collecting body, improves battery potential Self discharge problem, battery has the cycle performance of stabilization.Battery has internal parallel structure, compared to parallel connection of the prior art Structure battery, battery more material-saving in the present invention and compact conformation, light so that the battery in the present invention is in energy There is obvious advantage in density and volume；Secondly, battery uses aqueous electrolyte, aqueous electrolyte have it is relatively high from Sub- conductivity, improves the high rate performance of battery；Battery is simple using safe and environment-friendly and manufacture craft, in preparation process, Battery with different output capacities can be prepared according to use demand, battery use is extensive, with commercial application prospect.

Implementation method three

Refer to shown in Fig. 6, a kind of battery 40, including housing 22, it is arranged at positive pole 2, negative pole 4, water system in housing 22 Electrolyte 6 and barrier film.

Battery includes n to positive pole 2 and negative pole 4, and n >=2, positive pole 2, negative pole 4 are arranged alternately, and two adjacent positive poles 2 are shared Negative pole 4 between two positive poles 2, two adjacent negative poles 4 share the positive pole 2 between two negative poles 4.Specific to figure In 6, battery 300 includes two pairs of positive poles 2 and negative pole 4, and two adjacent positive poles 2 share the negative pole 4 between two positive poles 2, Two adjacent negative poles 4 share the positive pole 2 between two negative poles 4.

Positive pole 2 includes composite current collector 8 and positive active material 10, and composite current collector 8 includes plus plate current-collecting body 12 and bag Overlay on the conducting film 14 on plus plate current-collecting body 12, composite current collector 8 has the two sides being oppositely arranged, wherein, at least composite current collecting Be provided with positive active material 10 in the one side relative with negative pole 4 of body 8, positive active material can it is reversible deviate from-embedded ion.

Specifically, referring to shown in Fig. 6, positive pole composite current collector 8 has the two sides being oppositely arranged, when positive pole 2 is located at two When between individual negative pole 4, the two sides that composite current collector 8 is oppositely arranged is relative with negative pole 4, therefore composite current collector 8 is oppositely arranged Two sides on be both needed to set positive active material 10；And for positioned at outermost positive pole 2, composite current collector 8 only have one side with Negative pole 4 is relative, therefore positive active material 10, composite current collector are set at least in the one side relative with negative pole 4 of composite current collector 8 8 one sides opposite with negative pole 4 are not particularly limited, can according to the setting positive active material of actual fabrication process selectivity, Be show diagrammatically in Fig. 7 in outermost layer positive pole, positive pole is also equipped with the one side of the composite current collector opposite with negative pole Active material 10.

Negative pole 4 is selected from metal, alloy or carbon-based material；Aqueous electrolyte includes electrolyte, and electrolyte can at least be ionized Go out active ion, active ion is reduced when charging and is deposited on formation negative electrode active material of negative pole 4 (not shown), negative electrode active Material is oxidized in being dissolved in aqueous electrolyte 6 in electric discharge.The selection of positive pole and preparation method, negative pole in implementation method three With aqueous electrolyte with implementation method one, introduction is not repeated herein.

The battery 40 shown in Fig. 6 contains two pairs of positive poles and negative pole, in parallel equivalent to 3 battery unit (not shown), but It is that, in actual fabrication battery, the battery structure that the present invention is provided can readily increase positive pole or negative according to use demand Pole or positive pole and negative pole, such as be superimposed negative pole at the outermost positive pole of battery 40 or be sequentially overlapped negative pole and positive pole, or Positive pole is superimposed at the outermost negative pole of battery 40 or positive pole and negative pole is sequentially overlapped, the positive pole and negative pole of superposition are alternately arranged. The number of positive pole and negative pole according to use demand determine, as shown in Figure 8, although the total output voltage of battery 50 does not have change, but electric Pond 50 has capacity higher, and battery structure is flexibly, widely used, with commercial application prospect.

In the battery system containing neutral aqueous electrolyte, it is difficult to find while meeting existing certain mechanical performance, excellent Good electric conductivity, again can in neutral aqueous electrolyte stable existence plus plate current-collecting body, therefore water system battery commercialization Process is stagnated always.The battery that the present invention is provided just can solve the problem that this problem, and the positive pole of battery uses composite current collecting On the one hand body, the plus plate current-collecting body that composite current collector is coated using conducting film, conducting film can improve the conduction of plus plate current-collecting body Performance, it is often more important that played a protective role to plus plate current-collecting body, corrosion of the neutral aqueous electrolyte of isolation to plus plate current-collecting body, Make plus plate current-collecting body in discharge process can stablize collection and derive electronics so that ensure battery have stabilization cyclicity Can, the battery that the present invention is provided has good Commercial Prospect.

【Bipolar battery】

Present invention also offers a kind of battery, specifically, battery is water system bipolar battery.Below by specific implementation Mode introduces water system bipolar battery.

Implementation method four

Refer to shown in Fig. 9 and Figure 10, a kind of battery 100, including housing (not shown), the positive extraction electricity in housing Pole 54, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6.Positive extraction electrode 54, bipolar electrode 52 Be arranged in housing with the stacking of negative extraction electrode 58, positive extraction electrode 54 and negative extraction electrode 58 be located at respectively the superiors and most under Layer, bipolar electrode 52 and aqueous electrolyte 6 are arranged between positive extraction electrode 54 and negative extraction electrode 58.In specific to Fig. 9, Battery 100 includes two bipolar electrodes 52.

Housing could be arranged to square.Specifically, positive extraction electrode 54, bipolar electrode 52 and negative extraction electrode 58 are laminated Arrangement forms tabular, is placed in housing.So as to battery 100 may be designed as rectangular cell, such as cuboid or square.The electricity The simple structure of pond 100, convenient manufacture, cost are simple.

The selection of housing is same to be set with implementation method one, likewise, battery 100 also includes and housing phase in implementation method four The lid (not shown) of connection, positive extraction electrode 54 and the extension of negative extraction electrode 58 pass lid, are connected with external circuit, and just The end that extraction electrode 54 and the extension of negative extraction electrode 58 pass lid is provided with seal cap, and seal cap can prevent aqueous electrolyte From the hole evaporation that positive extraction electrode 54 and negative extraction electrode 58 are passed, so as to reduce the consumption of aqueous electrolyte 6.

Likewise, battery 100 also includes safety valve and the fluid infusion (not shown) being arranged on housing, safety valve and fluid infusion The setting of mouth is just not repeated to introduce here with reference to implementation method one.

Positive extraction electrode 54 includes plus plate current-collecting body 12 and the positive active material 10 for being arranged on the one side of plus plate current-collecting body 12, Positive active material 10 can it is reversible deviate from-embedded ion.The He of positive active material 10 is had been described above in implementation method one Plus plate current-collecting body 12, is just not repeated to introduce here.

Figure 10 is the summary section of the bipolar electrode 52 for constituting battery 100, and bipolar electrode 52 includes bipolarity collection Fluid 56 and positive active material 10, bipolar current collector 56 have the first face 61 and the second face 62 being oppositely arranged, positive-active Material 10 is arranged on the first face 61 of bipolar current collector 56.First face 61 of bipolar current collector 56 and the polarity of the second face 62 Conversely, the first face 61 is equivalent to positive pole, and the second face 62 is equivalent to negative pole.

The production method of bipolar electrode 52 is not particularly limited, and positive active material 10 can be by way of coating It is attached in bipolar current collector 56, for example, positive active material 10 is made slurry, is then coated in by slurry method bipolar On property collector 56；Bipolar current collector 56 can also be coated on compressing positive active material 10；Can also pass through Be attached to positive active material 10 in bipolar current collector 56 by the mode of stacking, such as by by the bipolarity of predefined size shaping Collector 56 and positive active material 10 are suppressed, and make to be made electrical contact between positive active material 10 and bipolar current collector 56 good It is good, form bipolar electrode 52.The thickness range of positive active material 10 is 100-400 μm.Positive pole in bipolar electrode 52 Positive active material 10 in active material 10 and positive extraction electrode 54 specifically can refer to positive active material in implementation method one.

