CN107256946A - Battery - Google Patents

Battery Download PDF

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Publication number
CN107256946A
CN107256946A CN201710304878.8A CN201710304878A CN107256946A CN 107256946 A CN107256946 A CN 107256946A CN 201710304878 A CN201710304878 A CN 201710304878A CN 107256946 A CN107256946 A CN 107256946A
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CN
China
Prior art keywords
battery
active material
ion
electrolyte
negative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710304878.8A
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Chinese (zh)
Inventor
陈璞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Positec Power Tools Suzhou Co Ltd
Original Assignee
Positec Power Tools Suzhou Co Ltd
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Publication date
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Publication of CN107256946A publication Critical patent/CN107256946A/en
Pending legal-status Critical Current

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/661—Metal or alloys, e.g. alloy 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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H01M4/662—Alloys
    • 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
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/666—Composites in the form of mixed 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
    • H01M4/669—Steels
    • H—ELECTRICITY
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    • 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
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Present invention is disclosed a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, and the positive active material being capable of reversible abjection embedded ion；The negative pole includes being not involved in the negative current collector of electrochemical reaction and is formed at the negative electrode active material on the negative current collector surface；The electrolyte includes that electrolyte can be dissolved and makes the solvent of the electrolyte ionization；The electrolyte, which can be ionized out, to be occurred the active ion of reduction deposition and oxidation dissolution in the negative pole in charge and discharge process or/and is capable of the embedded ion of reversible abjection in the positive pole；The negative electrode active material in discharge process can oxidation dissolution be the active ion.The battery safe operation that the present invention is provided, production cost is low, and cycle performance is excellent and the life-span is permanent, is suitable as the energy storage system in large-scale energy storage field and the substitute of lead-acid battery.

Description

Battery
Technical field
The invention belongs to electrochemical energy storage field, and in particular to a kind of battery.
Background technology
The mankind result in the rapidly expansion in secondary cell market to the extensive utilization of new energy.In current new energy system Requirement to secondary cell is ubiquitous.Either electric automobile, wind energy, solar grid-connected or peak load regulation network, are all badly in need of one Plant cheap, reliably, the secondary cell of safety and long lifespan.The secondary cell developed at present is concentrated mainly on lithium ion battery, The high temperature sodium-sulphur battery, sodium nickel chlorine battery and vanadium flow battery.These batteries all have respective advantage, such as lithium ion battery and The high temperature sodium-sulphur battery long lifespan and energy density are high, and vanadium flow battery even more possesses unlimited life-span etc. in theory.But no matter Which kind of battery, can not all meet cheap simultaneously, reliably, the requirement of safety and long lifespan.Traditional lithium ion battery is prohibitively expensive, And have potential safety hazard；The high temperature sodium-sulphur battery manufacturing technology threshold is high, and price is expensive；The multinomial technical bottleneck of vanadium flow battery is current all Fail to obtain breakthrough etc..
The research of aquo-lithium ion battery is devoted to for this Many researchers, it is desirable to which lithium ion battery is greatly reduced with this Cost and improve security, and propose some with LiMn2O4For positive pole, the oxide such as LiV of vanadium3O8Deng for negative pole, water Stability difference and vanadium for the battery of electrolyte, but therefore class negative pole discharge and recharge in water have certain toxicity, so as to limit The development of such battery is made.So far, it has been suggested that the structure of aquo-lithium ion secondary cell all fail to break away to be based on The structure of lithium ion abjection-embedding principle, such as the VO having had been reported that2/LiMn2O4, LiV3O8/LiNi0.81Co0.19O2, TiP2O7/LiMn2O4, LiTi2(PO4)3/LiMn2O4, LiV3O8/LiCoO2Deng.
The content of the invention
The present invention is intended to provide a kind of inexpensive, safe and reliable and function admirable battery.
