CN103682476A - Battery - Google Patents

Battery Download PDF

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Publication number
CN103682476A
CN103682476A CN201310381682.0A CN201310381682A CN103682476A CN 103682476 A CN103682476 A CN 103682476A CN 201310381682 A CN201310381682 A CN 201310381682A CN 103682476 A CN103682476 A CN 103682476A
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CN
China
Prior art keywords
battery
positive
negative pole
negative
active material
Prior art date
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Granted
Application number
CN201310381682.0A
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Chinese (zh)
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CN103682476B (en
Inventor
颜竞
刘洋
陈璞
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Positec Power Tools Suzhou Co Ltd
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Positec Power Tools Suzhou Co Ltd
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Priority to CN201310381682.0A priority Critical patent/CN103682476B/en
Priority to CN201710381918.9A priority patent/CN107293811B/en
Priority to CN201710395324.3A priority patent/CN107093773B/en
Publication of CN103682476A publication Critical patent/CN103682476A/en
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Publication of CN103682476B publication Critical patent/CN103682476B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a battery which comprises a shell, and positive electrodes, negative electrodes, aqueous electrolyte and a membrane which are arranged in the shell, wherein each positive electrode comprises a composite current collector and a positive active material; each composite current collector is provided with two opposite surfaces; at least one surface, opposite to the negative electrode, of each composite current collector is provided with the positive active material; the battery comprises n pairs of positive electrodes and negative electrodes, n is larger than or equal to 2; the adjacent two positive electrodes share two negative electrodes between two positive electrodes; the adjacent two negative electrodes share two positive electrodes between two negative electrodes; the positive and negative electrodes are alternately stacked and arranged in the shell. The battery provided by the invention has an excellent cycle performance and relatively high energy, the battery is expected to be widely applied to the fields such as accumulation energy in large scale and power grid pitch peak.

Description

Battery
Technical field
The invention belongs to electrochemical energy storage field, be specifically related to a kind of battery.
Background technology
The extensive utilization of the mankind to new forms of energy, has caused the expansion rapidly in secondary cell market.In current new forms of energy system to secondary cell require ubiquitous.No matter be electric automobile, wind energy, solar grid-connected or peak load regulation network, is all badly in need of a kind of cheapness, reliable, the secondary cell that safety and life-span are long.The secondary cell developing at present mainly concentrates on lithium ion battery, high temperature sodium-sulphur battery, sodium nickel chlorine battery and vanadium flow battery.These batteries all have advantages of separately, and such as lithium ion battery with high-temperature sodium sulphur battery life is long and energy density is high, vanadium flow battery possesses the unlimited life-span etc. especially in theory.But which kind of battery no matter, all cannot meet simultaneously cheap, reliable, the requirement that safety and life-span are long.Traditional lithium ion battery is too expensive, and has potential safety hazard; High-temperature sodium sulphur battery manufacture technical threshold is high, fetch long price; The multinomial technical bottleneck of vanadium flow battery all fails to obtain breakthrough etc. at present.
Many researchers is all devoted to the research of aquo-lithium ion battery for this reason, wishes significantly reduce the cost of lithium ion battery and improve fail safe with this, and has proposed some with LiMn 2o 4for positive pole, the oxide of vanadium is LiV for example 3o 8on the battery that is electrolyte for negative pole, water, but the poor stability and the vanadium that because of this type of negative pole, in water, discharge and recharge have certain toxicity, thereby have limited the development of this type of battery.So far, the structure of the aquo-lithium ion secondary cell having proposed all fails to break away from the structure based on deviate from-embedding principle of lithium ion, such as there being the VO of report 2/ LiMn 2o 4, LiV 3o 8/ LiNi 0.81co 0.19o 2, TiP 2o 7/ LiMn 2o 4, LiTi 2(PO 4) 3/ LiMn 2o 4, LiV 3o 8/ LiCoO 2deng.
Summary of the invention
The present invention aims to provide a kind of simple in structure, low-cost, safe and reliable and battery that cycle life is longer.
The invention provides a kind of battery, comprise housing, be arranged at the positive pole in described housing, two negative poles, aqueous electrolyte and barrier films, described positive pole comprises composite current collector and positive active material, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described composite current collector has the first surface that is oppositely arranged and second, it is upper that described positive active material is arranged on described first surface and second, described positive active material can be reversible deviate from-embedded ion; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge; Described barrier film keeps described aqueous electrolyte; Described positive pole and negative pole are stacked to be arranged in described housing, and described positive pole is placed between described two negative poles, and described two negative poles share described positive pole, and described barrier film is between described positive pole and negative pole.
The present invention also provides a kind of battery, comprise housing, be arranged at two positive poles, negative pole, aqueous electrolyte and barrier films in described housing, described positive pole comprises composite current collector and positive active material, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described composite current collector has the first surface that is oppositely arranged and second, described first surface is relative with described negative pole, on at least described first surface, be provided with described positive active material, described positive active material can be reversible deviate from-embedded ion; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge; Described barrier film keeps described aqueous electrolyte; Described positive pole and negative pole are stacked to be arranged in described housing, and described negative pole is placed between described two positive poles, and described two positive poles share described negative pole, and described barrier film is between described positive pole and negative pole.
The present invention also provides a kind of battery, comprise housing, be arranged at positive pole, negative pole, aqueous electrolyte and barrier film in described housing, described positive pole comprises composite current collector and positive active material, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described composite current collector has the two sides being oppositely arranged, wherein, in at least described composite current collector one side relative with described negative pole, be provided with positive active material, described positive active material can be reversible deviate from-embedded ion; Described battery comprises that n is to described positive pole and negative pole, n >=2, and two adjacent positive poles share the negative pole between two positive poles, and two adjacent negative poles share the positive pole between two negative poles; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge; Described barrier film keeps described aqueous electrolyte; The stacked arrangement that described positive pole, negative pole replace is in described housing, and described barrier film is between described positive pole and negative pole.
Battery provided by the invention can well solve self discharge problem, battery-operated safety, production method is simple, cycle performance is good and the life-span is permanent, can according to user demand setting, have the battery of different output discharge capacities, battery tool has been widely used simultaneously.
Preferably, described housing is square.
Preferably, described positive pole, barrier film and negative pole form tabular.
Preferably, described positive pole, barrier film and negative pole winding shaping.
Preferably, described housing is cylinder barrel shaped, described positive pole, described barrier film and described negative pole and described housing arranged in co-axial alignment.
Preferably, described positive pole, described barrier film and described negative pole form cylindrical being arranged in described housing by coiling.
Preferably, the material of described conducting film comprises polymer and conductive filler.
Preferably, described polymer is selected from polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.
Preferably, described conductive filler is selected from conducting polymer, carbon-based material or metal oxide.
Preferably, the material of described conducting film is selected from conducting polymer.
Preferably, described housing is set to aluminum plastic film.
Preferably, described housing is provided with fluid infusion mouth, and described fluid infusion mouth is for supplementing described aqueous electrolyte.
Preferably, described battery also comprises for controlling the safety valve of described housing internal pressure.
Preferably, described positive active material has spinel structure, layer structure or olivine structural.
Preferably, the material of described plus plate current-collecting body is selected from a kind of in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a kind of through in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or a kind of through in the above-mentioned alloy of Passivation Treatment.
Preferably, the material of described negative pole is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process described metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
Preferably, described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Preferably, described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
The present invention also provides a kind of battery, comprise housing, be located at positive extraction electrode, at least one bipolar electrode, negative extraction electrode and aqueous electrolyte in described housing, described positive extraction electrode comprises plus plate current-collecting body and is arranged on the positive active material of described plus plate current-collecting body one side, described positive active material can be reversible deviate from-embedded ion; Described bipolar electrode is arranged between described positive extraction electrode and negative extraction electrode, described bipolar electrode comprises bipolarity collector and described positive active material, described bipolarity collector has the first surface that is oppositely arranged and second, and described positive active material is arranged on the first surface of described bipolarity collector; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced second the formation negative electrode active material that is deposited on described bipolarity collector when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge; Described negative extraction electrode is selected from metal, alloy or carbon-based material; Described aqueous electrolyte is arranged between described positive extraction electrode and negative extraction electrode; Described positive extraction electrode, bipolar electrode and negative extraction electrode are stacked to be arranged in described housing.
A kind of battery-operated safety provided by the invention, production method is simple, cycle performance is good and the life-span is permanent, can according to user demand setting, have the battery of different output voltages simultaneously, and battery tool has been widely used.
Preferably, described housing is set to square.
Preferably, described positive extraction electrode, described bipolar electrode and described negative extraction electrode form tabular.
Preferably, described battery also comprises barrier film, and described barrier film keeps described aqueous electrolyte.
Preferably, on described plus plate current-collecting body, be coated with conducting film.
Preferably, the peripheral part of described bipolarity collector is provided with for sealing the sealing of described aqueous electrolyte.
Preferably, the material of described bipolarity collector comprises the stainless steel of conductive plastics, stainless steel or process Passivation Treatment.
Preferably, the material of described conductive plastics is selected from conducting polymer.
Preferably, the material of described conductive plastics comprises polymer and conductive agent.
Preferably, described housing is set to aluminum plastic film.
Preferably, described housing is provided with fluid infusion mouth, and described fluid infusion mouth is for supplementing described electrolyte.
Preferably, described battery also comprises for controlling the safety valve of described housing internal pressure.
Preferably, described positive active material has spinel structure, layer structure or olivine structural.
Preferably, the material of described plus plate current-collecting body is selected from a kind of in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a kind of through in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or a kind of through in the above-mentioned alloy of Passivation Treatment.
Preferably, the material of described negative extraction electrode is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process described metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
Preferably, described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Preferably, described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
The present invention also provides a kind of battery, comprise housing, be located at positive pole, barrier film, negative pole and aqueous electrolyte in described housing, described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, described positive active material comprise can be reversible the compound of deviate from-embedded ion; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge; Described positive pole, described barrier film and described negative pole are stacked to be arranged in described housing, and described barrier film is between described positive pole and described negative pole.
Battery provided by the invention, battery structure is simple, handling safety, and production cost is low, has considerable useful life, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery.
Preferably, described housing is square.
Preferably, described positive pole, barrier film and negative pole form tabular.
Preferably, described positive pole, barrier film and negative pole winding shaping.
Preferably, described housing is aluminum plastic film.
Preferably, described housing is provided with fluid infusion mouth, and described fluid infusion mouth is for supplementing described aqueous electrolyte.
Preferably, described battery also comprises for controlling the safety valve of described housing internal pressure.
Preferably, described positive active material has spinel structure, layer structure or olivine structural.
Preferably, the material of described plus plate current-collecting body is selected from a kind of in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a kind of through in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or a kind of through in the above-mentioned alloy of Passivation Treatment.
Preferably, the material of described negative pole is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process described metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
Preferably, described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Preferably, described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
The present invention also provides battery, comprise housing, be located at positive pole, barrier film, negative pole and aqueous electrolyte in described housing, described positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, described positive active material comprise can be reversible the compound of deviate from-embedded ion; Described negative pole is selected from metal, alloy or carbon-based material; Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge; Described positive pole, described barrier film and described negative pole are stacked to be arranged in described housing, and described barrier film is between described positive pole and described negative pole.
Battery provided by the invention, has energy density high, safety non-toxic, and environmental protection, easily recovery and with low cost, the battery in the present invention, as green energy resource of new generation, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery very much.
Preferably, described housing is set to cylinder barrel shaped, described positive pole, barrier film and described negative pole and described housing arranged in co-axial alignment.
Preferably, described positive pole, barrier film and negative pole form cylindrical being arranged in described housing by coiling.
Preferably, described negative pole and described barrier film are cylinder barrel shaped, and described plus plate current-collecting body is cylindrical, and described positive active material is arranged between described barrier film and described plus plate current-collecting body.
Preferably, described battery also comprises retainer ring, and described retainer ring is fixed described plus plate current-collecting body, described barrier film, described negative pole and described housing; The material of described retainer ring is polyvinyl chloride, and described retainer ring is two, is arranged at respectively the two ends of described housing.
Preferably, described retainer ring comprises upper strata Huan He lower floor ring, and described upper strata ring and described lower floor ring are formed in one, the fixing described plus plate current-collecting body of described upper strata ring and described barrier film, the fixing described barrier film of described lower floor's ring and described negative pole.