The material of bipolar current collector 56 can be conductive plastics, it is preferred that the thickness range of bipolar current collector 56 is 50 to 100 μm.

The material of conductive plastics is selected from conducting polymer, specifically, conducting polymer includes but are not limited to polyacetylene, gathers At least one in pyrroles, polythiophene, polyphenylene sulfide, polyaniline, poly quinoline or polyparaphenylene.Conducting polymer inherently has Electric conductivity, it is also possible to being doped to conducting polymer or being modified further to improve its conductive capability.

Conductive plastics can also be compound conductive plastics, composite conductive plastic with polymer as main matrix, and Mix conductive agent wherein to be formulated, here, whether conduction is not particularly limited polymer in itself, compound conductive plastics Conductive capability be mainly by conductive agent realize.Specifically, conductive plastics include polymer and conductive agent, polymer include but not It is only limitted to polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, makrolon, poly-methyl methacrylate Ester, polyformaldehyde, polyphenylene oxide, polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.Specifically, polymer can be Polytetrafluoroethylene (PTFE) in fluororesin, can also be copolymer, such as copolymerization of polytetrafluoroethylene (PTFE) (PTFE) and butadiene-styrene rubber (SBR) Thing.

Conductive agent includes carbon-based material, metal or metal oxide.Mass percent model of the conductive agent in conductive plastics It is 10-90% to enclose.

Carbon-based material is selected from the one kind in graphite, CNT or amorphous carbon.Amorphous carbon includes but are not limited to live Property charcoal and carbon black.

The form of metal is not limited, and can be metal powder, sheet metal, metal strand, metallic fiber.Metal oxide includes But it is not limited only to lead oxide, tin oxide.

Specifically, by polymer and conductive agent with certain complex method as disperseed compound being processed of compound, level to obtain The plastics of the conductive energy for obtaining.

The material of bipolar current collector 56 can also be stainless steel or the stainless steel by Passivation Treatment, the machinery of stainless steel Performance is better than conductive plastics, therefore, when using stainless steel as bipolar current collector 56, the thickness of bipolar current collector 56 can With thinner, specifically, the thickness range of bipolar current collector 56 is 20-100 μm.

The method of passivation for stainless steel treatment is not limited, and can be physical method passivation, chemical method passivation or electrochemistry Method is passivated.The purpose of passivation is in order to improve the compatibility of bipolar current collector 56 and aqueous electrolyte 6, so as to reduce secondary anti- The generation answered, makes battery have the cycle performance of stabilization.

It is high for constituting the mechanical property requirements of bipolar current collector 56 of bipolar electrode 52 in the present invention, you can To use the conductive plastics of lighter in weight or the stainless steel of thinner thickness as bipolar current collector 56, the overall weight of battery 100 It is reduced, therefore the energy density of battery 100 is significantly improved.

Negative extraction electrode 58 is selected from metal, alloy or carbon-based material.

Specifically, negative extraction electrode 58 is selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the gold by Passivation Treatment At least one at least one in category, or the alloy containing above-mentioned metal, or graphite foil, graphite flake, carbon cloth, carbon felt, carbon At least one in fiber, or copper is tin plating, or brass.

Negative extraction electrode 58 is also selected from the metal containing hydrogen-evolution overpotential plating/coating high, so that it is secondary anti-to reduce negative pole The generation answered.Plating/coating is selected from least one of the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy, or oxide. The thickness range of plating/coating is 1-1000nm.For example：Lead or silver on the plated surface of negative extraction electrode 58 of copper, or to coat Form cover one layer of carbon.The thickness range of plus plate current-collecting body 12 and negative extraction electrode 58 is 1-10mm.

Negative extraction electrode 58 with the negative pole 4 in implementation method one, that is, bear extraction electrode 58 only can be collected as electronics and The matrix of conduction is not involved in electrode reaction, or negative extraction electrode 58 includes negative current collector and negative electrode active material, such as negative extraction Electrode 58 is filtter gold and zinc paper tinsel, and zinc paper tinsel is consistent with negative electrode active material.

Aqueous electrolyte 6 is arranged between positive extraction electrode 54 and negative extraction electrode 58, positive extraction electrode 54, bipolarity electricity Pole 52 and negative extraction electrode 58 are stacked, when bipolar electrode 52 is one in battery 100, positive extraction electrode 54 and adjacent Bipolar electrode 52 between, between bipolar electrode 52 and adjacent negative extraction electrode 58 be provided with aqueous electrolyte 6.When In battery 100 during 52 more than one of bipolar electrode, between positive extraction electrode 54 and adjacent bipolar electrode 52, adjacent double Aqueous electrolyte 6 is provided between polar electric pole 52, between bipolar electrode 52 and adjacent negative extraction electrode 58.

Aqueous electrolyte 6 includes electrolyte, and electrolyte can at least ionize out active ion, active ion quilt when charging The second face that reduction is deposited on bipolar current collector 56 forms negative electrode active material, and negative electrode active material is oxidized molten in electric discharge In aqueous electrolyte 6, active ion is with least one shape in hydrochloride, sulfate, acetate, nitrate or formates for solution Formula is present in aqueous electrolyte 6.

Aqueous electrolyte 6 and the active ion by the agency of in implementation method one, just repeat no more here.

Preferably, also include in aqueous electrolyte 6 with positive active material 10 can it is reversible deviate from-embedded ion is corresponding Ion, ion include lithium ion, sodium ion or magnesium ion at least one.Specifically, as positive active material 10 can During reversible abjection-insertion lithium ion, then corresponding in aqueous electrolyte 6 also to contain lithium ion, so, positive pole work can be improved Property material 10 and aqueous electrolyte 6 in ion-exchange speed, improve the high rate charge-discharge performance of battery 100.

Battery 100 in implementation method four also includes barrier film 16, and it is double with adjacent that barrier film 16 is arranged on positive extraction electrode 54 Between polar electric pole 52, between bipolar electrode 52 and adjacent negative extraction electrode 58, battery 100 includes two in implementation method four Individual bipolar electrode 52, therefore, it is also equipped with barrier film 16 between adjacent bipolar electrode 52.On the one hand, barrier film 16 is used for Keeping aqueous electrolyte 6, another aspect barrier film 16 prevents the short circuit of battery 100.

Barrier film 16 can use porous septum, bonded fabric or glass fibre.Porous septum includes but are not limited to poly- second The lamination barrier film of alkene (PE), polypropylene (PP), the one kind in polyimides, or PE-PP, PP-PE-PP.Bonded fabric include but It is not limited only to artificial silk, acetate fiber, nylon.Impregnation amount of the aqueous electrolyte 6 in barrier film 16 can be in the holding of barrier film 16 In limit of power, it is also possible to more than hold in range, because battery 100 is provided with sealing 60, can prevent aqueous electrolyte 6 from letting out Leakage.

The peripheral part of bipolar current collector 56 is provided with the sealing 60 for sealing aqueous electrolyte 6, does not limit especially Fixed, sealing 60 can use sealing ring, sealing ring it is preferably rectangular in shape, as long as the selection of sealing ring is in battery Excellent sealing effectiveness can be realized under 100 use environment.