A kind of battery, including positive pole, negative pole, electrolyte, the positive pole include positive active material, the positive electrode active material Matter can it is reversible deviate from-embedded ion；The negative pole includes being not involved in the negative current collector of electrochemical reaction and is formed at described The negative electrode active material on negative current collector surface；The electrolyte includes that electrolyte can be dissolved and makes the electrolyte ionization Solvent；The electrolyte can ionize out the activity in negative pole generation reduction-deposition and oxidation-dissolving in charge and discharge process Ion or/and the positive pole can it is reversible deviate from-ion that is embedded in；The negative electrode active material being capable of oxygen in discharge process Change-be dissolved as the active ion.
It is preferred that, the negative electrode active material is formed at the negative current collector by the method for coating, plating or sputtering On.
It is preferred that, the negative electrode active material includes metal simple-substance, and the metal is in Zn, Fe, Cr, Cu, Mn, Ni It is at least one.
It is preferred that, the material of the negative current collector is selected from W metal, Cu, Ag, Pb, Sn, Fe, Al or passes through Passivation Treatment Above-mentioned metal in one kind.
It is preferred that, the material of the negative current collector is selected from carbon-based material, stainless steel, silicon or the metal with plating/coating, Plating/the coating contains at least one of C, Sn, In, Ag, Pb, Co simple substance, alloy or oxide.
It is preferred that, the thickness range of the plating/coating is between 1-1000nm.
It is preferred that, the negative pole also includes the porous layer for being formed at the negative current collector surface, and the porous layer has Micron or sub-micron or nanoscale hole.
It is preferred that, the porous layer includes carbon-based material, and the carbon-based material is selected from section's qin carbon black, activated carbon, carbon nanometer At least one of pipe, carbon fiber, graphite.
It is preferred that, the porous layer includes carbon-based material, and the carbon-based material is the mixing of activated carbon powder and binding agent Thing, the weight percentage ranges that the activated carbon powder accounts for the porous layer are 20-99%.
It is preferred that, the negative pole also includes the graphene layer for being formed at the negative current collector surface.
It is preferred that, the negative current collector is copper, and the negative electrode active material is zinc.
It is preferred that, the negative electrode active material is formed at the negative current collector by surface preparation, and the surface is located in advance Reason is selected from least one of mechanical treatment, chemical treatment or electrochemical treatments.
It is preferred that, the pH value range of the electrolyte is 3-7.
It is preferred that, the active ion with chlorate, sulfate, nitrate, acetate, formates, phosphate extremely A kind of few form is present in the electrolyte.
It is preferred that, the positive active material can it is reversible deviate from-be embedded in lithium ion, sodium ion, magnesium ion or zinc ion.
It is preferred that, the material of the plus plate current-collecting body be selected from graphite, stainless steel, aluminium alloy, the stainless steel through transpassivation or Aluminium alloy.
Present invention also offers a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, The positive active material can it is reversible deviate from-embedded ion；The negative pole includes the negative electrode active material for participating in electrochemical reaction Matter；The electrolyte includes at least one solvent that can be dissolved electrolyte and ionize the electrolyte；The electrolysis mass-energy At least one the ion of reversible abjection-insertion can occur in the positive pole for enough ionize out；The positive active material does not include The ion of the reversible abjection-insertion；The battery work first be the reversible abjection-insertion ion insertion it is described just Pole active material, the negative electrode active material aoxidize-are dissolved as the discharge process of the active ion.
Present invention also offers a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, The positive active material can it is reversible deviate from-embedded ion；The negative pole includes the negative electrode active material for participating in electrochemical reaction Matter；The electrolyte includes at least one solvent that can be dissolved electrolyte and ionize the electrolyte；The electrolysis mass-energy Enough ionizing out at least one active ion for occurring reduction-deposition in the negative pole can occur with least one in the positive pole The ion of reversible abjection-insertion；The ion of the reversible abjection-insertion can be deviate from and be embedded in the positive active material；Institute It is ion, the active ion for deviating from the reversible abjection-insertion in the positive active material to state working first for battery Reduce-be deposited as the charging process of the negative electrode active material or the ion of the reversible abjection-insertion be embedded into it is described just Pole active material, the negative electrode active material aoxidize-are dissolved as the discharge process of the active ion.