Preferably, the external diameter of described upper strata ring is identical with the internal diameter of described negative pole, and the internal diameter of described upper strata ring is identical with the diameter of described plus plate current-collecting body; The external diameter of described lower floor ring is identical with the internal diameter of described barrier film, and the internal diameter of described lower floor ring is identical with the diameter of described plus plate current-collecting body.
Preferably, described housing is aluminum plastic film.
Preferably, described housing is provided with fluid infusion mouth, and described fluid infusion mouth is for supplementing described aqueous electrolyte.
Preferably, described battery also comprises for controlling the safety valve of described housing internal pressure.
Preferably, described positive active material has spinel structure, layer structure or olivine structural.
Preferably, the material of described plus plate current-collecting body is selected from a kind of in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a kind of through in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or a kind of through in the above-mentioned alloy of Passivation Treatment.
Preferably, the material of described negative pole is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process described metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
Preferably, described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Preferably, described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
Accompanying drawing explanation
Fig. 1 is the generalized section of the cell integrated structure that provides of execution mode one;
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, summary show battery unit;
Fig. 4 is the generalized section of the cell integrated structure that provides of execution mode two;
Fig. 5 is the generalized section of the cell integrated structure that provides of execution mode two, wherein, on the two sides that composite current collector is oppositely arranged, is provided with positive active material;
Fig. 6 is the generalized section of the cell integrated structure that provides of execution mode three, and wherein, battery comprises two pairs of positive poles and negative pole;
Fig. 7 is the generalized section of the battery core that provides of execution mode three, wherein, is positioned on the two sides that outermost anodal composite current collector is oppositely arranged and is provided with positive active material;
Fig. 8 is the generalized section of the cell integrated structure that provides of execution mode three, and wherein, logarithm anodal and negative pole is greater than 2;
Fig. 9 is the generalized section of the cell integrated structure that provides of execution mode four;
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, summary show battery unit;
Figure 12 is the charging principle schematic diagram of the battery that provides of execution mode four;
Figure 13 is the generalized section of the cell integrated structure that provides of execution mode five;
Figure 14 is battery structure schematic diagram in Figure 13, wherein, summary show battery unit;
Figure 15 is the generalized section of the cell integrated structure that provides of execution mode six;
Figure 16 is the generalized section of the cell integrated structure that provides of execution mode seven;
Figure 17 is the structural representation of the battery that provides of execution mode eight;
Figure 18 is the structural representation of the battery that provides of execution mode eight, and barrier film is folding 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 provides of execution mode eight, and wherein, battery winding is shaped;
Figure 21 is that the structure of battery in execution mode nine splits schematic diagram;
Figure 22 be in Figure 21 in the structural representation of retainer ring in battery;
The battery charging and discharging cycle performance figure that Figure 23 provides for embodiment 1.
Wherein:
1. battery 2,72. positive pole 4,74,160. negative poles
6,78. aqueous electrolyte 8. composite current collector 10,82. positive active materials
12,80,152. plus plate current-collecting body 14. conducting film 16,76,156. barrier films
20. battery unit 22,70. housing 24,84. lids
26,86. sealing cap 28,88. safety valve 81. first surfaces
82. second 30,40,50. battery 100. batteries
The positive extraction electrode 56. bipolarity collectors of 52. bipolar electrode 54.
61. 62. second of first surfaces, 58. negative extraction electrodes
60. sealing 64,68. battery unit 90. planes
110,120,130. battery 140,150. battery 92. curved portions
94. anodal coiling clearing end 96. negative pole coiling clearing end 154. retainer rings
164. lower floor's rings are encircled on 158. positive active material 162. upper stratas
Embodiment
Battery provided by the invention has higher energy density, stable cycle performance, and as portable type electronic products such as mobile phone, notebook computers, electric automobile, the fields such as electric tool have considerable application prospect.
[battery with internal parallel structure]
A battery, battery has internal parallel structure.Below in conjunction with accompanying drawing and embodiment, set forth the battery with internal parallel structure.
Execution mode one
Refer to shown in Fig. 1, a kind of battery 1, comprises housing 22, is arranged at positive pole in housing 22 2, two negative poles 4, aqueous electrolyte 6 and barrier films 16.Anodal 2 and negative pole 4 is stacked is arranged in housing 22, anodal 2 and is placed between two negative poles 4, it is anodal 2 that two negative poles 4 share, barrier film 16 anodal 2 and negative pole 4 between, barrier film 16 keeps aqueous electrolytes 6.
Housing 22 can be set to the composite membrane of metal, plastics or metal and plastics, as steel, aluminium, acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), nylon or aluminum plastic film etc.Preferably, housing 22 is set to aluminum plastic film, thereby makes housing thinner, when reducing battery weight, has also increased the space of inside battery.Aluminum plastic film comprises one deck aluminium flake and is arranged at the plastic sheet of aluminium flake one side.Preferably, aluminum plastic film comprises one deck aluminium flake and the ground floor plastic sheet and the second layer plastic sheet that are arranged at aluminium flake both sides.
Housing 22 can be set to square.
Concrete, the stacked formation tabular of arranging of order according to negative pole 4, barrier film 16, positive pole 2, barrier film 16 and negative pole 4, is placed in housing 22, as shown in Figure 1.Thereby battery 1 can be designed to rectangular cell, as cuboid or square.This battery structure is simple, convenience is manufactured, cost is simple.
In addition, according to the stacked formation tabular of arranging of order of negative pole 4, barrier film 16, anodal 2, barrier film 16 and negative pole 4, winding shaping then, thus form tabular battery core.Preferably, positive pole 2, barrier film 16 and negative pole 4 are all set to strip.According to battery design, need to be wound into the different number of turns.
Housing can also be set to cylinder barrel shaped (not shown).
Concrete, the stacked formation tabular of arranging of order according to negative pole 4, barrier film 16, positive pole 2, barrier film 16 and negative pole 4, then forms cylindrical battery core by coiling and is arranged in housing, positive pole 2, barrier film 16, negative pole 4 and housing arranged in co-axial alignment.Thereby battery can be designed to cylindrical battery, battery structure is simple, convenient manufacture.
In execution mode one, battery also comprises the lid 24 being connected with housing 22, and anodal 2 extensions pass lid 24, and the end that anodal 2 extensions pass lid 24 is provided with sealing cap 26.Sealing cap 26 need to have good conductivity and chemical stability.In addition, sealing cap 26 also can prevent that aqueous electrolyte is from the anodal 2 hole evaporations that pass, thereby reduces the consumption of aqueous electrolyte 6.Anodal 2 are connected with external circuit.
Negative pole 4 also extends and passes lid 24, thereby is connected with external circuit.Equally, negative pole 4 extends the end that passes lid 24 and is provided with sealing cap (not shown).
In addition, battery 1 is in charging process, and especially fast approaching while charging the later stage, due to the decomposition of aqueous electrolyte 6, can produce hydrogen, carrier of oxygen, and the pressure in battery container also can rise, and when pressure rise is to certain value, battery container 22 can deform.Therefore, battery 1 also comprises for controlling the safety valve 28 of housing 22 internal pressures.Pressure in the housing 22 of battery arrives default when driving valve and pressing, and safety valve 28 is opened, and by earth pressure release, prevents housing 22 distortion, thus the life-span and the fail safe that have improved battery 1.
In addition, pressure in housing 22 arrives default when closing valve and pressing, and safety valve 28 closures, prevent that internal gas is to outward leakage.Meanwhile, also preventing that extraneous air from entering in housing 22 causes harmful effect.And can also prevent that the hydrogen of separating out from producing tempering while meeting naked light, thereby ignite housing 22 internal gas.
On housing 22, also can be provided with for supplementing the fluid infusion mouth (not shown) of aqueous electrolyte 6.Like this, when aqueous electrolyte consumes, can inject electrolyte by fluid infusion mouth.
Preferably, fluid infusion mouth is the installing hole (not shown) at mounting safety valve 28 places.
Anodal 2 are arranged between two negative poles 4, between positive pole 2 and negative pole 4, be provided with aqueous electrolyte 6, anodal 2 comprise composite current collector 8 and positive active material 10, composite current collector 8 has the first surface 81 that is oppositely arranged and second 82, positive active material 10 is arranged on first surface 81 and second 82, as shown in Figure 2.
Anodal 2 production method is not particularly limited, and positive active material 10 can be that the mode by applying is attached on composite current collector 8, for example, positive active material 10 is made to slurry, then by slurry method, is coated on composite current collector 8; Can also positive active material 10 be attached on composite current collector 8 by stacked mode, for example will suppress by the composite current collector of pre-sizing moulding 8 and positive active material 10, make to electrically contact well between positive active material 10 and composite current collector 8, form anodal 2.The coating density range of positive active material 10 is 100-1000g/m 2.
Concrete, positive active material 10 has spinel structure, layer structure or olivine structural.
Concrete, lithium ion, sodium ion or magnesium ion can reversiblely be deviate from-embed to positive active material 10.
Positive active material 10 can be to meet general formula Li 1+xmn ym zo kcan the reversible compound of deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, Ni.Preferably, positive active material contains LiMn 2o 4.Preferred, positive active material contains the LiMn through overdoping or coated modification 2o 4.
Positive active material 10 can be to meet general formula Li 1+xm ym ' zm " co 2+ncan the reversible compound of deviating from-embed the layer structure of lithium ion, wherein,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " be selected from respectively Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al at least one.Preferably, positive active material contains LiCoO 2.
Positive active material 10 can be to meet general formula Li xm 1-ym ' y(XO 4) ncan the reversible compound of deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' be selected from Mg, Ti, Cr, V or Al at least one, X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO 4.
At present in Lithium Battery Industry, nearly all positive active material all can be through overdoping, the modification such as coated.But doping, it is complicated that the means such as coated modification cause the chemical general formula of material to express, as LiMn 2o 4can not represent the general formula of now widely used " LiMn2O4 ", and should be with general formula Li 1+xmn ym zo kbe as the criterion, comprise widely the LiMn through various modifications 2o 4positive active material.Same, LiFePO 4and LiCoO 2also should be interpreted as widely to comprise through various doping, the modification such as coated, general formula meets respectively Li xm 1-ym ' y(XO 4) nand Li 1+xm ym ' zm " co 2+npositive active material.
When compound is deviate from-embedded to positive active material 10 for lithium ion, can select as LiMn 2o 4, LiFePO 4, LiCoO 2, LiM xpO 4, LiM xsiO ycompounds such as (wherein M are a kind of variable valency metal).
In addition, can deviate from-embed the compound N aVPO of sodium ion 4f, can deviate from-embed the compound Mg M of magnesium ion xo y(wherein M is a kind of metal, 0.5<x<3,2<y<6) and there is similar functions, the compound of can deviate from-embedded ion or functional group can be as the positive active material of battery of the present invention, therefore, the present invention is not limited to lithium ion battery.
In concrete execution mode, when preparation is anodal, also can in anode sizing agent, add binding agent, binding agent is conducive to make positive active material 10 to be bonded together uniformly.The weight percentage ranges of binding agent solid content in anode sizing agent is 0.5-10%.Concrete, binding agent is selected from but is not limited only to polymer, and polymer is selected from least one in polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC), sodium carboxymethylcellulose derivative (CMC derivation), butadiene-styrene rubber (SBR), butadiene-styrene rubber derivative (SBR derivation).Butadiene-styrene rubber derivative has hydrophilic butadiene-styrene rubber (PSBR100) as what obtain by chemical modification.
In concrete execution mode, when preparation is anodal, also can in anode sizing agent, add conductive agent, conductive agent mainly plays the electronic capability of leading that improves positive active material 10, and the weight percentage ranges of conductive agent solid content in anode sizing agent is 0.5-30%.Conductive agent comprises at least one being selected from conducting polymer, carbon nano-tube, activated carbon, Graphene, carbon black, graphite, carbon fiber, conductivity ceramics.Carbon black includes but are not limited to acetylene black, section's qin carbon black (Ketjen black, KB) and super-p carbon black.Conductive agent can also comprise metal oxide.Metal oxide includes but are not limited to lead oxide and tin oxide.
Fig. 2 is the generalized schematic of composite current collector 8, and composite current collector 8 comprises plus plate current-collecting body 12 and is coated on the conducting film 14 on plus plate current-collecting body 12.
Be coated on conducting film 14 on plus plate current-collecting body 12 must meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, swelling do not occur, high voltage can not be oxidized, be easy to be processed into densification, the film of waterproof and conduction.On the one hand, conducting film can play a protective role to plus plate current-collecting body, avoids the corrosion of aqueous electrolyte to plus plate current-collecting body.On the other hand, be conducive to reduce the internal resistance that contacts between positive active material and plus plate current-collecting body, improve the energy of battery.