It is not particularly limited, the material of sealing 60 is rubber, and rubber is selected from but is not limited only to silicon class rubber, fluorine class rubber One kind in glue, olefin rubber, nitrile rubber, wherein, olefin rubber includes but are not limited to butadiene-styrene rubber (SBR), chlorine Buna (CR).The rubber resin of these sealings have good sealing (fluid tight), resistance to acids and bases, resistance to chemical reagents, Durability, weatherability and heat resistance, and can for a long time be kept under the use environment of battery 100 these excellent performances without Can deteriorate, therefore can effectively prevent aqueous electrolyte 6 from being oozed out from battery 100, so as to prevent due to aqueous electrolyte 6 The short circuit of battery 100 for leaking and causing, it is ensured that the stable circulation performance of battery 100.

As long as additionally, action effect of the invention can be realized effectively, such as there is each of acid resistance and sealing Planting rubber can be used as the material of sealing of the present invention 60.

It is not particularly limited, when sealing 60 is using sealing ring, the enveloping surface of the area less than sealing ring of barrier film 16 Product, and sealing ring thickness sum of the height not less than barrier film 16 and positive active material 10, in assembled battery, will be soaked with The barrier film 16 of aqueous electrolyte 6 is placed in the circle of sealing ring, and barrier film 16 is not involved in sealing, can so be avoided because using porous Barrier film and the leakage of aqueous electrolyte 6 that is likely to result in.Certainly, the area of barrier film 16 can also be more than being arranged on bipolar electrode The encirclement area of the sealing 60 of 52 peripheral parts, as long as barrier film 16 is finally integrally formed with sealing 60, will not cause water system electricity Solution liquid 6 is revealed just.

Refer to shown in Figure 11, be arranged on to the stacking of bipolar electrode 52 positive extraction electrode 54 and negative extraction electrode 58 it Between, electronics is only derived or imported from positive extraction electrode 54 and negative extraction electrode 58, and battery 100 is equivalent in 3 battery units 64 Portion connects, and has positive pole, negative pole, aqueous electrolyte and barrier film in each battery unit 64, and aqueous electrolyte 6 passes through sealing 60 sealings, it is to avoid the short circuit between the battery unit 64 caused due to the leakage of aqueous electrolyte 6, so as to ensure battery 100 Normal work.

For example, one of battery unit 64 includes plus plate current-collecting body 12, positive active material 10, barrier film 16, water system electricity Second face 62 of solution liquid 6, sealing 60 and the bipolar current collector 56 as negative pole.Sealing 60 is used to seal each battery list Unit 64 in aqueous electrolyte 6, with avoid because the leakage of aqueous electrolyte 6 and caused by battery 100 short circuit.Shown in Figure 11 Battery 100 only includes two bipolar electrodes 52, but can essentially easily set battery 100 according to use demand The number of bipolar electrode 52, so that the battery with different output voltages and the battery with high output voltage are prepared, this The battery tool for providing is invented to have been widely used.

Battery preparation technique in the present invention is simple, can prepare battery by way of stacking, specifically, in negative extraction Ground is laminated on electrode and places rectangular seal, sealing ring is fitted with the peripheral part of negative extraction electrode, then in the circle of sealing ring Placement is soaked with the barrier film of aqueous electrolyte, then stacks gradually bipolar electrode and positive extraction electrode, positive extraction electrode and bipolarity Positive active material in electrode is placed simultaneously towards negative extraction electrode, and aqueous electrolyte is sealed by sealing ring.Bipolarity electricity The number of pole determines the last output voltage of battery, therefore, it can be set according to use demand the number of bipolar electrode, electricity Pond tool has been widely used.

Refer to shown in Figure 12, the charge-discharge principle of the battery 100 that the present invention is provided is：In a battery unit 64, During charging, can it is reversible deviate from-positive active material 10 of embedded ion in deviate from the ion, while in aqueous electrolyte 6 Active ion obtains electronics and is reduced in the second face 62 of bipolar current collector 56, and is deposited on the second face 62, forms negative pole Active material.In the battery unit 64 containing negative extraction electrode 58, active ion obtains electronics quilt on negative extraction electrode 58 Reduction, is deposited on negative extraction electrode 58.Discharge process is then the inverse process for charging.

In the present invention, the bipolar electrode 52 for constituting battery 100 is only set just in the first face 61 of bipolar current collector 56 Pole active material 10, and the second face 62 of bipolar current collector 56 is then equivalent to negative pole, is that active ion obtains electron reduction-deposition Carrier is provided, active ion is present in aqueous electrolyte 6, relative in the prior art in the first face of bipolar current collector 56 61 and second face 62 be respectively provided with positive active material 10, the structure of battery 100 in the present invention is compacter, and battery 100 has excellent Different energy density and power density.In addition, the battery 100 in the present invention uses aqueous electrolyte 6, relative to current business The lithium ion battery of the use organic system electrolyte of industry is more safe and environment-friendly.

Battery 100 in the present invention, connects equivalent to several battery units 64 and is formed, and each battery unit 64 leads to Cross sealing 60 to be sealed well, so as to the short circuit for preventing from causing due to the leakage of aqueous electrolyte 6.In addition, this hair Even if bright battery is not provided with special leakage-proof part or insulating element, prevented also from the short circuit between battery unit, so as to provide Bipolar battery with excellent ionic conductance, charge-discharge performance.In addition, different numbers can be set according to use demand The bipolar electrode 52 of amount, so as to prepare the battery 100 with different output voltages, the purposes of battery 100 is widely.

Implementation method five

Refer to shown in Figure 13, implementation method five provides a kind of battery 110, battery 110 includes housing (not shown), if In the positive extraction electrode 54 in housing, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6.Bipolarity Electrode 52 stacking is arranged between positive extraction electrode 54 and negative extraction electrode 58,58 points of positive extraction electrode 54 and negative extraction electrode Wei Yu not the superiors and orlop.

Positive extraction electrode 54 includes plus plate current-collecting body 12 and the positive active material 10 for being arranged on the one side of plus plate current-collecting body 12, Difference with implementation method five is that plus plate current-collecting body 12 is coated with conducting film 14.

Conducting film 14 can be bonded by binding agent, hot pressing is compound or vacuum coated method is coated on plus plate current-collecting body 12 One side, then positive active material 10 is set on conducting film 14 again, the thickness of conducting film 14 is 0.01-0.2mm.Specific to In Figure 13, conducting film 14 is coated with the two sides of plus plate current-collecting body 12.

The material of conducting film 14 has been discussed in detail in implementation method one, is just not repeated here.

On the one hand, the compound using conducting polymer or containing conductive agent can improve anode collection as conducting film 14 Body 12 leads electronic capability；On the other hand, it is coated on the conducting film 14 on plus plate current-collecting body, it is to avoid plus plate current-collecting body 12 and water It is the directly contact of electrolyte 6, solves aqueous electrolyte 6 to the potential etching problem of plus plate current-collecting body 12, it is ensured that anode collection The stability of body 12, improves the possible self discharge problem of battery 110, so that battery 110 has the cycle performance of stabilization.

Refer to shown in Figure 14, battery unit 68 is sealed by sealing 60, and sealing 60 is arranged on bipolar current collector 56 peripheral part, for sealing aqueous electrolyte 6.

Remaining composition of battery 110 and assembling mode are no longer repeated one by one here with implementation method four in implementation method five.

The battery provided in implementation method five, the plus plate current-collecting body coated using conducting film, has prevented aqueous electrolyte pair The potential etching problem of plus plate current-collecting body, make battery except with high output voltage, it is safe and environment-friendly the features such as in addition to, further Improve the stable circulation performance of battery.

Implementation method six

Refer to shown in Figure 15, implementation method six provides a kind of battery 120, battery 120 includes housing (not shown), if In the positive extraction electrode 54 in housing, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6.Bipolarity Electrode 52 stacking is arranged between positive extraction electrode 54 and negative extraction electrode 58,58 points of positive extraction electrode 54 and negative extraction electrode Wei Yu not the superiors and orlop.Difference with implementation method four is that battery 120 does not include barrier film.