It is preferred that, the battery work first be the positive active material deviate from the reversible abjection-insertion ion, The active ion reduces-is deposited as the charging process of the negative electrode active material.
Present invention also offers a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, The positive active material can it is reversible deviate from-embedded ion；The negative pole includes the negative electrode active material for participating in electrochemical reaction Matter；The electrolyte includes at least one solvent that can be dissolved electrolyte and ionize the electrolyte；The electrolysis mass-energy At least one the ion of reversible abjection-insertion can occur in the positive pole for enough ionize out；The positive active material can take off Go out and be embedded in the ion of the reversible abjection-insertion；The battery work first be the reversible abjection-insertion ion it is embedding Enter to the positive active material, the negative electrode active material to aoxidize-be dissolved as the discharge process of the active ion.
Present invention also offers a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, The positive active material can it is reversible deviate from-embedded ion；The negative pole includes the negative electrode active material for participating in electrochemical reaction Matter；The electrolyte includes at least one solvent that can be dissolved electrolyte and ionize the electrolyte；The electrolysis mass-energy It is enough to ionize out at least one active ion in negative pole generation reduction-deposition；The positive active material can deviate from and The ion of the embedded reversible abjection-insertion；The battery work first be deviate from the positive active material it is described can Inverse abjection-ion of insertion, the active ion are in described cathodic reduction-is deposited as the charging of the negative electrode active material Journey.
Present invention also offers a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, The positive active material can it is reversible deviate from-embedded ion；The negative pole includes the negative electrode active material for participating in electrochemical reaction Matter；The electrolyte includes at least one solvent that can be dissolved electrolyte and ionize the electrolyte；The electrolysis mass-energy It is enough to ionize out at least one active ion in negative pole generation reduction-deposition；It is reversible described in the positive active material The ion of abjection-insertion is in saturation state；The battery work first be deviate from the positive active material it is described can Ion, the active ion of inverse abjection-insertion are deposited as the charging process of the negative electrode active material in the cathodic reduction.
Present invention also offers a kind of battery, including positive pole, negative pole, electrolyte, the positive pole includes positive active material, The positive active material can it is reversible deviate from-embedded ion；The negative pole includes the negative electrode active material for participating in electrochemical reaction Matter；The electrolyte includes at least one solvent that can be dissolved electrolyte and ionize the electrolyte；The electrolysis mass-energy It is enough to ionize out at least one active ion in negative pole generation reduction-deposition；It is reversible described in the positive active material The ion of abjection-insertion is in hypersaturated state, the surface of the positive active material by metal or modified metal oxide or Cladding；Working first for the battery is to deviate from the ion of the reversible abjection-insertion, the work in the positive active material Charging process of the property ion in the cathodic reduction-the be deposited as negative electrode active material.
It is preferred that, the metal is aluminium, and the metal oxide is aluminum oxide.
A kind of battery safe operation that the present invention is provided, production cost are low, cycle performance is excellent and the life-span is permanent, simultaneously Battery is worked with various modes first, facilitates user according to self-demand to select, and the battery in the present invention is suitable as greatly The energy storage system in type energy storage field and the substitute of lead-acid battery.