For the effectively effect of performance conducting film 14, the thickness of conducting film 14 needs effectively to control.The too thin easy breakage of conducting film 14 thickness, thickness homogeneity is also bad, and aqueous electrolyte 6 easily penetrates; The too thick conductive capability that affects of conducting film 14.Preferably, the thickness of conducting film 14 is 10 μ m-2mm, and conducting film 14 not only can effectively play the effect of protection plus plate current-collecting body 12, and is conducive to reduce the internal resistance that contacts between positive active material 10 and plus plate current-collecting body 12.
Plus plate current-collecting body 12 has the first surface that is oppositely arranged and second, preferred, and the first surface of plus plate current-collecting body 12 and second are all coated with conducting film 14.
The method that conducting film 14 can be bonding by binding agent, hot pressing is compound or vacuumize is coated on plus plate current-collecting body 12, example, plus plate current-collecting body 12 is placed between two conducting films 14, compound by heating, make conducting film 14 clad anode collectors 12, and guarantee that the part that conducting film 14 has more than plus plate current-collecting body 12 seals intact.
Conducting film 14 comprises the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50-95%, and preferred, polymer is selected from thermoplastic polymer.For conducting film can be conducted electricity, there are two kinds of feasible forms: (1) polymer is conducting polymer; (2) conducting film also comprises conductive filler.
Conducting polymer choice requirement, can be as the ionic conduction of charge transfer medium for having electric conductivity but electrochemistry inertia.Concrete, conducting polymer includes but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and any mixture thereof.Conducting polymer itself just has conductivity, but can also to conducting polymer adulterate or modification further to improve its conductive capability.Stable use from electric conductivity and battery is considered, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler be surface area little, be difficult to oxidation, degree of crystallinity high, there is conductivity but electrochemistry inertia, can be 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.The mass percent scope of conductive filler in conducting film is 5-50%.The average grain diameter of conductive filler is not particularly limited, conventionally scope at 100nm to 100 μ m.
Preferably, conductive filler is carbon-based material, and form or the mechanical performance of carbon-based material do not have special requirement, example, carbon-based material is selected from a kind of in graphite, carbon nano-tube or amorphous carbon.Amorphous carbon includes but are not limited to active carbon and carbon black.The preferred carbon black of carbon-based material and graphite, it has large potential window, thereby the both positive and negative polarity electromotive force of relative broad range is stablized and had high conductivity.Metal oxide includes but are not limited to lead oxide, tin oxide.
While comprising conductive filler in conducting film, the polymer in conducting film preferably comprises the non-conductive polymer playing in conjunction with conductive filler effect, and non-conductive polymer has strengthened the combination of conductive filler, has improved the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.
Concrete, thermoplastic polymer includes but are not limited to polyolefin as polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, be preferably polyolefin, polyamide and Kynoar.These polymer easily melt by heat, therefore easily and plus plate current-collecting body and positive plate be combined with each other.In addition, these polymer have large potential window, thereby make positive stabilizer pole, are also battery output density saving in weight.
Concrete, the slurry that can contain thermoplastic polymer by preparation coating and cure pastes form conducting film.Certainly, what conductive filler can be extra is contained in slurry, concrete, and compound processing of polymer and conductive filler is as compound in disperseed with certain complex method, level obtains the conducting film with electric conductivity.Preferably, polymer monomer and conductive filler are mixed, because polymer monomer is little molecule, conductive filler can be good at being dispersed in polymer monomer, then under the effect of initator, makes polymer monomer generation polymerization, prepares conducting film.
Plus plate current-collecting body 12 is mainly the carrier as electrical conductivity and collection, does not participate in electrochemical reaction, and, in battery 1 operating voltage range, what plus plate current-collecting body 12 can be stable is present in aqueous electrolyte 6, thereby guarantees that battery 1 has stable cycle performance.Plus plate current-collecting body 12 need to meet that surface area is large, good mechanical property, the requirement such as conduct electricity very well.The material of plus plate current-collecting body 12 comprises a kind of in carbon-based material, metal or alloy.
Carbon-based material is selected from a kind of in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In concrete execution mode, plus plate current-collecting body is graphite, and as the paper tinsel of business-like graphite compacting, wherein the shared part by weight scope of graphite is 90-100%.
Metal comprises Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a kind of through in the above-mentioned metal of Passivation Treatment.In concrete execution mode, plus plate current-collecting body 12 is nickel foam.The composite current collector that contains nickel foam is difficult for being corroded in aqueous electrolyte 6, thereby positive pole 2 performances that make to contain this composite current collector 8 are more stable.
The main purpose of metal being carried out to Passivation Treatment is to make metallic surface form one deck passivating film, thereby in battery charge and discharge process, can play stable collection and the effect of conduction electron, and can not participate in anodal reaction, guarantees battery performance.
Alloy comprises stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or a kind of through in the above-mentioned metal of Passivation Treatment.
Stainless steel comprises stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to a kind of in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Same, by stainless steel carry out Passivation Treatment be also can be stable play and collect and the effect of conduction electron, and can not participate in electrode reaction, assurance battery performance.In embodiment, the stainless detailed process of passivation is: at 50 ℃, stainless steel is inserted to half an hour in 20% nitric acid, make stainless steel surfaces form one deck passivating film.Stainless steel after passivation is used as collector.
The thickness of plus plate current-collecting body 12 has certain influence to anodal 2 chemical property, and the thickness of plus plate current-collecting body 12 is too thin, can affect the mechanical strength of plus plate current-collecting body 12; The thickness of plus plate current-collecting body 12 is too thick, can increase by anodal 2 weight, thus the energy density of impact anodal 2, and in the present invention, in order to make battery have high energy density output, preferred, the thickness of plus plate current-collecting body 12 is 10 μ m-100 μ m.
Preferably, before using plus plate current-collecting body 12, plus plate current-collecting body 12 is through transpassivation, punching, polishing or weak acid corrosion treatment, treated plus plate current-collecting body 12 has larger specific area, be conducive to improve the Compound Degree of plus plate current-collecting body 12 and conducting film 14, thereby reduce the contact internal resistance between positive active material 10 and composite current collector 8.
In the present invention, anodal 2 adopt composite current collector 8, at the surperficial coated with conductive film 14 of plus plate current-collecting body 12, conducting film 14 adopts polymer or the composition polymer with superior electrical conductivity energy, on the one hand, conducting film 14 can further improve the electronic capability of leading of plus plate current-collecting body 12, thereby improves the large high rate performance of battery; On the other hand, be coated on the conducting film 14 on plus plate current-collecting body 12, avoided plus plate current-collecting body 12 directly to contact with aqueous electrolyte 6,6 pairs of potential etching problems of plus plate current-collecting body 12 of aqueous electrolyte have been solved, guarantee the stability of plus plate current-collecting body 12, solve the possible self discharge problem of battery 1, thereby make battery 1 there is stable cycle performance.
Negative pole 4 is selected from metal, alloy or carbon-based material, and the thickness range of negative current collector is 20 to 500 μ m.
Concrete, negative pole 4 is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
In the execution mode of a negative pole 4, negative pole 4 only comprises negative current collector, and negative current collector, as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.The material of negative current collector is selected from but is not limited only at least one in metal Cu, Ag, Pb, Sn, Fe, Al or the process above-mentioned metal of Passivation Treatment, or carbon-based material, or stainless steel.Wherein, carbon-based material comprises graphite material, and such as the paper tinsel of business-like graphite compacting, wherein the shared part by weight scope of 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 can also be selected from the metal that contains plating/coating that hydrogen-evolution overpotential is high, thereby reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance that contains C, Sn, In, Ag, Pb, Co, Zn, alloy, or in oxide at least one.The thickness range of plating/coating is 1-1000nm.For example: plumbous or silver-colored on the negative current collector plated surface of copper, or cover one deck carbon with the form applying.
In the execution mode of another negative pole 4, negative pole 4 only comprises negative current collector, but the selection of negative current collector and active ion in electrolyte is corresponding, and the simple substance that material of negative current collector is active ion, if active ion in electrolyte is Zn 2+, negative pole 4 corresponds to Metal Zn.Now, negative pole 4 is not only the deposition carrier as active ion, also can participate in cell reaction simultaneously.
In the execution mode of another negative pole 4, negative pole 4 comprises negative current collector and negative electrode active material, the selection of negative electrode active material is corresponding with active ion in electrolyte, and the simple substance that material of negative electrode active material is active ion, if active ion in electrolyte is Zn 2+, negative electrode active material corresponds to Metal Zn.Example, negative pole 4 comprises filtter gold and zinc paper tinsel, and filtter gold is as negative current collector, and the corresponding negative electrode active material of zinc paper tinsel, can participate in negative pole 4 reactions.
Aqueous electrolyte 6 comprises electrolyte, electrolyte at least can ionize out active ion, active ion is reduced and is deposited on negative pole 4 formation negative electrode active materials (not shown) when charging, and negative electrode active material is oxidized being dissolved in aqueous electrolyte 6 when electric discharge.
Active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.In a preferred embodiment, active ion is Zn 2+.The concentration range of active ion is 0.5-15mol/L.
Preferred, in aqueous electrolyte 6, also comprise a kind of electrolyte, this electrolyte can ionize out correspondence can there is the reversible ion of deviating from-embedding at positive pole.
In aqueous electrolyte 6, containing can the reversible ion of deviating from-embedding, thereby can improve positive active material 10 and aqueous electrolyte 6 intermediate ion exchange velocities.Concrete, positive active material 10 is for can the reversible compound of deviating from-embeds lithium ion, and in electrolyte, correspondence also comprises the lithium salts that can ionize out lithium ion.The reversible ion of deviating from-embedding comprises lithium ion or sodium ion or magnesium ion, and the concentration range of the reversible ion of deviating from-embedding in aqueous electrolyte is 0.1-10mol/L.
Active ion is present in aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
In order to guarantee battery capacity, the concentration of the active ion in aqueous electrolyte 6 must reach certain limit, when aqueous electrolyte is crossed alkali, can affect the solubility of active ion in electrolyte; When aqueous electrolyte peracid, there will be the problems such as proton embeds altogether in electrode material corrosion and charge and discharge process, therefore, the pH value scope of aqueous electrolyte is 3-7.
Barrier film 16 is arranged between positive pole 2 and negative pole 4, and on the one hand, barrier film 16 prevents battery 1 short circuit; On the other hand, barrier film 16 can keep aqueous electrolyte 6, concrete, after negative pole 4, barrier film 16, positive pole 2, barrier film 16 and negative pole 4 stacked arrangement are good, be placed on housing 22, inject the rear encapsulation of a certain amount of aqueous electrolyte 6, barrier film 16 is immersed in aqueous electrolyte 6, be in barrier film 16, to have absorbed aqueous electrolyte 6, guaranteed the ionic conduction path between positive pole 2 and negative pole 4; In addition, also can first barrier film 16 be immersed in aqueous electrolyte 6, and then the barrier film 16 that has absorbed aqueous electrolyte 6 is placed between positive pole 2 and negative pole 4.
Barrier film 16 can be used porous septum, bonded fabric or glass fibre.Porous septum includes but are not limited to polyethylene (PE), polypropylene (PP), a kind of in polyimides, or the lamination barrier film of PE-PP, PP-PE-PP.Bonded fabric includes but are not limited to artificial silk, acetate fiber, nylon.The impregnation amount of aqueous electrolyte in barrier film can also can surpass hold in range within the scope of the hold facility of barrier film, because battery 1 is provided with housing, can prevent that aqueous electrolyte 6 from leaking.
Refer to shown in Fig. 1 and Fig. 3, anodal 2 are arranged between negative pole 4 stackedly, negative pole 4 shares anodal 2, electronics is derived or is imported from plus plate current-collecting body 12 and negative pole 4, battery 1 is equivalent to 2 battery unit 20 internal parallels, in each battery unit 20, have positive pole 2, negative pole 4, aqueous electrolyte 6 and barrier film 16, barrier film 16 keeps aqueous electrolytes 6.In battery structure provided by the invention, owing to being in parallel between battery unit 20, aqueous electrolyte 6 can shuttle back and forth and can not cause battery unit 20 short circuits, the work that battery 1 can be normal, stable in any battery unit 20.
The charge-discharge principle of battery provided by the invention is: in a battery unit 20, during charging, can be reversible deviate from this ion in the positive active material 10 of deviate from-embedded ion, active ion in while aqueous electrolyte 6 obtains electronics at negative pole 4 and is reduced, and be deposited on negative pole 4, form negative electrode active material.Discharge process is the inverse process for charging.