Likewise, battery unit (not shown) is sealed by sealing 60, sealing 60 is arranged on bipolar current collector 56 Peripheral part, for sealing aqueous electrolyte 6.Example, sealing 60 can use sealing ring, and the height of sealing ring is more than just The thickness of pole active material 10, by the sealing ring with certain altitude so that positive extraction electrode 54 and adjacent bipolarity electricity Between the bipolar current collector 56 of pole 52 and bipolar electrode 52 bipolar current collector 56 and adjacent negative extraction electrode 58 it Between keep certain distance, to avoid the short circuit of battery 120.When the number more than one of bipolar electrode 52 in battery 120, it is adjacent Bipolar electrode 52 bipolar current collector 56 and bipolar current collector 56 between be again provided with sealing 60.

It is the positive extraction electrode 54 that will first can be prepared by predetermined dimension, bipolar when preparing the battery in implementation method six Property electrode 52 and negative extraction electrode 58 are arranged and sealed.Specifically, on positive extraction electrode 54 and bipolar electrode 52 just Pole active material 10 is arranged simultaneously towards negative extraction electrode 58, and sealing 60 can be higher by the thickness of positive active material 10 using having The elastomeric material of degree such as sealing ring, sealing ring is arranged on the peripheral part of bipolar current collector 56, finally by the mode of injection Injection aqueous electrolyte 6；Sealing 60 can also use thermoplastic rubber material, in preliminary sealing, can only in bipolarity The peripheral part on the side of collector 56 3 sets thermoplastic rubber material, retains openings at one side, by positive extraction electrode 54, bipolar electrode 52 and after negative extraction electrode 58 arranges, by heating or heating pressurization is molded Cure of Rubber, then by unencapsulated one side The aqueous electrolyte 6 of place's injection scheduled volume, all battery units are fully sealed again finally.

Remaining composition of battery 120 and assembling mode are no longer repeated one by one here with implementation method four in implementation method six.

Not using barrier film, battery 120 can not only give normal, lasting work to battery 120 in implementation method six, and And because weight is lighter, therefore battery 120 has more excellent energy density and specific power.In addition, when battery 120 is prepared, Sealing 60 can be easily formed, the short circuit caused due to the leakage of aqueous electrolyte 6 is prevented.Even if battery 120 is not Special leakage-proof part is set, you can prevent the short circuit between battery unit, battery 120 with excellent cycle performance and Cycle life.

Implementation method seven

Refer to shown in Figure 16, implementation method seven provides a kind of battery 130, battery 130 includes housing (not shown), if In the positive extraction electrode 54 in housing, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6.Bipolarity Electrode 52 stacking is arranged between positive extraction electrode 54 and negative extraction electrode 58,58 points of positive extraction electrode 54 and negative extraction electrode Wei Yu not the superiors and orlop.

Positive extraction electrode 54 includes plus plate current-collecting body 12 and the positive active material 10 for being arranged on the one side of plus plate current-collecting body 12, Difference with implementation method six is that plus plate current-collecting body 12 is coated with conducting film 14.

Selection, the molding mode of conducting film 14 are just no longer repeated one by one here with implementation method one.

Battery 130 in implementation method seven, the conducting film 14 being coated on plus plate current-collecting body 12 has completely cut off plus plate current-collecting body 12 contacts with aqueous electrolyte 6, improve the stabilization of plus plate current-collecting body 12, so as to ensure that battery 130 has the circulation of stabilization Performance.It is lighter without the weight of battery 130 using barrier film, while being easy to user to carry, there is provided excellent performance.

Battery in the present invention, bipolar current collector in bipolar electrode can be using conductive plastics or thinner thickness Stainless steel, while normal battery operation is ensured, the weight of battery is lighter so that the battery in the present invention is close in energy There is obvious advantage on degree and volume；Secondly, battery uses aqueous electrolyte, and aqueous electrolyte is with ion relatively higher Conductivity, improves the high rate performance of battery；Battery is simple using safe and environment-friendly and manufacture craft, in preparation process, can The battery with different output voltages is prepared with according to use demand, battery use is extensive, with commercial application prospect.

The battery containing bipolar electrode is provided in the present invention, the only one side in bipolar electrode coats positive electrode active material Matter, same the scribbling in the relative one side of positive active material of bipolar electrode does not have negative electrode active material before battery first charge-discharge Material, the active ion of negative pole is present in aqueous electrolyte, when being charged to battery, is deposited on bipolar electrode uncoated The one side of positive active material, battery has excellent cycle performance.Meanwhile, battery uses aqueous electrolyte, relative to Using the lithium ion battery of organic system electrolyte, the battery in the present invention is more safe and environment-friendly.In addition, it is double by setting The number of polar electric pole can be prepared with different output voltages, the battery with high output voltage, battery use extensively and Preparation process is simple, battery has commercial applications potentiality.

【Plank frame battery】

Present invention also offers a kind of battery, battery has plank frame.

Implementation method eight

As shown in figure 17, a kind of battery 140, battery 140 includes housing 70, positive pole 72, negative pole 74 in housing 70, Barrier film 76 and aqueous electrolyte 78.And barrier film 76 is arranged between positive pole 72 and negative pole 74.

Positive pole 72 includes plus plate current-collecting body 80 and participates in the positive active material 82 of electrochemical reaction, positive active material 82 Including can it is reversible deviate from-compound of embedded ion；Negative pole 74 is selected from metal, alloy or carbon-based material；Aqueous electrolyte 78 Including electrolyte, electrolyte can at least ionize out active ion, and active ion is reduced when charging and is deposited on the shape of negative pole 74 Into negative electrode active material, negative electrode active material is oxidized in being dissolved in aqueous electrolyte 78 in electric discharge.

Positive pole 72, negative pole 74, aqueous electrolyte 78 and barrier film 76 are just not repeated to introduce here with implementation method one.

Positive pole 72, barrier film 76 and negative pole 74 form tabular, and barrier film 76 is located between positive pole 72 and negative pole 74.Accordingly , housing 70 is set to square.So as to battery may be designed as rectangular cell, such as cuboid or square.Battery structure letter Single, convenient manufacture, cost are simple.

Battery 140 is designed as stacked.The stacking arrangement of positive pole 72, barrier film 76 and negative pole 74 forms tabular, and barrier film 76 Between positive pole 72 and negative pole 74.Accordingly, housing 70 is also configured as square.

Specific in Figure 17, positive pole 72 is set to 4, and negative pole 74 is set to 5, is negative pole 74 near housing 70.

Battery may also be configured to include some independent battery units, independent battery unit include independent positive pole, every Film and negative pole.Wherein battery unit is connected with parallel way.Independent battery unit may be configured as 2~10 groups.Certainly, also can root Independent battery unit is arranged to different groups of numbers, such as 12 groups or more according to different needs.In addition, independent battery unit Can connect in a series arrangement as needed.

Housing 70 may be configured as the composite membrane of metal, plastics or metal and plastics, such as steel, aluminium, acrylonitrile-butadiene-benzene Ethylene copolymer (ABS), polypropylene (PP), nylon or aluminum plastic film etc..Preferably, housing 70 is set to aluminum plastic film, so that Housing is relatively thin.While reducing battery weight, the space of inside battery is also increased.Aluminum plastic film includes one layer of aluminium flake and ground floor Plastic sheet.Preferably, aluminum plastic film also includes being arranged at relative to ground floor plastic sheet the second layer plastics of above-mentioned aluminium flake opposite side Piece.