Brief description of the drawings
Fig. 1 is first embodiment of the invention battery structure schematic diagram；
Fig. 2 is first embodiment of the invention battery charging process schematic diagram；
Fig. 3 is first embodiment of the invention battery discharge procedure schematic diagram；
Fig. 4 is second embodiment of the invention battery structure schematic diagram；
Fig. 5 is cyclic voltammetry curve of the stainless steel 304 of unpassivated processing in embodiment 1-1 in stannous sulphate electrolyte Figure；
Fig. 6 is cyclic voltammetry curve of the Stainless steel 316 in stannous sulphate electrolyte Jing Guo Passivation Treatment in embodiment 1-2 Figure；
Fig. 7 is that cyclic voltammetrics of the Stainless steel 316 P in nitric acid salt electrolyte in embodiment 1-3 Jing Guo Passivation Treatment is bent Line chart；
Fig. 8 is cyclic voltammetry curve figure of the aluminium alloy being passivated in embodiment 1-4 in acetic acid salt electrolyte；
Fig. 9 is cyclic voltammetry curve figure of the aluminium alloy being passivated in embodiment 1-5 in stannous sulphate electrolyte；
Figure 10 is cyclic voltammetry curve figure of the graphite foil in hydrochloric acid salt electrolyte in embodiment 1-6；
Figure 11 is not to be passivated cyclic voltammetry curve figure of the stainless steel in hydrochloric acid salt electrolyte in embodiment 1-7；
Figure 12 is the voltage and the graph of relation of discharge capacity for the battery that embodiment 3-1 is provided；
Figure 13 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 3-1 is provided；
Figure 14 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 3-2 is provided；
Figure 15 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 3-3 is provided；
Figure 16 is the coulombic efficiency and the graph of relation of cycle-index for the battery that embodiment 3-3 is provided；
Figure 17 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 3-4 is provided；
Figure 18 is the structural representation that negative current collector surface is formed with porous layer in embodiment 4-1；
Figure 19 is the close-up schematic view of porous layer in Figure 18；
Figure 20 is the curve map for the battery first charge-discharge voltage-capacity that embodiment 4-1 is provided；
Figure 21 is the cyclic voltammetry curve figure for the battery that embodiment 5-1 is provided；
Figure 22 is the cyclic voltammetry curve figure for the battery that embodiment 5-2 is provided；
Figure 23 is the cyclic voltammetry curve figure for the battery that embodiment 5-3 is provided；
Figure 24 is the cyclic voltammetry curve figure for the battery that embodiment 5-4 is provided；
Figure 25 is the cyclic voltammetry curve figure for the battery that embodiment 5-6 is provided；
Figure 26 is the cyclic voltammetry curve figure for the battery that embodiment 5-9 is provided；
Figure 27 is the relation curve of the battery first charge-discharge that embodiment 6-1 is provided and voltage；
Figure 28 is the discharge capacity of the cell that embodiment 6-1 is provided and the graph of relation of cycle-index；
Figure 29 is the battery coulombic efficiency that embodiment 6-1 is provided and the graph of relation of cycle-index；
Figure 30 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 6-2 is provided；
Figure 31 is the battery coulombic efficiency that embodiment 6-2 is provided and the graph of relation of cycle-index；
Figure 32 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 6-4 is provided；
Figure 33 is the discharge capacity and the graph of relation of cycle-index for the battery that embodiment 6-5 is provided.
Wherein：
10. the active ion of 20. negative pole of positive pole 28.
12. the porous layer of 22. negative current collector of plus plate current-collecting body 30.
14. the negative electrode active material of positive active material 24.
16. the active ion sedimentary of ion 26. of reversible abjection-insertion
Embodiment
The battery that the present invention is provided has higher energy density, stable cycle performance, in such as mobile phone, notebook computer Deng portable type electronic product, electric automobile, the field such as electric tool has considerable application prospect.
A kind of battery, including positive pole 10, negative pole 20 and electrolyte (not shown).Positive pole 10 includes plus plate current-collecting body 12 and ginseng With the positive active material 14 of electrochemical reaction, positive active material 14 can it is reversible deviate from-embedded ion；Negative pole 20 is at least wrapped Include negative current collector 22；Electrolyte includes at least one solvent that can be dissolved electrolyte and ionize electrolyte；It is electrolysed mass-energy Enough active ions 28 ionized out at least one charge and discharge process in negative pole generation reduction-deposition and oxidation-dissolving.
Refer to shown in Fig. 1, Fig. 1 is first embodiment of the invention battery structure schematic diagram, in the first embodiment, GND 20 only includes negative current collector 22.
Positive active material 14 participates in positive pole reaction, and can it is reversible deviate from-embedded ion or functional group.Specifically , positive active material 14 can it is reversible deviate from-be embedded in lithium ion, sodium ion, zinc ion or magnesium ion.