In the present invention, anodal 2 adopt composite current collector 8, and the conducting film 14 being coated on plus plate current-collecting body 12 is equivalent to diaphragm, can effectively prevent the corrosion of 6 pairs of plus plate current-collecting bodies 12 of aqueous electrolyte, improves the impact of battery 1 self discharge.In addition, with respect to the battery forming with the parallel connection of independent battery unit in prior art, in the present invention, only adopt cleverly a positive pole 2 to form the battery 1 with parallel-connection structure, two negative poles 4 share a positive pole 2, the first surface 81 of composite current collector 8 and second 82 have been utilized fully, and on first surface 81 and second 82, positive active material 10 is set simultaneously, not only saved positive electrode, and make battery 1 structure compacter, alleviated the weight of battery 1, so the battery in the present invention 1 have excellent energy density and power density.In addition, the battery in the present invention 1 adopts aqueous electrolyte 6,, environmental protection safer with respect to the lithium ion battery of current business-like employing organic system electrolyte.
Battery preparation technique in the present invention is simple, can prepare battery by stacked mode, concrete, and negative pole, the barrier film that is soaked with aqueous electrolyte, positive pole and negative pole stack gradually to arrange and be placed in housing, then it are encapsulated.Battery 1 is equivalent to 2 battery units 20 formation in parallel, between battery unit 20 and battery unit 20, seal member need not be set especially, there is the work that the battery 1 of this internal parallel structure can be normal, stable, there is excellent charge-discharge performance, and battery 1 can be exported higher capacity, battery 1 is widely used.
Execution mode two
Refer to shown in Fig. 4, execution mode two provides a kind of battery 30, comprises housing 22, is arranged at two positive poles 2, negative pole 4, aqueous electrolyte 6 and barrier film in housing 22.Anodal 2 and negative pole 4 is stacked is arranged in housing 22, negative pole 4 is arranged between two positive poles 2, and two positive poles 2 share negative poles 4, between negative pole 4 and anodal 2, are provided with barrier film, barrier film maintenance aqueous electrolyte.
Anodal 2 comprise composite current collector 8 and positive active material 10, and composite current collector 8 comprises plus plate current-collecting body 12 and is coated on the conducting film 14 on plus plate current-collecting body.Composite current collector 8 has the first surface 81 that is oppositely arranged and second 82, and first surface 81 is relative with negative pole 4, and positive active material 10 is at least arranged on first surface 81, certainly, be not particularly limited, positive active material 10 also can be arranged on second 82, as shown in Figure 5 simultaneously.Negative pole 4 is selected from metal, alloy or carbon-based material; Aqueous electrolyte comprises electrolyte, electrolyte at least can ionize out active ion, active ion is reduced and is deposited on negative pole 4 formation negative electrode active materials (not shown) when charging, and negative electrode active material is oxidized being dissolved in aqueous electrolyte 6 when electric discharge.
Positive active material 10, composite current collector 8, negative pole and aqueous electrolyte 6 be by the agency of, here just no longer repetition in execution mode one.
Same, conducting film 14 can further improve the conductive capability of plus plate current-collecting body 12 on the one hand, the main isolated plus plate current-collecting body 12 of another side conducting film 14 contacts with aqueous electrolyte 6, thereby avoids the corrosion of 6 pairs of plus plate current-collecting bodies 12 of aqueous electrolyte, guarantees the stability of plus plate current-collecting body 12.
Housing 22 can be arranged to square or cylinder barrel shaped, corresponding, battery 30 can be designed to rectangular cell or cylindrical battery.
Concrete, positive pole 2, barrier film 16, negative pole 4, barrier film 16 and the anodal 2 stacked formation tabulars of arranging, be placed in housing 22, as shown in Figure 4.Thereby battery 30 can be designed to rectangular cell, as cuboid or square.This battery structure is simple, convenience is manufactured, cost is simple.
In addition, anodal 2, barrier film 16, negative pole 4, barrier film 16 and the anodal 2 stacked formation tabulars of arranging, winding shaping then, thus form tabular battery core.Preferably, positive pole 2, barrier film 16 and negative pole 4 are all set to strip.According to battery design, need to be wound into the different number of turns.
Housing 22 can also be set to cylinder barrel shaped.
Concrete, positive pole 2, barrier film 16, negative pole 4, barrier film 16 and the anodal 2 stacked formation tabulars of arranging, then form cylindrical battery core by coiling and be arranged in housing 22, positive pole 2, barrier film 16, negative pole 4 and housing 22 arranged in co-axial alignment.Thereby battery can be designed to cylindrical battery, battery structure is simple, convenient manufacture.
In execution mode two, battery 30 all the other formations, with execution mode one, repeat here no longer one by one.
Battery in execution mode one, two is to be all equivalent to two battery unit parallel connections, difference is, battery 1 in execution mode one is that two negative poles 4 share a positive pole 2, and battery 30 in execution mode two to be two positive poles 2 share negative poles 4, therefore, battery provided by the invention has flexibly to be selected, when Practical manufacturing battery, can be in conjunction with factors such as the weight of manufacture craft, both positive and negative polarity, material costs, select to make the battery of structure as shown in execution mode one or two, make the final battery obtaining have more cost and performance advantage.
Battery in the present invention; the anodal composite current collector that adopts; adopt and there is the coated plus plate current-collecting body of conducting film; conducting film is as the diaphragm of plus plate current-collecting body; prevent the corrosion of aqueous electrolyte to plus plate current-collecting body; improved the potential self discharge problem of battery, battery has stable cycle performance.Battery has internal parallel structure, and than parallel-connection structure battery of the prior art, the battery in the present invention is saved material and compact conformation, light more, makes the battery in the present invention on energy density and volume, have obvious advantage; Secondly, battery adopts aqueous electrolyte, and aqueous electrolyte has higher ionic conductance relatively, has improved the high rate performance of battery; Battery is used safety, environmental protection and manufacture craft simple, in preparation process, can according to user demand preparation, have the battery of different output capacities, and battery use is extensive, has commercial application prospect.
Execution mode three
Refer to shown in Fig. 6, a kind of battery 40, comprises housing 22, is arranged at positive pole 2, negative pole 4, aqueous electrolyte 6 and barrier film in housing 22.
Battery comprises that n is to positive pole 2 and negative pole 4, n >=2, and positive pole 2, negative pole 4 are arranged alternately, and two adjacent positive poles 2 share the negative pole 4 between two positive poles 2, and two adjacent negative poles 4 share the positive pole 2 between two negative poles 4.In Fig. 6, battery 300 comprises 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, and two adjacent negative poles 4 share the positive pole 2 between two negative poles 4.
Anodal 2 comprise composite current collector 8 and positive active material 10, composite current collector 8 comprises plus plate current-collecting body 12 and is coated on the conducting film 14 on plus plate current-collecting body 12, composite current collector 8 has the two sides being oppositely arranged, wherein, in the one side that at least composite current collector 8 is relative with negative pole 4, be provided with positive active material 10, positive active material can be reversible deviate from-embedded ion.
Concrete, refer to shown in Fig. 6, anodal composite current collector 8 has the two sides being oppositely arranged, when positive pole 2 is between two negative poles 4, the two sides that composite current collector 8 is oppositely arranged is all relative with negative pole 4, so all needs to arrange positive active material 10 on the two sides that is oppositely arranged of composite current collector 8; And for being positioned at outermost anodal 2, composite current collector 8 only has one side relative with negative pole 4, therefore in the one side that at least composite current collector 8 is relative with negative pole 4, positive active material 10 is set, the opposing one side of composite current collector 8 and negative pole 4 is not particularly limited, can be according to the positive active material that arranges of actual fabrication process choice, in Fig. 7, showing of summary is arranged in outermost layer positive pole, and is also provided with positive active material 10 in the one side of the opposing composite current collector of negative pole.
Negative pole 4 is selected from metal, alloy or carbon-based material; Aqueous electrolyte comprises electrolyte, electrolyte at least can ionize out active ion, active ion is reduced and is deposited on negative pole 4 formation negative electrode active materials (not shown) when charging, and negative electrode active material is oxidized being dissolved in aqueous electrolyte 6 when electric discharge.Selection and the manufacture method of positive pole in execution mode three, negative pole and aqueous electrolyte, with execution mode one, no longer repeat to introduce here.
Battery 40 shown in Fig. 6 contains two pairs of positive poles and negative pole, be equivalent to 3 battery unit (not shown) in parallel, but when actual fabrication battery, battery structure provided by the invention can be easy to increase positive pole or negative pole or positive pole and negative pole according to user demand, for example, at battery 40 outermost anodal place stack negative pole or superpose successively negative pole and positive pole, or anodal or superpose successively positive pole and negative pole, the positive pole of stack and negative pole alternative arrangement in the stack of the outermost negative pole of battery 40 place.Number anodal and negative pole is determined according to user demand, as shown in Figure 8, although the total output voltage of battery 50, does not become, and battery 50 has higher capacity, and battery structure is flexible, of many uses, has commercial application prospect.
In containing the battery system of neutral aqueous electrolyte, be difficult to find and meet existing certain mechanical performance, good electric conductivity simultaneously, again can be in neutral aqueous electrolyte the plus plate current-collecting body of stable existence, so the commercialization process of water system battery is stagnated always.Battery provided by the invention just in time can address this problem; the positive pole of battery adopts composite current collector; composite current collector adopts the coated plus plate current-collecting body of conducting film; conducting film can improve the electric conductivity of plus plate current-collecting body on the one hand; the more important thing is plus plate current-collecting body is played a protective role; the corrosion of isolated neutral aqueous electrolyte to plus plate current-collecting body; make the collection that plus plate current-collecting body can be stable in discharge process and derive electronics; thereby guarantee that battery has stable cycle performance, battery provided by the invention has good Commercial Prospect.
[bipolar battery]
The present invention also provides a kind of battery, concrete, and battery is water system bipolar battery.Below by concrete execution mode, introduce water system bipolar battery.
Execution mode four
Refer to shown in Fig. 9 and Figure 10, a kind of battery 100, comprises housing (not shown), is located at positive extraction electrode 54, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6 in housing.Positive extraction electrode 54, bipolar electrode 52 and negative extraction electrode 58 is stacked is arranged in housing, positive extraction electrode 54 and negative extraction electrode 58 lay respectively at the superiors and orlop, and bipolar electrode 52 and aqueous electrolyte 6 are arranged between positive extraction electrode 54 and negative extraction electrode 58.In Fig. 9, battery 100 comprises two bipolar electrodes 52.
Housing can be set to square.Concrete, positive extraction electrode 54, bipolar electrode 52 and the stacked formation tabular of arranging of negative extraction electrode 58, be placed in housing.Thereby battery 100 can be designed to rectangular cell, as cuboid or square.This battery 100 is simple in structure, convenience is manufactured, cost is simple.
The selection of housing is with same execution mode one is set, same, in execution mode four, battery 100 also comprises the lid (not shown) being connected with housing, positive extraction electrode 54 and 58 extensions of negative extraction electrode pass lid, be connected with external circuit, and positive extraction electrode 54 and negative extraction electrode 58 extend the end that passes lid and be provided with sealing cap, sealing cap can prevent the hole evaporation that aqueous electrolyte passes from positive extraction electrode 54 and negative extraction electrode 58, thereby reduces the consumption of aqueous electrolyte 6.
Same, battery 100 also comprises safety valve and is arranged on the fluid infusion mouth (not shown) on housing, and arranging with reference to execution mode one of safety valve and fluid infusion mouth, just no longer repeats to introduce here.
Positive extraction electrode 54 comprises plus plate current-collecting body 12 and is arranged on the positive active material 10 of plus plate current-collecting body 12 one sides, positive active material 10 can be reversible deviate from-embedded ion.In execution mode one by the agency of positive active material 10 and plus plate current-collecting body 12, just no longer repeat here to introduce.
Figure 10 is for forming the summary section of the bipolar electrode 52 of battery 100, bipolar electrode 52 comprises bipolarity collector 56 and positive active material 10, bipolarity collector 56 has the first surface 61 that is oppositely arranged and second 62, and positive active material 10 is arranged on the first surface 61 of bipolarity collector 56.The first surface 61 of bipolarity collector 56 is contrary with second 62 polarity, and first surface 61 is equivalent to positive pole, and second 62 is equivalent to negative pole.