Battery also includes the lid 84 being connected with housing 70, and the extension of plus plate current-collecting body 80 passes lid 84, anode collection The end that the extension of body 80 passes lid 84 is provided with seal cap 86.Seal cap 86 is needed with preferable electric conductivity and chemically stable Property.In addition, seal cap 86 can also prevent the hole that aqueous electrolyte 78 is passed from plus plate current-collecting body 80 from evaporating, so as to reduce water system electricity Solve the consumption of liquid 78.Positive pole 72 is connected with external circuit.

Negative pole 74 also extends and passes lid 84, so as to be connected with external circuit.Equally, negative pole 74 extends the end for passing lid 24 Portion is provided with seal cap (not shown).

In addition, battery is in charging process, especially it is fast close to charge the later stage when, because charging current is by water decomposition, meeting Discharge a large amount of hydrogen, carrier of oxygen.As the hydrogen and oxygen that produce are more and more, the pressure in battery container is also on constantly Rise, when pressure rises to certain value, battery container can deform.Therefore, battery is also included for controlling pressure in housing 70 Safety valve 88.When the pressure in the housing 70 of battery reaches default valve opening presses, safety valve 88 is opened, and pressure is discharged, Housing distortion is prevented, so as to improve life-span and the security of battery.

In addition, when the pressure in housing 70 reaches default valve closing and presses, safety valve 88 is closed, and prevents internal gas outside Leakage.Meanwhile, it is also prevented from extraneous air and is had undesirable effect into housing 70 is interior.And the hydrogen for being also prevented from separating out meets naked light When produce tempering, so as to ignite the internal gas of housing 70.

The fluid infusion (not shown) for supplementing aqueous electrolyte 78 is also provided with housing 70.So, when water system electricity When solution liquid 78 is less, aqueous electrolyte 78 can be injected by fluid infusion.

Preferably, fluid infusion is to install the mounting hole (not shown) at safety valve 88.

Refer to shown in Figure 18 and 19, battery is stacked.Specifically, banded structure of the barrier film 76 for monoblock type, and every Film 76 is folded with Z-shaped.Positive pole 72 and the stacking of negative pole 74 are arranged at the lap seam of barrier film 76.Now, barrier film 76 is located at positive pole 72 And negative pole 74 between, so that insulated from each other between positive pole 72 and negative pole 74.

Positive pole 72, barrier film 76 and negative pole 74 are equally pressed into square plate shape.Accordingly, the side of being also configured as of housing 70 Shape, such as cuboid or square, so that, battery may be designed as rectangular cell.

Refer to shown in 20, battery is takeup type, battery includes positive pole 72, negative pole 74 and barrier film 76.Positive pole 72, barrier film 76 With the winding shaping of negative pole 74, so as to form tabular battery core, and barrier film 76 is located between positive pole 72 and negative pole 74.Accordingly, shell Body 70 be also configured as it is square, such as cuboid or square so that, the battery in the present embodiment may be designed as rectangular cell.

Preferably, positive pole 72, barrier film 76 and negative pole 74 are disposed as strip.Different circles can be as needed wound into Number.

Specifically, tabular battery core includes two relative planes 90, above-mentioned two plane 90 and two arcs being oppositely arranged are connected Shape portion 92.Positive pole winds the curved portions 92 of at least one of clearing end 94 and negative pole winding clearing end 96 positioned at tabular battery core Place.

Preferably, positive pole winding clearing end 94 and negative pole winding clearing end 96 are located at what tabular battery core was oppositely arranged respectively At two curved portions 92.

Preferably, positive pole winding clearing end 94 and negative pole winding clearing end 96 are located at the same curved portions 92 of tabular battery core Place.

When battery is in charge and discharge process, pole piece thickness can expand, so as to cause tabular battery core integral thickness to increase.And Positive pole is wound clearing end 94 and negative pole winding clearing end 96 is arranged at curved portions 92, due between curved portions 92 and housing 70 Space is left, the space serves cushioning effect for the expansion of tabular battery core.So that will not be produced at curved portions 92 Larger stress concentration, and then avoid and occur obvious fold at curved portions 92, effectively reduce reversible abjection-insertion from The crystallization of son.

In Figure 20, the method for winding of tabular battery core is, since inner ring, barrier film 76 is wound as two-layer, and two-layer barrier film 76 is bonded to each other, according to design requirement, the second circle is wound again after two-layer barrier film 76 fits certain length, is now opened from inner ring Begin, be followed successively by two-layer barrier film 76, negative pole 74 is wound up into the barrier film 76 of the second circle, and positive pole 72 is wound up into the barrier film 76 of the second circle, Then proceed to wind negative pole 74, barrier film 76, positive pole 72, barrier film 76 to the designed number of turns.Certainly, such as people in the art Member is known, also other method for winding, as long as ensureing positive pole and negative insulation.

A kind of battery that the present invention is provided, power density (up to the 60%-80% of lithium ion battery) high with energy density (it is expected to reach the 200% of lithium ion battery, even more high) greatly, it is easy to manufacture, totally nontoxic, environmental protection, easily reclaims and low cost Honest and clean (battery of same capacity, it is expected to reach the 60% of lead-acid battery, the 20% of lithium ion battery, even lower) the features such as, and With good cycle performance, in a specific embodiment, battery capacity after circulating 4000 weeks is still maintained at more than 90%.Cause This, the present invention in battery as a new generation green energy resource, be highly suitable as large-scale energy storage field energy storage system and The substitute of lead-acid battery.

【Pole structure battery】

Present invention also offers a kind of battery, battery has column type structure.

Implementation method nine

A kind of battery, battery includes housing, and positive pole, negative pole, barrier film and aqueous electrolyte in housing, barrier film are set Between positive pole and negative pole.

Positive pole includes plus plate current-collecting body and participates in the positive active material of electrochemical reaction, and positive active material includes can The compound of reversible abjection-embedded ion；Negative pole is selected from metal, alloy or carbon-based material；Aqueous electrolyte includes electrolyte, electricity Solution matter can at least ionize out active ion, and active ion is reduced when charging and is deposited on negative pole formation negative electrode active material, Negative electrode active material is oxidized in being dissolved in aqueous electrolyte in electric discharge.

Plus plate current-collecting body, positive active material, negative pole, aqueous electrolyte and barrier film with implementation method one, here just no longer Repeat one by one.

Likewise, the setting of negative pole includes negative current collector with implementation method one, i.e. negative pole, now negative pole can only conduct Electronics is collected and the matrix of conduction is not involved in electrode reaction；Or negative pole includes negative current collector and negative electrode active material, such as negative pole It is filtter gold and zinc paper tinsel, zinc paper tinsel is consistent with negative electrode active material.

Housing is set to cylinder barrel shaped, positive pole, barrier film, negative pole and housing arranged in co-axial alignment.

Specifically, the positive pole, barrier film and negative pole in battery can be arranged in housing by winding the cylindrical battery core of formation.

Refer to shown in Figure 21 and 22, the negative pole 160 and barrier film 156 of battery 150 are cylinder barrel shaped, plus plate current-collecting body 152 is cylinder, and positive active material 158 is arranged between barrier film 156 and plus plate current-collecting body 152.Battery 150 also includes fixing Ring 154, retainer ring 154 fixes plus plate current-collecting body 152, barrier film 156, negative pole 160 and housing (not shown).Retainer ring 154 Material is polyvinyl chloride, and retainer ring 154 is two, is respectively arranged at the two ends of housing.Retainer ring 154 includes the He of upper strata ring 162 Lower floor's ring 164, upper strata ring 162 and lower floor's ring 164 are formed in one, and upper strata ring 162 fixes plus plate current-collecting body 152 and barrier film 156, Lower floor's ring 164 fixes barrier film 156 and negative pole 160.The external diameter of upper strata ring 162 is identical with the internal diameter of negative pole 160, upper strata ring 162 Internal diameter is identical with the diameter of plus plate current-collecting body 152；The external diameter of lower floor's ring 164 is identical with the internal diameter of barrier film 156, lower floor's ring 164 Internal diameter is identical with the diameter of plus plate current-collecting body 152.