Positive active material 14 can meet formula Li1+xMnyMzOkCan it is reversible deviate from-point that is embedded in lithium ion is brilliant The compound of stone structure, wherein, -1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M be selected from Na, Li, Co, Mg, At least one of Ti, Cr, V, Zn, Zr, Si, Al.It is preferred that, positive active material 14 contains LiMn2O4.It is furthermore preferred that positive pole Active material 14 contains the LiMn through overdoping or coating modification2O4。
Positive active material 14 can meet formula Li1+xMyM′zM″cO2+nCan it is reversible deviate from-be embedded in lithium ion The compound of layer structure, wherein, -1<X≤0.5,0≤y≤1,0≤z≤1,0≤c≤1, -0.2≤n≤0.2, M, M ', M " Be respectively selected from Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al at least one of.It is preferred that, positive active material 14 contains There is LiCoO2。
Positive active material 14 can meet formula LixM1-yM′y(XO4)nCan it is reversible deviate from-be embedded in lithium ion The compound of olivine structural, wherein, 0<X≤2,0≤y≤0.6,1≤n≤1.5, M be selected from Fe, Mn, V or Co, M ' be selected from Mg, At least one of Ti, Cr, V or Al, X is selected from least one of S, P or Si.It is preferred that, positive active material 14 contains LiFePO4。
In current Lithium Battery Industry, nearly all positive active material 14 all can be through modifications such as overdoping, claddings. But adulterate, the means such as coating modification cause the chemical general formula of material to express complicated, such as LiMn2O4It can not represent wide at present The formula of general " LiMn2O4 " used, and should be with formula Li1+xMnyMzOkIt is defined, widely including by various modifications LiMn2O4.Likewise, LiFePO4And LiCoO2Also it should be construed broadly to include modified by various doping, cladding etc. , formula corresponds with LixM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nPositive active material.
When the positive active material 14 of the present invention is reversible abjection-insertion lithium ion compound, such as LiMn can be selected2O4、 LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).In addition, can deviate from-it is embedded in sodium The compound of ion such as NaVPO4F, can deviate from-be embedded in the compound such as γ-MnO of zinc ion2, can deviate from-be embedded in the change of magnesium ion Compound such as MgMxOy(wherein M is a kind of metal, 0.5<x<3,2<y<6) and with similar functions ,-embedded ion can be deviate from Or the compound of functional group can serve as the positive active material 14 of battery of the present invention.
In specific embodiment, when preparing anode sizing agent, in anode sizing agent in addition to positive active material 14, also Conductive agent and binding agent need to be added.
Conductive agent be selected from conducting polymer, activated carbon, graphene, carbon black, carbon fiber, metallic fiber, metal dust and One or more in sheet metal.
Binding agent is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination Polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, one kind in glycol dimethacrylates or The mixture and derivative of above-mentioned polymer.In a specific embodiment, binding agent is selected from polytetrafluoroethylene (PTFE) (PTFE) or poly- inclined PVF (PVDF).
The carrier that plus plate current-collecting body 12 only conducts and collected as electronics, is not involved in electrochemical reaction, i.e., worked in battery In voltage range, what plus plate current-collecting body 12 can be stablized is present in electrolyte without other side reactions generation, so as to ensure Battery has stable cycle performance.The one kind of the material of plus plate current-collecting body 12 in carbon-based material, metal or alloy.
Specifically, carbon-based material is selected from vitreous carbon, graphite, carbon felt, carbon fiber or the conduction material with 3D bicontinuous structures One kind in material.Wherein, the conductive material with 3D bicontinuous structures includes but are not limited to foamy carbon.Graphite is included but not only It is limited to graphite foil and graphite cake.
One kind in above-mentioned metal of the metal selected from Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or Jing Guo Passivation Treatment.
Alloy is selected from stainless steel, aluminium alloy, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-Rh alloys Or one kind in the above-mentioned alloy Jing Guo Passivation Treatment.Stainless steel includes stainless steel foil or stainless (steel) wire, specifically, stainless steel Model can be but not limited to the stainless steel of 300 series, such as stainless steel 304,316,316L or 316P.The model of aluminium alloy can be with It is but not limited to the aluminium alloy of 6000 series, such as aluminium alloy 6061.