The production method of bipolar electrode 52 is not particularly limited, and positive active material 10 can be that the mode by applying is attached on bipolarity collector 56, for example, positive active material 10 is made to slurry, then by slurry method, is coated on bipolarity collector 56; Also can on compressing positive active material 10, apply bipolarity collector 56; Can also positive active material 10 be attached on bipolarity collector 56 by stacked mode, for example the bipolarity collector 56 by pre-sizing moulding and positive active material 10 are suppressed, make to electrically contact well between positive active material 10 and bipolarity collector 56, form bipolar electrode 52.The thickness range of positive active material 10 is 100-400 μ m.Positive active material 10 in positive active material 10 in bipolar electrode 52 and positive extraction electrode 54 specifically can be with reference to positive active material in execution mode one.
The material of bipolarity collector 56 can be conductive plastics, and preferred, the thickness range of bipolarity collector 56 is 50 to 100 μ m.
The material of conductive plastics is selected from conducting polymer, concrete, and conducting polymer includes but are not limited at least one in polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, poly quinoline or polyparaphenylene.Conducting polymer itself just has conductivity, but can also to conducting polymer adulterate or modification further to improve its conductive capability.
Conductive plastics can also be compound conductive plastics, composite conductive plastic be take polymer as main matrix, and it is formulated to mix therein conductive agent, here, whether polymer itself conducts electricity is not particularly limited, and the conductive capability of compound conductive plastics is mainly to realize by conductive agent.Concrete, conductive plastics comprises polymer and conductive agent, polymer includes but are not limited to polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.Concrete, polymer can be the polytetrafluoroethylene in fluororesin, can also be copolymer, as the copolymer of polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).
Conductive agent comprises carbon-based material, metal or metal oxide.The mass percent scope of conductive agent in conductive plastics is 10-90%.
Carbon-based material is selected from a kind of in graphite, carbon nano-tube or amorphous carbon.Amorphous carbon includes but are not limited to active carbon and carbon black.
The form of metal is not limit, and can be metal powder, sheet metal, metal strand, metallic fiber.Metal oxide includes but are not limited to lead oxide, tin oxide.
Concrete, the compound plastics with electric conductivity that obtain of processing of polymer and conductive agent is as compound in disperseed with certain complex method, level.
The material of bipolarity collector 56 can also be the stainless steel of stainless steel or process Passivation Treatment, stainless mechanical performance is better than conductive plastics, therefore, when using stainless steel as bipolarity collector 56, the thickness of bipolarity collector 56 can be thinner, concrete, the thickness range of bipolarity collector 56 is 20-100 μ m.
The method that passivation for stainless steel is processed is restriction not, can be physical method passivation, chemical method passivation or electrochemical method passivation.The object of passivation is in order to improve the compatibility of bipolarity collector 56 and aqueous electrolyte 6, thereby reduces the generation of side reaction, makes battery have stable cycle performance.
In the present invention, less demanding for the mechanical performance of bipolarity collector 56 that forms bipolar electrode 52, can adopt the stainless steel of conductive plastics that weight is lighter or thinner thickness as bipolarity collector 56, battery 100 overall weight are reduced, so the energy density of battery 100 is significantly improved.
Negative extraction electrode 58 is selected from metal, alloy or carbon-based material.
Concrete, negative extraction electrode 58 is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
Negative extraction electrode 58 can also be selected from the metal that contains plating/coating that hydrogen-evolution overpotential is high, thereby reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance that contains C, Sn, In, Ag, Pb, Co, Zn, alloy, or in oxide at least one.The thickness range of plating/coating is 1-1000nm.For example: plumbous or silver-colored on negative extraction electrode 58 plated surfaces of copper, or cover one deck carbon with the form applying.The thickness range of plus plate current-collecting body 12 and negative extraction electrode 58 is 1-10mm.
Negative extraction electrode 58 is with the negative pole 4 in execution mode one, negative extraction electrode 58 can be only participate in electrode reaction as the matrix of electron collection and conduction, or negative extraction electrode 58 comprises negative current collector and negative electrode active material, if negative extraction electrode 58 is filtter gold and zinc paper tinsel, 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, bipolar electrode 52 and the stacked setting of negative extraction electrode 58, when in battery 100, bipolar electrode 52 is one, between positive extraction electrode 54 and adjacent bipolar electrode 52, be provided with aqueous electrolyte 6 between bipolar electrode 52 and adjacent negative extraction electrode 58.In battery 100 during more than one of bipolar electrode 52, between positive extraction electrode 54 and adjacent bipolar electrode 52, between adjacent bipolar electrode 52, be provided with aqueous electrolyte 6 between bipolar electrode 52 and adjacent negative extraction electrode 58.
Aqueous electrolyte 6 comprises electrolyte, electrolyte at least can ionize out active ion, active ion is reduced second the formation negative electrode active material that is deposited on bipolarity collector 56 when charging, negative electrode active material is oxidized being dissolved in aqueous electrolyte 6 when electric discharge, and active ion is present in aqueous electrolyte 6 with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
Aqueous electrolyte 6 and active ion by the agency of in execution mode one, just repeats no more here.
Preferably, in aqueous electrolyte 6, also comprise with positive active material 10 can be reversible the corresponding ion of deviate from-embedded ion, ion comprises at least one in lithium ion, sodium ion or magnesium ion.Concrete, as positive active material 10 can be reversible deviate from-while embedding lithium ion, the corresponding lithium ion that also contains in aqueous electrolyte 6 so, like this, can improve the ion-exchange speed in positive active material 10 and aqueous electrolyte 6, improve the high rate charge-discharge performance of battery 100.
Battery 100 in execution mode four also comprises barrier film 16, barrier film 16 is arranged between positive extraction electrode 54 and adjacent bipolar electrode 52, between bipolar electrode 52 and adjacent negative extraction electrode 58, in execution mode four, battery 100 comprises two bipolar electrodes 52, therefore, between adjacent bipolar electrode 52, be also provided with barrier film 16.On the one hand, barrier film 16 is for keeping aqueous electrolyte 6, and barrier film 16 prevents battery 100 short circuits on the other hand.
Barrier film 16 can be used porous septum, bonded fabric or glass fibre.Porous septum includes but are not limited to polyethylene (PE), polypropylene (PP), a kind of in polyimides, or the lamination barrier film of PE-PP, PP-PE-PP.Bonded fabric includes but are not limited to artificial silk, acetate fiber, nylon.The impregnation amount of aqueous electrolyte 6 in barrier film 16 can also can surpass hold in range within the scope of the hold facility of barrier film 16, because battery 100 is provided with sealing 60, can prevent that aqueous electrolyte 6 from leaking.
The peripheral part of bipolarity collector 56 is provided with for sealing the sealing 60 of aqueous electrolyte 6, be not particularly limited, sealing 60 can adopt sealing ring, the shape of sealing ring is preferably rectangle, and the selection of sealing ring so long as can realize excellent sealing effectiveness under the environment for use of battery 100.
Be not particularly limited, the material of sealing 60 is rubber, and rubber is selected from but is not limited only to a kind of in silicon class rubber, fluorine class rubber, olefin rubber, nitrile rubber, wherein, olefin rubber includes but are not limited to butadiene-styrene rubber (SBR), neoprene (CR).The rubber resin of these sealing use has good sealing (liquid-tight property), resistance to acids and bases, resistance to chemical reagents, durability, weatherability and thermal endurance, and these excellent performances can be kept under the environment for use of battery 100 and can be not deteriorated for a long time, therefore can effectively prevent that aqueous electrolyte 6 from oozing out from battery 100, thereby prevent battery 100 short circuits that the leakage due to aqueous electrolyte 6 causes, guarantee the stable circulation performance of battery 100.
In addition, so long as can effectively realize action effect of the present invention, as the various rubber with acid resistance and sealing all can be used as the material of sealing 60 of the present invention.
Be not particularly limited, when sealing 60 adopts sealing ring, the area of barrier film 16 is less than the encirclement area of sealing ring, and the height of sealing ring is not less than the thickness sum of barrier film 16 and positive active material 10, when assembled battery, the barrier film 16 that is soaked with aqueous electrolyte 6 is placed in the circle of sealing ring, and barrier film 16 does not participate in sealing, can avoid like this because adopting the leakage of the aqueous electrolyte 6 that porous septum may cause.Certainly, the area of barrier film 16 also can be greater than the encirclement area of the sealing 60 that is arranged on bipolar electrode 52 peripheral parts, as long as barrier film 16 is finally one-body molded with sealing 60, can not cause aqueous electrolyte 6 to be revealed just.
Refer to shown in Figure 11, bipolar electrode 52 is arranged between positive extraction electrode 54 and negative extraction electrode 58 stackedly, electronics is only derived or is imported from positive extraction electrode 54 and negative extraction electrode 58, battery 100 is equivalent to 3 battery unit 64 internal series-connections, in each battery unit 64, there are positive pole, negative pole, aqueous electrolyte and barrier film, aqueous electrolyte 6 seals by sealing 60, avoid the short circuit between battery unit 64 that the leakage due to aqueous electrolyte 6 causes, thereby guarantee the normal work of battery 100.
For example, one of them battery unit 64 comprises plus plate current-collecting body 12, positive active material 10, barrier film 16, aqueous electrolyte 6, sealing 60 and as second 62 of the bipolarity collector 56 of negative pole.Sealing 60 is for sealing the aqueous electrolyte 6 of each battery unit 64, to avoid causing because of the leakage of aqueous electrolyte 6 short circuit of battery 100.Battery 100 shown in Figure 11 only comprises two bipolar electrodes 52, but in fact the number of bipolar electrode 52 in battery 100 can be set according to user demand easily, thereby the battery that preparation has the battery of different output voltages and has high output voltage, battery tool provided by the invention has been widely used.
Battery preparation technique in the present invention is simple, can prepare battery by stacked mode, concrete, on negative extraction electrode, place rectangular seal stackedly, the peripheral part laminating of sealing ring and negative extraction electrode is then placed and is soaked with the barrier film of aqueous electrolyte in the circle of sealing ring, then stacks gradually bipolar electrode and positive extraction electrode, positive active material in positive extraction electrode and bipolar electrode is placed towards negative extraction electrode simultaneously, and aqueous electrolyte seals by sealing ring.The number of bipolar electrode determines the last output voltage of battery, therefore, can the number of bipolar electrode be set according to user demand, and battery tool has been widely used.
Please refer to shown in Figure 12, the charge-discharge principle of battery 100 provided by the invention is: in a battery unit 64, during charging, can be reversible deviate from this ion in the positive active material 10 of deviate from-embedded ion, simultaneously the active ion in aqueous electrolyte 6 obtains electronics second 62 of bipolarity collector 56 and is reduced, and be deposited on second 62, form negative electrode active material.In the battery unit 64 that contains negative extraction electrode 58, active ion obtains electronics and is reduced on negative extraction electrode 58, is deposited on negative extraction electrode 58.Discharge process is the inverse process for charging.
In the present invention, the bipolar electrode 52 that forms battery 100 only arranges positive active material 10 at the first surface 61 of bipolarity collector 56, second 62 of bipolarity collector 56 is equivalent to negative pole, for obtaining electron reduction-deposition, active ion provides carrier, active ion is present in aqueous electrolyte 6, with respect to the first surface 61 of bipolarity collector 56 and second 62, positive active material 10 being all set in prior art, battery 100 structures in the present invention are compacter, and battery 100 has excellent energy density and power density.In addition, the battery in the present invention 100 adopts aqueous electrolyte 6,, environmental protection safer with respect to the lithium ion battery of current business-like employing organic system electrolyte.
Battery 100 in the present invention, is equivalent to 64 series connection of several battery units and forms, and each battery unit 64 is well sealed by sealing 60, thereby prevents the short circuit that the leakage due to aqueous electrolyte 6 causes.In addition, even if battery of the present invention does not arrange special leakage-proof part or insulating element, also can prevent the short circuit between battery unit, thereby the bipolar battery with excellent ionic conductance, charge-discharge performance is provided.In addition, the bipolar electrode 52 of varying number can be set according to user demand, thereby preparation has the battery 100 of different output voltages, battery 100 purposes are very extensive.
Execution mode five
Refer to shown in Figure 13, execution mode five provides a kind of battery 110, and battery 110 comprises housing (not shown), is located at positive extraction electrode 54, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6 in housing.What bipolar electrode 52 was stacked is arranged between positive extraction electrode 54 and negative extraction electrode 58, and positive extraction electrode 54 and negative extraction electrode 58 lay respectively at the superiors and orlop.