In implementation method of the plus plate current-collecting body 152 for cylinder, specifically, as shown in Figure 21 and Figure 22：A kind of electricity Pond 150, including plus plate current-collecting body 152, positive active material 158, barrier film 156, negative pole 160, aqueous electrolyte (do not show in figure Go out), retainer ring 154 and housing；Plus plate current-collecting body 152 is same with positive active material 158, barrier film 156, negative pole 160 and housing Axle is arranged；Negative pole 160 and barrier film 156 are cylinder barrel shaped；Positive active material 158 is arranged at plus plate current-collecting body 152 and barrier film Between 156；Barrier film 156 is arranged between positive active material 158 and negative pole 160；Negative pole 160 is arranged at barrier film 156 and housing Between；Aqueous electrolyte is arranged in housing；Retainer ring 154 is arranged at one end of housing, and retainer ring 154 fixes plus plate current-collecting body 152 with barrier film 156 and negative pole 160；Preferably, plus plate current-collecting body 152 is graphite rod.

Specifically, the material of retainer ring 154 is polyvinyl chloride, retainer ring 154 is two, is respectively arranged at housing in battery Two ends, a top for being arranged at battery, another is arranged at the bottom of battery.As shown in Figure 22：Retainer ring 154 includes Upper strata ring 162 and lower floor's ring 164, upper strata ring 162 and lower floor's ring 164 are formed in one, and upper strata ring 162 fixes plus plate current-collecting body 152 fix barrier film 156 and negative pole 160 with barrier film 156, lower floor's ring 164.The internal diameter phase of the external diameter of upper strata ring 162 and negative pole 160 Together, the internal diameter of upper strata ring 162 is identical with the diameter of plus plate current-collecting body 152；The internal diameter phase of the external diameter of lower floor's ring 164 and barrier film 156 Together, the internal diameter of lower floor's ring 164 is identical with the diameter of plus plate current-collecting body 152.

Plus plate current-collecting body be cylinder implementation method in, battery also include positive conductive agent, positive conductive agent with just It is arranged at together between plus plate current-collecting body 152 and barrier film 156 after pole active material 158 is well mixed.Specifically, first by cylinder Plus plate current-collecting body 152, cylinder barrel shaped barrier film 156 and it is arranged at the retainer ring 154 of battery bottom and assembles, positive conductive agent, Positive active material 158 and solvent are mixed together and are formed uniformly anode sizing agent, then anode sizing agent is poured into barrier film 156 and positive pole collection In the gap of the composition of fluid 152, dry, i.e., positive conductive agent is formed between plus plate current-collecting body 152 and barrier film 156 and is lived with positive pole Property material 158.Positive conductive agent is selected from conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal powder One or more in end and sheet metal.Solvent is selected from deionized water or ethanol.

In the implementation method that plus plate current-collecting body is cylinder, the negative pole 160 of cylinder barrel shaped can be initially formed cylindrical drum The negative current collector of shape, by the negative current collector of the barrier film 156, cylinder barrel shaped of cylindrical plus plate current-collecting body 152, cylinder barrel shaped with And after being arranged at the fixation of the retainer ring of battery bottom, then the barrier film 156 and cylinder that negative electrode active material is added to cylinder barrel shaped Obtained between the negative current collector of tubular；It can also be the method shape that negative electrode active material is first passed through into coating, plating or sputtering Into the negative pole 160 for after on negative current collector, re-forming cylinder barrel shaped.

The battery that the present invention is provided, high with energy density, power density is big, it is easy to manufacture, safety non-toxic, environmental protection, holds Easily reclaim and it is with low cost the features such as, and battery has good cycle performance, therefore, the battery in the present invention is used as new one The green energy resource in generation, is highly suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery.

The unit in weight, percent by volume in the present invention is well-known to those skilled in the art, such as volume hundred Divide the weight than referring to the solute in 100 milliliters of solution.Unless otherwise defined, all specialties used in text are used with science Language is identical with meaning familiar to one skilled in the art institute.Additionally, any method similar to described content or impartial and material Material all can be applied in the inventive method.Preferable implementation described in text only presents a demonstration with material and is used.

With reference to embodiment, present disclosure is further illustrated.It should be appreciated that implementation of the invention is not limited to In the following examples.

Embodiment 1

By LiMn₂O₄(Hunan China fir China fir, LMO021 types), conductive black (TIMCAL, super P), bonding agent carboxymethyl cellulose Plain sodium (Si Bikai can, 30000) and water are according to mass ratio 90:6:1:50 ratio is well mixed, and adds 3 parts of SBR emulsions (South Korea great Jin), continues mixing 10min and is made active material slurry.Made with long 80 millimeters, wide 60 millimeters, thick 20 microns aluminium foil It is plus plate current-collecting body, aluminium foil is placed in the middle of 2 conducting films of 50 microns of thickness, conducting film size is more slightly larger than aluminium foil, by heating It is compound conducting film is coated on aluminium foil, and it is intact to ensure that conducting film has more part sealing than aluminium foil.Active material slurry is equal Even the first face and the second face for being coated in composite current collector, coating density is 700g/m², dried at 60 DEG C, on roll squeezer Apply 10 tons of pressure to roll, obtain positive pole.

Specifically, conducting film is the composite containing polypropylene and conductive black.

Barrier film is the AGM fibreglass diaphragms of 2 millimeters of thickness, and size is 70 × 70 millimeters.Negative pole is thick 50 microns zinc Plate, size is suitable with barrier film.Electrolyte is the ZnSO of 2mol/L₄With the Li of 1mol/L₂SO₄Mixed aqueous solution.

Battery is assembled in such a way：The positive pole that will be obtained is inserted between two negative poles, is respectively set between positive pole and negative pole A piece of barrier film is put, after being completed, 12 milliliters of electrolyte, static 3 hours is injected, you can start charge-discharge test.

Embodiment 2

In example 2, plus plate current-collecting body is Copper Foil, and remaining composition of battery and method of testing are with embodiment 1.

Embodiment 3

In embodiment 3, plus plate current-collecting body is stainless steel foil, and remaining composition of battery and method of testing are with embodiment 1.

Embodiment 4

In example 4, conductive film thickness is 100 microns, and remaining composition of battery and method of testing are with embodiment 1.

Battery performance test

Battery in embodiment 1 to 4 is carried out into charge and discharge cycles test at room temperature.The condition of charge and discharge cycles test For：To be charged to 2.1V under 0.25C constant currents, stop 10 minutes, then 1.4V is discharged under 1C constant currents, then stop 10 Minute, as a circulation.

Figure 23 be embodiment 1 in battery charging and discharging cycle performance figure, it can be seen that battery can normal work, And performance is highly stable over numerous cycles.Likewise, the work that the battery in embodiment 2 to 4 can continue, stablize.

Embodiment 5

By positive active material LiMn₂O₄, conductive agent acetylene black (AB), binding agent Kynoar (PVDF) is according to weight Than 80:10:10 mixing, using 1-METHYLPYRROLIDONE as solvent, make anode sizing agent, in the collector that thickness is 100 μm Simultaneously upper coating anode sizing agent, is put into vacuum drying chamber, and 0.5h is dried at 60 DEG C, and it is 400 μm bipolar to form thickness Property electrode.Collector uses conductive plastics, specifically, conductive plastics be containing polypropylene and conductive black composite.