Negative pole 20 only includes negative current collector 22, and the carrier that negative current collector 22 only conducts and collected as electronics, It is not involved in electrochemical reaction.
The material of negative current collector 22 is selected from W metal, Cu, Ag, Pb, Mn, Sn, Fe, Al, Zn or by Passivation Treatment At least one of above-mentioned metal, either elemental silicon or carbon-based material, wherein, carbon-based material includes graphite material, such as business The paper tinsel of the graphite compacting of industry, the part by weight scope wherein shared by graphite is 90-100%.The material of negative current collector 22 is also Stainless steel or the stainless steel of passivated processing can be selected from.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, together Sample, the model of stainless steel can be but not limited to the stainless steel of 300 series, such as stainless steel 304,316,316L or 316P.
In addition, negative current collector 22 is also selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, so as to reduce negative pole The generation of side reaction.Plating/coating is selected from least one in the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy, or oxide Kind.The thickness range of plating/coating is 1-1000nm.For example：Plate tin on the negative current collector surface of copper foil or graphite foil, lead or Silver.
The main purpose that plus plate current-collecting body 12 or negative current collector 22 are passivated into processing is to make the surface shape of collector Into the oxide-film of one layer of passivation, so that in battery charge and discharge process, collection and the conduction electronics of stabilization can be played a part of, and It cannot participate in cell reaction, it is ensured that battery performance is stable.Collector deactivating process for the treatment of includes chemical passivation processing or electrochemistry Passivation Treatment.
Chemical passivation processing is included by oxidizing collector, makes collection liquid surface formation passivating film.Oxidant is selected The principle selected is that oxidant can make collection liquid surface one layer of passivating film of formation without dissolving collector.Oxidant is selected from but not only It is limited to concentrated nitric acid or ceric sulfate (Ce (SO4)2)。
Specifically, chemical passivation process step is：Collector is inserted in oxidizing agent solution, maintains 0.5-1 hours, makes collection Flow surface formation passivating film, finally takes out collector and cleans and dry.
In an embodiment that stainless (steel) wire or stainless steel foil are handled with chemical passivation, specific Passivation Treatment process is： At 50 DEG C, stainless steel is inserted to 20% concentrated nitric acid solution, 0.5 hour is maintained, makes stainless steel surfaces formation passivating film, most Stainless steel is taken out afterwards to be cleaned and dried in 50 DEG C of drying box with water.
In another embodiment that stainless (steel) wire or stainless steel foil are handled with chemical passivation, specific Passivation Treatment process For：Stainless steel is inserted to 0.75mol/L Ce (SO4)2In solution, 0.5 hour is maintained, makes stainless steel surfaces formation passivating film, Stainless steel is finally taken out to be cleaned and dried in 50 DEG C of drying box with water.
Electrochemical passivation processing includes carrying out collector discharge and recharge or the battery containing collector is carried out at discharge and recharge Reason, makes collection liquid surface formation passivating film.
Discharge and recharge directly is carried out to collector, i.e., in collector for the processing of battery assembling advance row pre-passivating, specifically, Discharge and recharge, then corresponding selection are carried out to the three-electrode system using collector as working electrode suitably to electrode and reference electricity Pole.Voltage is charged to 2.35-2.45V during charging, and voltage is put to 1.35-1.45V during electric discharge.Collector can be metal, such as Metallic aluminium；Collector can also be alloy, such as stainless steel or aluminium alloy.It is of course also possible to use using collector as working electrode Two electrode systems carry out discharge and recharge, voltage is charged to 2.35-2.45V during charging, and voltage is put to 1.35-1.45V during electric discharge.
In one the directly embodiment of passivation aluminium alloy collector, using aluminium alloy as working electrode, zinc paper tinsel conduct To electrode and reference electrode, electrolyte is the aqueous solution containing 1.5mol/L zinc acetates and 3mol/L lithium acetates, to three electrode bodies System carries out discharge and recharge, and voltage is charged to 2.4V during charging so that aluminum alloy surface aoxidizes the oxidation for forming one layer of passivation under 2.4V Film, blanking voltage is 1.4V during electric discharge.