Positive extraction electrode 54 comprises plus plate current-collecting body 12 and is arranged on the positive active material 10 of plus plate current-collecting body 12 one sides, is that plus plate current-collecting body 12 is coated with conducting film 14 with the difference of execution mode five.
Conducting film 14 can be bonding by binding agent, hot pressing is compound or the method for vacuum coated is coated on the one side of plus plate current-collecting body 12, and then positive active material 10 is set on conducting film 14, and the thickness of conducting film 14 is 0.01-0.2mm.In Figure 13, on the two sides of plus plate current-collecting body 12, be all coated with conducting film 14.
The material of conducting film 14 is introduced in detail in execution mode one, just no longer repeats here.
On the one hand, the compound that adopts conducting polymer or contain conductive agent can improve the electronic capability of leading of plus plate current-collecting body 12 as conducting film 14; On the other hand, be coated on the conducting film 14 on plus plate current-collecting body, avoided plus plate current-collecting body 12 directly to contact with aqueous electrolyte 6,6 pairs of potential etching problems of plus plate current-collecting body 12 of aqueous electrolyte have been solved, guarantee the stability of plus plate current-collecting body 12, improve the possible self discharge problem of battery 110, thereby make battery 110 there is stable cycle performance.
Refer to shown in Figure 14, battery unit 68 seals by sealing 60, and sealing 60 is arranged on the peripheral part of bipolarity collector 56, for sealing aqueous electrolyte 6.
In execution mode five, battery 110 all the other formations and assembling mode, with execution mode four, repeat here no longer one by one.
The battery providing in execution mode five, adopt the coated plus plate current-collecting body of conducting film, stop aqueous electrolyte to the potential etching problem of plus plate current-collecting body, made battery except thering is the features such as high output voltage, safety, environmental protection, further improved the stable circulation performance of battery.
Execution mode six
Refer to shown in Figure 15, execution mode six provides a kind of battery 120, and battery 120 comprises housing (not shown), is located at positive extraction electrode 54, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6 in housing.What bipolar electrode 52 was stacked is arranged between positive extraction electrode 54 and negative extraction electrode 58, and positive extraction electrode 54 and negative extraction electrode 58 lay respectively at the superiors and orlop.That battery 120 does not comprise barrier film with the difference of execution mode four.
Same, battery unit (not shown) seals by sealing 60, and sealing 60 is arranged on the peripheral part of bipolarity collector 56, for sealing aqueous electrolyte 6.Example, sealing 60 can adopt sealing ring, the height of sealing ring is greater than the thickness of positive active material 10, by thering is the sealing ring of certain altitude, make between positive extraction electrode 54 and the bipolarity collector 56 of adjacent bipolar electrode 52 and the bipolarity collector 56 of bipolar electrode 52 and adjacent negative extraction electrode 58 between keep certain distance, to avoid battery 120 short circuits.In battery 120 during more than one of the number of bipolar electrode 52, between the bipolarity collector 56 of adjacent bipolar electrode 52 and bipolarity collector 56, be provided with equally sealing 60.
While preparing the battery in execution mode six, can first the positive extraction electrode 54 preparing by predetermined dimension, bipolar electrode 52 and negative extraction electrode 58 be arranged and be sealed.Concrete, positive active material 10 on positive extraction electrode 54 and bipolar electrode 52 is arranged towards negative extraction electrode 58 simultaneously, sealing 60 can adopt have exceed positive active material 10 thickness elastomeric material as sealing ring, sealing ring is arranged on to the peripheral part of bipolarity collector 56, finally by the mode of injection, injects aqueous electrolyte 6; Sealing 60 can also adopt thermoplastic elastomer material, when preliminary sealing, only the peripheral part on bipolarity collector 56 3 limits arranges thermoplastic elastomer material, retain openings at one side, after positive extraction electrode 54, bipolar electrode 52 and negative extraction electrode 58 are arranged, by heating or heat pressurization, make Cure of Rubber moulding, then the aqueous electrolyte 6 that injects scheduled volume by place, unencapsulated one side, finally more all battery units are sealed completely.
In execution mode six, battery 120 all the other formations and assembling mode, with execution mode four, repeat here no longer one by one.
Battery 120 in execution mode six does not adopt barrier film, and battery 120 not only can be given normal, lasting work, and because weight is lighter, so battery 120 has more excellent energy density and specific power.In addition, when preparing battery 120, can form easily sealing 60, prevent the short circuit that the leakage due to aqueous electrolyte 6 causes.Even if battery 120 does not arrange special leakage-proof part, can prevent the short circuit between battery unit, battery 120 has excellent cycle performance and cycle life.
Execution mode seven
Refer to shown in Figure 16, execution mode seven provides a kind of battery 130, and battery 130 comprises housing (not shown), is located at positive extraction electrode 54, at least one bipolar electrode 52, negative extraction electrode 58 and aqueous electrolyte 6 in housing.What bipolar electrode 52 was stacked is arranged between positive extraction electrode 54 and negative extraction electrode 58, and positive extraction electrode 54 and negative extraction electrode 58 lay respectively at the superiors and orlop.
Positive extraction electrode 54 comprises plus plate current-collecting body 12 and is arranged on the positive active material 10 of plus plate current-collecting body 12 one sides, is that plus plate current-collecting body 12 is coated with conducting film 14 with the difference of execution mode six.
The selection of conducting film 14, molding mode, with execution mode one, just repeat here no longer one by one.
Battery 130 in execution mode seven, is coated on conducting film 14 on plus plate current-collecting body 12 and has completely cut off contacting of plus plate current-collecting body 12 and aqueous electrolyte 6, has improved the stable of plus plate current-collecting body 12, thereby guarantees that battery 130 has stable cycle performance.Do not use battery 130 weight of barrier film lighter, when being convenient to user and carrying, provide excellent performance.
Battery in the present invention, bipolarity collector in bipolar electrode can adopt the stainless steel of conductive plastics or thinner thickness, when guaranteeing the normal work of battery, the weight of battery is lighter, makes the battery in the present invention on energy density and volume, have obvious advantage; Secondly, battery adopts aqueous electrolyte, and aqueous electrolyte has higher ionic conductance relatively, has improved the high rate performance of battery; Battery is used safety, environmental protection and manufacture craft simple, in preparation process, can according to user demand preparation, have the battery of different output voltages, and battery use is extensive, has commercial application prospect.
The battery that contains bipolar electrode is provided in the present invention, only the one side at bipolar electrode applies positive active material, bipolar electrode does not have negative active core-shell material with scribbling in the one side that positive active material is relative before battery first charge-discharge, the active ion of negative pole is present in aqueous electrolyte, when battery is charged, be deposited on the one side of the uncoated positive active material of bipolar electrode, battery has excellent cycle performance.Meanwhile, what battery adopted is aqueous electrolyte, and with respect to the lithium ion battery that adopts organic system electrolyte, battery in the present invention is safer, environmental protection.In addition, by the number of bipolar electrode is set, can prepare the battery that has different output voltages, has high output voltage, battery use is extensive and preparation technology is simple, and battery has commercial applications potentiality.
[plank frame battery]
The present invention also provides a kind of battery, and battery has plank frame.
Execution mode eight
As shown in figure 17, a kind of battery 140, battery 140 comprises housing 70, is located at positive pole 72, negative pole 74, barrier film 76 and aqueous electrolyte 78 in housing 70.And barrier film 76 is arranged between positive pole 72 and negative pole 74.
Anodal 72 comprise plus plate current-collecting body 80 and participate in the positive active material 82 of electrochemical reaction, positive active material 82 comprise can be reversible the compound of deviate from-embedded ion; Negative pole 74 is selected from metal, alloy or carbon-based material; Aqueous electrolyte 78 comprises electrolyte, and electrolyte at least can ionize out active ion, and active ion is reduced and is deposited on negative pole 74 formation negative electrode active materials when charging, and negative electrode active material is oxidized being dissolved in aqueous electrolyte 78 when electric discharge.
Positive pole 72, negative pole 74, aqueous electrolyte 78 and barrier film 76, with execution mode one, just no longer repeat to introduce here.
Positive pole 72, barrier film 76 and negative pole 74 form tabulars, and barrier film 76 is between positive pole 72 and negative pole 74.Accordingly, housing 70 is set to square.Thereby battery can be designed to rectangular cell, as cuboid or square.This battery structure is simple, convenience is manufactured, cost is simple.
Battery 140 is designed to stacked.Positive pole 72, barrier film 76 and the stacked formation tabular of arranging of negative pole 74, and barrier film 76 is between positive pole 72 and negative pole 74.Accordingly, housing 70 is also set to square.
In Figure 17, anodal 72 are set to 4, and negative pole 74 is set to 5, the most close housing 70 be negative pole 74.
Battery also can be set to comprise some independently battery units, and independently battery unit comprises independently positive pole, barrier film and negative pole.Wherein battery unit connects with parallel way.Independently battery unit can be set to 2～10 groups.Certainly, also can battery unit independently need to be arranged to not count on the same group according to difference, as 12 groups or with first-class.In addition, independently battery unit also can connect with series system as required.
Housing 70 can be set to the composite membrane of metal, plastics or metal and plastics, as steel, aluminium, acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), nylon or aluminum plastic film etc.Preferably, housing 70 is set to aluminum plastic film, thereby makes housing thinner.When reducing battery weight, also increased the space of inside battery.Aluminum plastic film comprises one deck aluminium flake and ground floor plastic sheet.Preferably, aluminum plastic film also comprises the second layer plastic sheet that is arranged at above-mentioned aluminium flake opposite side with respect to ground floor plastic sheet.
Battery also comprises the lid 84 being connected with housing 70, and plus plate current-collecting body 80 extensions pass lid 84, and the end that plus plate current-collecting body 80 extensions pass lid 84 is provided with sealing cap 86.Sealing cap 86 need to have good conductivity and chemical stability.In addition, sealing cap 86 also can prevent the hole evaporation that aqueous electrolyte 78 passes from plus plate current-collecting body 80, thereby reduces the consumption of aqueous electrolyte 78.Anodal 72 are connected with external circuit.
Negative pole 74 also extends and passes lid 84, thereby is connected with external circuit.Equally, negative pole 74 extends the end that passes lid 24 and is provided with sealing cap (not shown).
In addition, battery is in charging process, and especially fast approaching while charging the later stage, because charging current is by water decomposition, can discharge a large amount of hydrogen, carrier of oxygen.Along with the hydrogen producing and oxygen get more and more, the pressure in battery container is also in continuous rising, and when pressure rise is to certain value, battery case cognition deforms.Therefore, battery also comprises for controlling the safety valve 88 of housing 70 internal pressures.Pressure in the housing 70 of battery arrives default when driving valve and pressing, and safety valve 88 is opened, and by earth pressure release, prevents housing distortion, thereby has improved life-span and the fail safe of battery.
In addition, pressure in housing 70 arrives default when closing valve and pressing, and safety valve 88 closures, prevent that internal gas is to outward leakage.Meanwhile, also preventing that extraneous air from entering in housing 70 causes harmful effect.And can also prevent that the hydrogen of separating out from producing tempering while meeting naked light, thereby ignite housing 70 internal gas.
On housing 70, also can be provided with for supplementing the fluid infusion mouth (not shown) of aqueous electrolyte 78.Like this, when aqueous electrolyte 78 is less, can inject aqueous electrolyte 78 by fluid infusion mouth.
Preferably, fluid infusion mouth is the installing hole (not shown) at mounting safety valve 88 places.
Refer to shown in Figure 18 and 19, battery is stacked.Concrete, barrier film 76 is all-in-one-piece banded structure, and barrier film 76 is folding with Z-shaped.Positive pole 72 and the stacked lap seam place that is arranged in barrier film 76 of negative pole 74.Now, barrier film 76 anodal 72 and negative pole 74 between, thereby make anodal 72 and negative pole 74 between insulated from each other.
Positive pole 72, barrier film 76 and negative pole 74 are pressed into square plate shape equally.Accordingly, housing 70 is also set to square, and as cuboid or square, thereby battery can be designed to rectangular cell.
Refer to shown in 20, battery is takeup type, and battery comprises positive pole 72, negative pole 74 and barrier film 76.Positive pole 72, barrier film 76 and negative pole 74 winding shapings, thus tabular battery core formed, and barrier film 76 is between positive pole 72 and negative pole 74.Accordingly, housing 70 is also set to square, and as cuboid or square, thereby the battery in the present embodiment can be designed to rectangular cell.
Preferably, positive pole 72, barrier film 76 and negative pole 74 are all set to strip.Can be wound into as required the different number of turns.