The material of plus plate current-collecting body and negative extraction electrode is stainless steel foil, and the one side of plus plate current-collecting body is compounded in by hot pressing Cladding a layer thickness is 50 μm of conducting film, and conducting film is the composite membrane of polyethylene and carbon black, according to preparing bipolar electrode Process, the one side for scribbling conducting film in plus plate current-collecting body coats the positive active material of same thickness.Plus plate current-collecting body draws with negative The thickness for going out electrode is 2mm.

Aqueous electrolyte is to contain the aqueous solution that concentration is 1mol/L lithium sulfates and 2mol/L zinc sulfate；Barrier film uses glass Fiber (AGM), the encirclement area of the area less than rectangular seal of barrier film, the thickness of barrier film is 600 μm；Sealing is using height It is the rectangular seal of 1mm, the area of rectangular seal is slightly less than the area of extraction electrode and collector.

Be laminated rectangular seal on negative extraction electrode, then placed in the circle of sealing ring be soaked with aqueous electrolyte every Film, then bipolar electrode and positive extraction electrode are stacked gradually, bipolar electrode and positive extraction electrode scribble positive active material Simultaneously placed towards negative extraction electrode, sealing ring is used to being sealingly disposed in positive extraction electrode and adjacent bipolar electrode and bipolar Aqueous electrolyte of the property between electrode and adjacent negative extraction electrode.

Battery performance test

Battery in embodiment 5 is carried out into charge and discharge cycles test at room temperature.Charge and discharge cycles test condition be： 4.2V is charged under 1C constant currents, stops 10 minutes, then 2.8V is discharged under 1C constant currents, then stop 10 minutes, made It is a circulation.

Embodiment 6

In embodiment 6, the number of bipolar electrode is 3, and remaining composition of battery and preparation method are with embodiment 5.

Battery performance test

Battery in embodiment 6 is carried out into charge and discharge cycles test at room temperature.Charge and discharge cycles test condition be： 8.4V is charged under 1C constant currents, stops 10 minutes, then 5.6V is discharged under 1C constant currents, then stop 10 minutes, made It is a circulation.

Embodiment 7

In embodiment 7, the number of bipolar electrode is 5, and remaining composition of battery and preparation method are with embodiment 5.

Battery performance test

Battery in embodiment 7 is carried out into charge and discharge cycles test at room temperature.Charge and discharge cycles test condition be： 12.6V is charged under 1C constant currents, stops 10 minutes, then 8.4V is discharged under 1C constant currents, then stop 10 minutes, made It is a circulation.

Embodiment 8

In embodiment 8, the collector of bipolar electrode uses stainless steel, and thickness is 50 μm, battery remaining constitute, prepare Method and battery performance test are with embodiment 5.

Embodiment 9

In embodiment 9, the one side of plus plate current-collecting body does not have a coated with conductive film, battery remaining constitute, preparation method and Battery performance test is with embodiment 5.

Table 1 is the battery discharge and recharge under 1C multiplying powers in embodiment 5 to 9, the battery performance that charge and discharge cycles are 100 times：

Table 1

Embodiment 10

By positive active material LiMn₂O₄, super-p carbon blacks, bonding agent PVDF is according to part by weight 8:1:1 is well mixed, Using NMP as solvent, anode sizing agent is obtained, is coated uniformly in the plus plate current-collecting body graphite foil of 80 μm of thickness, be subsequently dried, press Positive pole is obtained；Negative pole includes the graphite foil of 50 μm of zinc paper tinsel and thickness, and metallic zinc is plated in graphite foil as negative electrode active material； Barrier film is glass felt-cloth.

Gained positive pole, barrier film and negative pole are formed into cylindrical battery core by winding, is arranged in the housing of cylinder barrel shaped；Electricity The electrolyte added in pond is the aqueous solution containing 2mol/L lithium acetates and 1.5mol/L zinc acetates, is added dropwise by electrolyte The pH of the LiOH solution regulation electrolyte of 0.1mol/L is 4.At room temperature, after battery standing 12h, charged with the electric current of 100mA and Electric discharge, voltage range is 1.5-2.35V.

Embodiment 11

Mode same as in Example 10 manufactures battery, except that：Replace real with the 316 type stainless steels through transpassivation Apply the graphite foil in the negative pole of example 10.

Embodiment 12

Mode same as in Example 10 manufactures battery, except that：Replace the stone in the negative pole of embodiment 10 with Copper Foil Black paper tinsel.

Embodiment 13

A kind of battery, plus plate current-collecting body is graphite rod, and a diameter of 4mm, length is 62mm；The material of barrier film is non-woven fabrics, Barrier film is cylinder barrel shaped, and the external diameter of barrier film is 11mm, and the internal diameter of barrier film is 10mm, and the length of barrier film is 58mm；Negative pole includes copper Paper tinsel and zinc, zinc are formed on Copper Foil by sputtering, obtain cylinder barrel shaped negative pole, and the external diameter of negative pole is 17mm, and the internal diameter of negative pole is 16mm, the length of negative pole is 58mm, and negative pole is provided with the thick copper polar ears of 0.1mm, draws battery；The material of housing is polyvinyl chloride (PVC), the internal diameter of housing is 17mm, and the external diameter of housing is 18mm, and the length of housing is 60mm；The material of retainer ring is polychlorostyrene second Alkene (PVC), retainer ring has two, is respectively arranged at the two ends of battery, and be placed in cell top end is the first retainer ring, as battery Bottom is the second retainer ring, and retainer ring includes upper strata ring and lower floor's ring, and upper strata ring and lower floor's ring are formed in one, upper strata ring Internal diameter is 4mm, and the external diameter of upper strata ring is 10mm, and the thickness of upper strata ring is 3mm, and the internal diameter of lower floor's ring is 4mm, the external diameter of lower floor's ring It is 16mm, the thickness of lower floor's ring is 1mm.

Specifically the assembling process of battery is：With LiMn₂O₄It is positive active material, by positive active material, conductive agent Super-P, according to 90:10 part by weight mixing in deionized water, is well mixed prepared anode sizing agent；First by barrier film and After two retainer rings and graphite rod are assembled, anode sizing agent is poured into the gap that barrier film is formed with graphite rod, pour into positive pole slurry Doses is 10g, is dried at 80 DEG C, obtains positive pole, and positive active material and the mixture of conductive agent are 5g in barrier film；Again in circle Cylinder barrel shaped negative pole is set outside tubular barrier film, cylinder barrel shaped housing is set outside cylinder barrel shaped negative pole；Electrolyte is 544g chlorinations Zinc and 21g anhydrous Lithium chlorides, are dissolved in 600g deionized waters, then toward titrating 0.1mol/L lithium hydroxides by electrolyte in electrolyte PH value is adjusted to 4.3, then is settled to 1L with deionized water and obtains, and the 5g electrolyte is added in the battery of the present embodiment.By barrier film, After two retainer rings, graphite rod, positive pole, negative pole, housing and electrolyte are assembled, 12 hours are stood, then begun to 100mA's Electric current charging and discharging, it is 1.5-2.35V that charging/discharging voltage is interval.

Embodiment 14

A kind of battery, plus plate current-collecting body is graphite rod, and a diameter of 4mm, length is 62mm；The material of barrier film is non-woven fabrics, Barrier film is cylinder barrel shaped, and the external diameter of barrier film 3 is 11mm, and the internal diameter of barrier film is 10mm, and the length of barrier film is 58mm；Negative pole includes copper Paper tinsel and zinc, the external diameter of negative pole is 17mm, and the internal diameter of negative pole is 16mm, and the length of negative pole is 58mm, and negative pole is provided with 0.1mm thickness Copper polar ear, draws battery；The material of housing is polyvinyl chloride (PVC), and the internal diameter of housing is 17mm, and the external diameter of housing is 18mm, The length of housing is 60mm；The material of retainer ring is polyvinyl chloride (PVC), and retainer ring has two, is respectively arranged at the two of battery End, be placed in cell top end is the first retainer ring, is the second retainer ring as battery bottom, and retainer ring includes upper strata ring with Layer ring, upper strata ring and lower floor's ring are formed in one, and the internal diameter of upper strata ring is 4mm, and the external diameter of upper strata ring is 10mm, the thickness of upper strata ring It is 3mm to spend, and the internal diameter of lower floor's ring is 4mm, and the external diameter of lower floor's ring is 16mm, and the thickness of lower floor's ring is 1mm.