Concrete, tabular battery core comprises two relative planes 90, two curved portions 92 that connect above-mentioned two planes 90 and be oppositely arranged.At least one in anodal coiling clearing end 94 and negative pole coiling clearing end 96 is positioned at curved portions 92 places of tabular battery core.
Preferably, anodal coiling clearing end 94 and negative pole coiling clearing end 96 lay respectively at two curved portions 92 places that tabular battery core is oppositely arranged.
Preferably, anodal coiling clearing end 94 and negative pole coiling clearing end 96 are positioned at same curved portions 92 places of tabular battery core.
When battery is in charge and discharge process, pole piece thickness can expand, thereby causes tabular battery core integral thickness to increase.And positive pole coiling clearing end 94 and negative pole coiling clearing end 96 are arranged on to curved portions 92 places, owing to leaving space between curved portions 92 and housing 70, this space is that cushioning effect has been played in the expansion of tabular battery core.Thereby make can not produce larger stress at curved portions 92 places, concentrate, and then avoided curved portions 92 places to occur obvious fold, effectively reduced the crystallization of the reversible ion of deviating from-embedding.
In Figure 20, the method for winding of tabular battery core is, from inner ring, barrier film 76 is wound as two-layer, and two-layer barrier film 76 is bonded to each other, according to designing requirement, second circle of reeling again after two-layer barrier film 76 laminating certain lengths, now, from inner ring, is followed successively by two-layer barrier film 76, negative pole 74, is wound up into the barrier film 76 of the second circle, and anodal 72, the barrier film 76 that is wound up into the second circle, then continues coiling negative pole 74, barrier film 76, positive pole 72, barrier film 76 is to the designed number of turns.Certainly, as is known to the person skilled in the art, also has other method for winding, as long as guarantee anodal and negative pole insulation.
A kind of battery provided by the invention, there is energy density high (can reach the 60%-80% of lithium ion battery), power density (is expected to reach 200% of lithium ion battery greatly, even higher), be easy to manufacture, totally nontoxic, environmental protection, easily reclaim and with low cost (battery of same capacity, is expected to reach 60% of lead-acid battery, 20% of lithium ion battery, even lower) etc. feature, and have good cycle performance, in embodiment, battery still maintains more than 90% at 4000 weeks rear capacity of circulation.Therefore, the battery in the present invention, as green energy resource of new generation, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery very much.
[pole structure battery]
The present invention also provides a kind of battery, and battery has column type structure.
Execution mode nine
A battery, battery comprises housing, is located at positive pole, negative pole, barrier film and aqueous electrolyte in housing, barrier film is arranged between positive pole and negative pole.
Positive pole comprises plus plate current-collecting body and participates in the positive active material of electrochemical reaction, positive active material comprise can be reversible the compound of deviate from-embedded ion; Negative pole is selected from metal, alloy or carbon-based material; Aqueous electrolyte comprises electrolyte, and electrolyte at least can ionize out active ion, and active ion is reduced and is deposited on negative pole formation negative electrode active material when charging, and negative electrode active material is oxidized being dissolved in aqueous electrolyte when electric discharge.
Plus plate current-collecting body, positive active material, negative pole, aqueous electrolyte and barrier film, with execution mode one, just repeat here no longer one by one.
Same, negative pole same execution mode one is set, negative pole comprises negative current collector, now negative pole can be only participate in electrode reaction as the matrix of electron collection and conduction; Or negative pole comprises negative current collector and negative electrode active material, if negative pole 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.
Concrete, the positive pole in battery, barrier film and negative pole can form cylindrical battery core by coiling and be arranged in housing.
Refer to shown in Figure 21 and 22, negative pole 160 and the barrier film 156 of battery 150 are cylinder barrel shaped, and plus plate current-collecting body 152 is cylindrical, and positive active material 158 is arranged between barrier film 156 and plus plate current-collecting body 152.Battery 150 also comprises retainer ring 154, and retainer ring 154 is plus plate current-collecting body 152, barrier film 156, negative pole 160 and housing (not shown) fixedly.The material of retainer ring 154 is polyvinyl chloride, and retainer ring 154 is two, is arranged at respectively the two ends of housing.Retainer ring 154 comprises upper strata Huan162He lower floor ring 164, and upper strata Huan162He lower floor ring 164 is formed in one, and upper strata ring 162 is plus plate current-collecting body 152 and barrier film 156 fixedly, and lower floor's ring 164 is barrier film 156 and negative pole 160 fixedly.The external diameter of upper strata ring 162 is identical with the internal diameter of negative pole 160, and the internal diameter of upper strata ring 162 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, and the internal diameter of lower floor's ring 164 is identical with the diameter of plus plate current-collecting body 152.
At plus plate current-collecting body 152, be in columniform execution mode, concrete, as shown in Figure 21 and Figure 22: a kind of battery 150, comprises plus plate current-collecting body 152, positive active material 158, barrier film 156, negative pole 160, aqueous electrolyte (not shown), retainer ring 154 and housing; Plus plate current-collecting body 152 and positive active material 158, barrier film 156, negative pole 160 and housing arranged in co-axial alignment; Negative pole 160 and barrier film 156 are cylinder barrel shaped; Positive active material 158 is arranged between plus plate current-collecting body 152 and barrier film 156; Barrier film 156 is arranged between positive active material 158 and negative pole 160; Negative pole 160 is arranged between barrier film 156 and housing; Aqueous electrolyte is arranged in housing; Retainer ring 154 is arranged at one end of housing, and retainer ring 154 is plus plate current-collecting body 152 and barrier film 156 and negative pole 160 fixedly; Preferably, plus plate current-collecting body 152 is graphite rod.
Concrete, the material of retainer ring 154 is polyvinyl chloride, retainer ring 154 is two, is arranged at respectively the two ends of battery middle shell, and a top that is arranged at battery, another is arranged at the bottom of battery.As shown in Figure 22: retainer ring 154 comprises upper strata Huan162He lower floor ring 164, upper strata Huan162He lower floor ring 164 is formed in one, and upper strata ring 162 is plus plate current-collecting body 152 and barrier film 156 fixedly, and lower floor's ring 164 is barrier film 156 and negative pole 160 fixedly.The external diameter of upper strata ring 162 is identical with the internal diameter of negative pole 160, and the internal diameter of upper strata ring 162 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, and the internal diameter of lower floor's ring 164 is identical with the diameter of plus plate current-collecting body 152.
At plus plate current-collecting body, be in columniform execution mode, battery also comprises anodal conductive agent, is arranged between plus plate current-collecting body 152 and barrier film 156 together with after anodal conductive agent mixes with positive active material 158.Concrete, first cylindrical plus plate current-collecting body 152, cylinder barrel shaped barrier film 156 and the retainer ring 154 that is arranged at battery bottom are assembled, anodal conductive agent, positive active material 158 and solvent are mixed together even formation anode sizing agent, again anode sizing agent is poured in the gap of barrier film 156 and plus plate current-collecting body 152 compositions, dry, between plus plate current-collecting body 152 and barrier film 156, form anodal conductive agent and positive active material 158.Anodal conductive agent is selected from one or more in conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and sheet metal.Solvent is selected from deionized water or ethanol.
At plus plate current-collecting body, be in columniform execution mode, the negative pole 160 of cylinder barrel shaped can be the negative current collector that first forms cylinder barrel shaped, by the negative current collector of the barrier film 156 of cylindrical plus plate current-collecting body 152, cylinder barrel shaped, cylinder barrel shaped and be arranged at the retainer ring of battery bottom fixing after, then negative electrode active material is joined between the barrier film 156 of cylinder barrel shaped and the negative current collector of cylinder barrel shaped and is obtained; Also can be after first the method by coating, plating or sputter is formed on negative current collector by negative electrode active material, then form the negative pole 160 of cylinder barrel shaped.
Battery provided by the invention, there is energy density high, power density is large, is easy to manufacture safety non-toxic, environmental protection, the feature such as easily reclaim and with low cost, and battery has good cycle performance, therefore, battery in the present invention, as green energy resource of new generation, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery very much.
Weight, the unit in percent by volume in the present invention are well-known to those skilled in the art, and for example percent by volume refers to the weight of solute in the solution of 100 milliliters.Unless otherwise defined, the familiar meaning of all specialties of using in literary composition and scientific words and one skilled in the art is identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples.
Embodiment 1
By LiMn 2o 4(Hunan China fir China fir, LMO021 type), conductive black (TIMCAL, super P), (Si Bikai can for bonding agent sodium carboxymethylcellulose, 30000) and water according to the ratio of mass ratio 90:6:1:50, mix, add 3 parts of SBR emulsions (Korea S great Jin), continue to mix 10min and make active material slurry.Using long 80 millimeters, wide 60 millimeters, the aluminium foil of thick 20 microns as plus plate current-collecting body, aluminium foil is placed in the middle of 2 thick conducting films of 50 microns, conducting film size is slightly larger than aluminium foil, be coated on aluminium foil, and it is intact to guarantee that conducting film has more part sealing than aluminium foil by heating the compound conducting film that makes.Active material slurry is evenly coated in to the first surface of composite current collector and second, and coating density is 700g/m 2, at 60 ℃, dry, roll with applying 10 tons of pressure on roll squeezer, obtain positive pole.
Concrete, conducting film is the composite material that contains polypropylene and conductive black.
Barrier film is the AGM fibreglass diaphragm of 2 millimeters of thickness, is of a size of 70 * 70 millimeters.Negative pole is the zine plate of thick 50 microns, and size and barrier film are suitable.Electrolyte is the ZnSO of 2mol/L 4li with 1mol/L 2sO 4mixed aqueous solution.
Battery is assembled in such a way: the positive pole obtaining is inserted between two negative poles, a slice barrier film is respectively set between positive pole and negative pole, after having assembled, inject 12 milliliters of electrolyte, static 3 hours, can start charge-discharge test.
Embodiment 2
In embodiment 2, plus plate current-collecting body is Copper Foil, and all the other formations 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 all the other formations of battery and method of testing are with embodiment 1.
Embodiment 4
In embodiment 4, conducting film thickness is 100 microns, and all the other formations of battery and method of testing are with embodiment 1.
Battery performance test
Battery in embodiment 1 to 4 is at room temperature carried out to charge and discharge cycles test.The condition of charge and discharge cycles test is: to be charged to 2.1V under 0.25C constant current, stop 10 minutes, then discharge into 1.4V under 1C constant current, then stop 10 minutes, as a circulation.
Figure 23 is battery charging and discharging cycle performance figure in embodiment 1, and as can be seen from the figure, battery can normally be worked, and performance is highly stable after repeatedly circulating.Same, the battery in embodiment 2 to 4 can continue, stable work.
Embodiment 5
By positive active material LiMn 2o 4, conductive agent acetylene black (AB), binding agent Kynoar (PVDF) mixes according to weight ratio 80:10:10, using 1-METHYLPYRROLIDONE as solvent, make anode sizing agent, at thickness, be to be coated with anode sizing agent in the one side of collector of 100 μ m, put in vacuum drying chamber, dry 0.5h at 60 ℃, forming thickness is the bipolar electrode of 400 μ m.Collector adopts conductive plastics, concrete, and conductive plastics is the polypropylene that contains and the composite material of conductive black.
The material of plus plate current-collecting body and negative extraction electrode is stainless steel foil, the coated a layer thickness of one side that is compounded in plus plate current-collecting body by hot pressing is the conducting film of 50 μ m, conducting film is the composite membrane of polyethylene and carbon black, according to the process of preparing bipolar electrode, at plus plate current-collecting body, scribble the positive active material of the one side coating same thickness of conducting film.The thickness of plus plate current-collecting body and negative extraction electrode is 2mm.
Aqueous electrolyte is to contain the aqueous solution that concentration is 1mol/L lithium sulfate and 2mol/L zinc sulfate; Barrier film adopts glass fibre (AGM), and the area of barrier film is less than the encirclement area of rectangular seal, and the thickness of barrier film is 600 μ m; It is highly the rectangular seal of 1mm that sealing adopts, and the area of rectangular seal is slightly less than the area of extraction electrode and collector.
Stacked rectangular seal on negative extraction electrode, then in the circle of sealing ring, place the barrier film that is soaked with aqueous electrolyte, stack gradually again bipolar electrode and positive extraction electrode, bipolar electrode and positive extraction electrode scribble the one side of positive active material and place towards negative extraction electrode, and sealing ring is used for sealing the aqueous electrolyte being arranged between positive extraction electrode and adjacent bipolar electrode and bipolar electrode and adjacent negative extraction electrode.
Battery performance test
Battery in embodiment 5 is at room temperature carried out to charge and discharge cycles test.The condition of charge and discharge cycles test is: under 1C constant current, be charged to 4.2V, stop 10 minutes, then discharge into 2.8V under 1C constant current, then stop 10 minutes, as a circulation.
Embodiment 6
In embodiment 6, the number of bipolar electrode is 3, and all the other formations of battery and preparation method are with embodiment 5.
Battery performance test
Battery in embodiment 6 is at room temperature carried out to charge and discharge cycles test.The condition of charge and discharge cycles test is: under 1C constant current, be charged to 8.4V, stop 10 minutes, then discharge into 5.6V under 1C constant current, then stop 10 minutes, as a circulation.
Embodiment 7
In embodiment 7, the number of bipolar electrode is 5, and all the other formations of battery and preparation method are with embodiment 5.
Battery performance test
Battery in embodiment 7 is at room temperature carried out to charge and discharge cycles test.The condition of charge and discharge cycles test is: under 1C constant current, be charged to 12.6V, stop 10 minutes, then discharge into 8.4V under 1C constant current, then stop 10 minutes, as a circulation.
Embodiment 8
In embodiment 8, the collector of bipolar electrode adopts stainless steel, and thickness is 50 μ m, and all the other formations of battery, preparation 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 coated with conductive film, and all the other formations of battery, preparation method and battery performance test are with embodiment 5.
Table 1 is that the battery in embodiment 5 to 9 discharges and recharges under 1C multiplying power, the battery performance that charge and discharge cycles is 100 times:
Table 1
Figure BDA0000373452590000361
Embodiment 10
By positive active material LiMn 2o 4, super-p carbon black, bonding agent PVDF mix according to part by weight 8:1:1, usings NMP as solvent, makes anode sizing agent, is evenly coated in the plus plate current-collecting body graphite foil of thickness 80 μ m, subsequent drying, compacting obtain positive pole; Negative pole comprises the graphite foil of zinc paper tinsel and thickness 50 μ m, 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 to cylindrical battery core by coiling, be arranged in the housing of cylinder barrel shaped; The electrolyte adding in battery is the aqueous solution that contains 2mol/L lithium acetate and 1.5mol/L zinc acetate, by drip the pH of the LiOH solution adjusting electrolyte of 0.1mol/L in electrolyte, is 4.Under room temperature, after battery standing 12h, with current charges and the electric discharge of 100mA, voltage range is 1.5-2.35V.
Embodiment 11
The mode identical with embodiment 10 manufactured battery, and difference is: use the 316 type stainless steels through transpassivation to replace the graphite foil in embodiment 10 negative poles.
Embodiment 12
The mode identical with embodiment 10 manufactured battery, and difference is: with Copper Foil, replace the graphite foil in embodiment 10 negative poles.
Embodiment 13
A battery, plus plate current-collecting body is graphite rod, and diameter is 4mm, and length is 62mm; The material of barrier film is nonwoven fabrics, and 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 comprises Copper Foil and zinc, and zinc is formed on Copper Foil by sputter, obtains cylinder barrel shaped negative pole, and 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 the copper polar ear that 0.1mm is thick, 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, and the length of housing is 60mm; The material of retainer ring is polyvinyl chloride (PVC), and retainer ring has two, is arranged at respectively the two ends of battery, what be placed in battery top is the first retainer ring, as for battery bottom be the second retainer ring, retainer ring comprises upper strata Huan He lower floor ring, upper strata Huan He lower floor ring is formed in one, the internal diameter of upper strata ring is 4mm, 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 is 16mm, and the thickness of lower floor's ring is 1mm.
The assembling process of concrete battery is: with LiMn 2o 4for positive active material, by positive active material, conductive agent Super-P, be blended in deionized water according to the part by weight of 90:10, mix and make anode sizing agent; After first barrier film and the second retainer ring and graphite rod being assembled, anode sizing agent is poured in the gap of barrier film and graphite rod formation, pouring anode sizing agent amount into is 10g, dry at 80 ℃, obtain positive pole, in barrier film, the mixture of positive active material and conductive agent is 5g; At cylinder barrel shaped barrier film, cylinder barrel shaped negative pole is set outward again, cylinder barrel shaped negative pole arranges cylinder barrel shaped housing outward; Electrolyte is 544g zinc chloride and 21g anhydrous Lithium chloride, be dissolved in 600g deionized water, toward titration 0.1mol/L lithium hydroxide in electrolyte, the pH value of electrolyte is adjusted to 4.3 again, then with deionized water, is settled to 1L and obtains, in the battery of the present embodiment, add this electrolyte of 5g.After barrier film, the second retainer ring, graphite rod, positive pole, negative pole, housing and electrolyte are assembled, standing 12 hours, start subsequently current charges and electric discharge with 100mA, charging/discharging voltage interval is 1.5-2.35V.
Embodiment 14
A battery, plus plate current-collecting body is graphite rod, and diameter is 4mm, and length is 62mm; The material of barrier film is nonwoven fabrics, and 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 comprises Copper Foil and zinc, and 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 the copper polar ear that 0.1mm is thick, 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, and the length of housing is 60mm; The material of retainer ring is polyvinyl chloride (PVC), and retainer ring has two, is arranged at respectively the two ends of battery, what be placed in battery top is the first retainer ring, as for battery bottom be the second retainer ring, retainer ring comprises upper strata Huan He lower floor ring, upper strata Huan He lower floor ring is formed in one, the internal diameter of upper strata ring is 4mm, 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 is 16mm, and the thickness of lower floor's ring is 1mm.
The assembling process of concrete battery is: with LiMn 2o 4for positive active material, by positive active material 22, conductive agent Super-P, be blended in deionized water according to the part by weight of 90:10, mix and make anode sizing agent; After first barrier film and the second retainer ring and graphite rod being assembled, anode sizing agent is poured in barrier film, pouring anode sizing agent amount into is 12g, dry at 80 ℃, obtains positive pole, and in barrier film, the mixture of positive active material and conductive agent is 6g; After the retainer ring of the barrier film of the Copper Foil of cylinder barrel shaped and graphite rod, cylinder barrel shaped and second is fixed, then zinc is joined between the barrier film of cylinder barrel shaped and the Copper Foil of cylinder barrel shaped and obtains cylinder barrel shaped negative pole; Electrolyte is 544g zinc chloride and 21g anhydrous Lithium chloride, be dissolved in 600g deionized water, toward titration 0.1mol/L lithium hydroxide in electrolyte, the pH value of electrolyte is adjusted to 4.3 again, then with deionized water, is settled to 1L and obtains, in the battery of the present embodiment, add this electrolyte of 6g.After barrier film, the second retainer ring, graphite rod, positive pole, negative pole, housing and electrolyte are assembled, standing 12 hours, start subsequently current charges and electric discharge with 100mA, charging/discharging voltage interval is 1.5-2.35V.
Embodiment 15
The mode identical with embodiment 13 manufactured battery, and difference is: by graphite foil, replace the Copper Foil in negative pole.
The battery providing in embodiment 10 to 15, battery has good cycle performance.
Although inventor has done more detailed elaboration and has enumerated technical scheme of the present invention, be to be understood that, to those skilled in the art, above-described embodiment is modified and/or flexible or to adopt the replacement scheme being equal to be obvious, all can not depart from the essence of spirit of the present invention, the term occurring in the present invention, for to the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.

Claims (20)

1. a battery, comprises housing, is arranged at the positive pole in described housing, two negative poles, aqueous electrolyte and barrier films,
Described positive pole comprises composite current collector and positive active material, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described composite current collector has the first surface that is oppositely arranged and second, it is upper that described positive active material is arranged on described first surface and second, described positive active material can be reversible deviate from-embedded ion;
Described negative pole is selected from metal, alloy or carbon-based material;
Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge;
Described barrier film keeps described aqueous electrolyte;
Described positive pole and negative pole are stacked to be arranged in described housing, and described positive pole is placed between described two negative poles, and described two negative poles share described positive pole, and described barrier film is between described positive pole and negative pole.
2. a battery, comprises housing, is arranged at two positive poles, negative pole, aqueous electrolyte and barrier films in described housing,
Described positive pole comprises composite current collector and positive active material, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described composite current collector has the first surface that is oppositely arranged and second, described first surface is relative with described negative pole, on at least described first surface, be provided with described positive active material, described positive active material can be reversible deviate from-embedded ion;
Described negative pole is selected from metal, alloy or carbon-based material;
Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge;
Described barrier film keeps described aqueous electrolyte;
Described positive pole and negative pole are stacked to be arranged in described housing, and described negative pole is placed between described two positive poles, and described two positive poles share described negative pole, and described barrier film is between described positive pole and negative pole.
3. a battery, comprises housing, is arranged at positive pole, negative pole, aqueous electrolyte and barrier film in described housing,
Described positive pole comprises composite current collector and positive active material, described composite current collector comprises plus plate current-collecting body and is coated on the conducting film on described plus plate current-collecting body, described composite current collector has the two sides being oppositely arranged, wherein, in at least described composite current collector one side relative with described negative pole, be provided with positive active material, described positive active material can be reversible deviate from-embedded ion;
Described battery comprises that n is to described positive pole and negative pole, n >=2, and two adjacent positive poles share the negative pole between two positive poles, and two adjacent negative poles share the positive pole between two negative poles;
Described negative pole is selected from metal, alloy or carbon-based material;
Described aqueous electrolyte comprises electrolyte, described electrolyte at least can ionize out active ion, described active ion is reduced and is deposited on described negative pole formation negative electrode active material when charging, and described negative electrode active material is oxidized being dissolved in described aqueous electrolyte when electric discharge;
Described barrier film keeps described aqueous electrolyte;
The stacked arrangement that described positive pole, negative pole replace is in described housing, and described barrier film is between described positive pole and negative pole.
4. according to the battery described in any one in claim 1-3, it is characterized in that: described housing is square.
5. battery according to claim 4, is characterized in that: described positive pole, barrier film and negative pole form tabular.
6. battery according to claim 5, is characterized in that: described positive pole, barrier film and negative pole winding shaping.
7. according to the battery described in any one in claim 1-3, it is characterized in that: described housing is cylinder barrel shaped described positive pole, described barrier film, described negative pole and described housing arranged in co-axial alignment.
8. battery according to claim 7, is characterized in that: described positive pole, barrier film and negative pole form cylindrical being arranged in described housing by coiling.
9. according to the battery described in any one in claim 1-3, it is characterized in that: the material of described conducting film comprises polymer and conductive filler.
10. battery according to claim 9, is characterized in that: described polymer is selected from polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, at least one in polyether sulfone, butadiene-styrene rubber or fluororesin.
11. batteries according to claim 9, is characterized in that: described conductive filler is selected from conducting polymer, carbon-based material or metal oxide.
12. according to the battery described in any one in claim 1-3, it is characterized in that: the material of described conducting film is selected from conducting polymer.
13. according to the battery described in any one in claim 1-3, it is characterized in that: described housing is set to aluminum plastic film.
14. according to the battery described in any one in claim 1-3, it is characterized in that: described housing is provided with fluid infusion mouth, and described fluid infusion mouth is for supplementing described aqueous electrolyte.
15. according to the battery described in any one in claim 1-3, it is characterized in that: described battery also comprises for controlling the safety valve of described housing internal pressure.
16. according to the battery described in any one in claim 1-3, it is characterized in that: described positive active material has spinel structure, layer structure or olivine structural.
17. according to the battery described in any one in claim 1-3, it is characterized in that: the material of described plus plate current-collecting body is selected from a kind of in vitreous carbon, graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a kind of through in the above-mentioned metal of Passivation Treatment, or stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or a kind of through in the above-mentioned alloy of Passivation Treatment.
18. according to the battery described in any one in claim 1-3, it is characterized in that: the material of described negative pole is selected from least one in Metal Zn, Ni, Cu, Ag, Pb, Sn, Fe, Al or the process described metal of Passivation Treatment, or at least one in the alloy that contains above-mentioned metal, or at least one in graphite foil, graphite flake, carbon cloth, carbon felt, carbon fiber, or copper is zinc-plated, or brass.
19. according to the battery described in any one in claim 1-3, it is characterized in that: described active ion comprises metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
20. the battery according to described in any one in claim 1-3, is characterized in that: described active ion is present in described aqueous electrolyte with at least one form in hydrochloride, sulfate, acetate, nitrate or formates.
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