Specifically the assembling process of battery is：With LiMn₂O₄It is positive active material, by positive active material 22, conductive agent Super-P, according to 90:10 part by weight mixing in deionized water, is well mixed prepared anode sizing agent；First by barrier film and After two retainer rings and graphite rod are assembled, anode sizing agent is poured into barrier film, anode sizing agent amount is poured into for 12g, at 80 DEG C Dry, obtain positive pole, positive active material and the mixture of conductive agent are 6g in barrier film；By the Copper Foil and graphite of cylinder barrel shaped After rod, the barrier film of cylinder barrel shaped and second retainer ring are fixed, then the barrier film and cylindrical drum that zinc is added to cylinder barrel shaped Cylinder barrel shaped negative pole is obtained between the Copper Foil of shape；Electrolyte is 544g zinc chloride and 21g anhydrous Lithium chlorides, is dissolved in 600g deionizations Water, then the pH value of electrolyte is adjusted to 4.3 toward titration 0.1mol/L lithium hydroxides in electrolyte, then it is settled to 1L with deionized water Obtain, the 6g electrolyte is added in the battery of the present embodiment.By barrier film, the second retainer ring, graphite rod, positive pole, negative pole, housing with And after electrolyte is assembled, 12 hours are stood, and then beginning to the electric current charging and discharging of 100mA, charging/discharging voltage interval is 1.5-2.35V。

Embodiment 15

Battery is manufactured with the identical mode of embodiment 13, except that：Replace the Copper Foil in negative pole with graphite foil.

Battery provided in embodiment 10 to 15, battery has good cycle performance.

Although inventor has done elaboration in greater detail and has enumerated to technical scheme, it will be appreciated that for For those skilled in the art, above-described embodiment is modified and/or flexible or be obvious using equivalent alternative solution , can not all depart from the essence of spirit of the present invention, the term occurred in the present invention be used for the elaboration of technical solution of the present invention and Understand, can not be construed as limiting the invention.

Claims

1. a kind of battery, including housing, is arranged at positive pole, two negative poles, aqueous electrolyte and barrier films in the housing,

The positive pole includes composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body and is coated on Conducting film on the plus plate current-collecting body, the material of the conducting film includes polymer and conductive filler, and the polymer is accounted for leads The weight proportion of electrolemma is 50-95%, and the composite current collector has the first face and the second face being oppositely arranged, and the positive pole is lived Property material is arranged on first face and the second face, the positive active material can it is reversible deviate from-embedded ion；

The negative pole is selected from metal, alloy or carbon-based material；

The aqueous electrolyte includes electrolyte, and the electrolyte can at least ionize out active ion, and the active ion exists It is reduced during charging and is deposited on the negative pole formation negative electrode active material, the negative electrode active material is oxidized dissolving in electric discharge In the aqueous electrolyte；

The barrier film keeps the aqueous electrolyte；

The positive pole and negative pole stacking are arranged in the housing, and the positive pole is placed between described two negative poles, described two Negative pole shares the positive pole, and the barrier film is located between the positive pole and negative pole.

2. a kind of battery, including housing, is arranged at two positive poles, negative pole, aqueous electrolyte and barrier films in the housing,

The positive pole includes composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body and is coated on Conducting film on the plus plate current-collecting body, the material of the conducting film includes polymer and conductive filler, and the polymer is accounted for leads The weight proportion of electrolemma is 50-95%, and the composite current collector has the first face and the second face being oppositely arranged, first face It is relative with the negative pole, the positive active material is provided with least described first face, the positive active material can Inverse abjection-embedded ion；

The negative pole is selected from metal, alloy or carbon-based material；

The barrier film keeps the aqueous electrolyte；

The positive pole and negative pole stacking are arranged in the housing, and the negative pole is placed between described two positive poles, described two Positive pole shares the negative pole, and the barrier film is located between the positive pole and negative pole.

3. a kind of battery, including housing, is arranged at positive pole in the housing, negative pole, aqueous electrolyte and barrier film,

The positive pole includes composite current collector and positive active material, and the composite current collector includes plus plate current-collecting body and is coated on Conducting film on the plus plate current-collecting body, the material of the conducting film includes polymer and conductive filler, and the polymer is accounted for leads The weight proportion of electrolemma is 50-95%, and the composite current collector has the two sides being oppositely arranged, wherein, at least described Composite Set Be provided with positive active material in the fluid one side relative with the negative pole, the positive active material can it is reversible deviate from-it is embedding Enter ion；

The battery includes n to the positive pole and negative pole, and n >=2, two adjacent positive poles share negative between two positive poles Pole, two adjacent negative poles share the positive pole between two negative poles；

The negative pole is selected from metal, alloy or carbon-based material；

The barrier film keeps the aqueous electrolyte；

In the housing, the barrier film is located between the positive pole and negative pole the alternate stacked arrangement of the positive pole, negative pole.

4. the battery according to any one in claim 1-3, it is characterised in that：The housing is square.

5. battery according to claim 4, it is characterised in that：The positive pole, barrier film and negative pole form tabular.

6. battery according to claim 5, it is characterised in that：The positive pole, barrier film and negative pole winding shaping.

7. the battery according to any one in claim 1-3, it is characterised in that：The housing is cylinder barrel shaped, described Positive pole, the barrier film, the negative pole and the housing arranged in co-axial alignment.

8. battery according to claim 7, it is characterised in that：The positive pole, barrier film and negative pole form cylinder by winding Shape is arranged in the housing.

9. the battery according to any one in claim 1-3, it is characterised in that：The polymer is selected from polyethylene, gathers Propylene, polybutene, polyvinyl chloride, polystyrene, polyamide, makrolon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, Polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.

10. the battery according to any one in claim 1-3, it is characterised in that：The conductive filler is selected from conductive poly- Compound, carbon-based material or metal oxide.

11. battery according to any one in claim 1-3, it is characterised in that：The material of the conducting film is selected from and leads Electric polymer.

12. battery according to any one in claim 1-3, it is characterised in that：The housing is set to aluminum plastic film.

13. battery according to any one in claim 1-3, it is characterised in that：The housing is provided with fluid infusion, institute Fluid infusion is stated for supplementing the aqueous electrolyte.

14. battery according to any one in claim 1-3, it is characterised in that：The battery is also included for controlling The safety valve of pressure in the housing.

15. battery according to any one in claim 1-3, it is characterised in that：The positive active material has point Spinel structure, layer structure or olivine structural.

16. battery according to any one in claim 1-3, it is characterised in that：The material choosing of the plus plate current-collecting body One kind from vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or by the one kind in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloys, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-Rh alloys or by the one kind in the above-mentioned alloy of Passivation Treatment.

17. battery according to any one in claim 1-3, it is characterised in that：The material of the negative pole is selected from metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or by least one in the metal of Passivation Treatment, or contain above-mentioned metal At least one at least one in alloy, or graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is tin plating, or yellow Copper.

18. battery according to any one in claim 1-3, it is characterised in that：The active ion include metal from Son, metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.

19. battery according to any one in claim 1-3, it is characterised in that：The active ion is with hydrochloride, sulphur At least one form in hydrochlorate, acetate, nitrate or formates is present in the aqueous electrolyte.