The battery containing collector can also be carried out discharge and recharge to reach the purpose for being passivated collector, charged When voltage be charged to 2.35-2.45V, voltage is put to 1.35-1.45V during electric discharge, and discharge and recharge number of times is not less than 1.Collector can To be metal, such as metallic aluminium；Collector can also be alloy, such as stainless steel or aluminium alloy.
Collector is assembled into after battery in the embodiment of progress Passivation Treatment at one, positive active material 14 is LiMn2O4, plus plate current-collecting body 12 is aluminium alloy, and negative current collector 22 is copper foil, electrolyte be containing 1.5mol/L zinc acetates and The aqueous solution of 3mol/L lithium acetates, voltage is charged to 2.4V during charging, that is, blanking voltage when charging is 2.4V so that aluminium alloy Surface aoxidizes one layer of passivating film of formation under 2.4V；Blanking voltage is 1.4V during electric discharge, and it is not small to carry out discharge and recharge number of times to battery In 1 time.The number of times of battery charging and discharging is more, and the effect of aluminium alloy passivation is better, more stable in the electrolytic solution.
In the method for aluminium alloy is handled using electrochemical passivation, when voltage reaches after 2.4V and is kept for one section during charging Between, the corrosion current of aluminium alloy can be significantly reduced with the increase held time.Tieed up specifically, charging voltage reaches after 2.4V Holding the time progressively extended to 1 hour from 10 minutes, and the corrosion current of aluminium alloy can be remarkably decreased, and be held time from 1 hour progressively 24 hours are extended to, it is not it is obvious that therefore, it is furthermore preferred that charging voltage reaches after 2.4V and maintained extremely that corrosion current, which declines, It is few 1 hour.
Electrolyte is weak acid or neutral aqueous solution, such as chlorate, sulfate, nitrate, acetate, formates or phosphoric acid Salt, plus plate current-collecting body 12 and negative current collector 22 can keep stable in the electrolytic solution, i.e., do not have under battery operating voltage window There is side reaction, so as to ensure the stability of battery performance.The deactivating process for the treatment of for the collector that the present invention is provided, to positive pole Collector 12 and negative current collector 22 are all suitable for.
In order that the active ion 28 in electrolyte deposited on the surface of negative pole 20 it is more uniform, the surface of negative pole 20 is formed with Porous layer 30, porous layer 30 is such as coated in any suitable manner, compacting mode is formed at the surface of negative pole 20.
The thickness range of porous layer 30 is 0.05-1mm, and porous layer 30 has micron or sub-micron or nanoscale hole, micro- The volume range that rice or submicron order hole account for porous layer 30 is 50-95%.Nanoscale hole accounts for the volume range of porous layer 30 10-99%, the scope of the average diameter of nanoscale hole is 1-999nm, it is preferred that the scope of the average diameter of nanoscale hole For 1-150nm.
Porous layer 30 is not involved in the electrochemical reaction of negative pole 20, and porous layer 30 has very big specific surface area, can be to fill The active ion 28 for occurring deposition-reduction in electric process provides bigger deposition specific surface area so that active ion 28 is in negative pole The surface of collector 22 deposits more uniform, the effective generation for reducing negative pole dendrite.In addition, by being formed at negative current collector The porous layer 30 on 22 surfaces, can also shorten migration distance in the charge and discharge process of active ion 28, and active ion 28 only needs to expand Charge and discharge process can just be completed by dissipating shorter distance, solve in the course of reaction of active ion 28 and there is asking for diffusional resistance Topic.Simultaneously as being provided with porous layer 30 in negative pole 20, thinner barrier film can be used when preparing battery, battery is charged During, especially overcharge when the oxygen that produces of positive pole can more readily migrate into negative pole 20 and reduced, strengthen battery Invertibity.
The material of porous layer 30 is selected from carbon-based material, and carbon-based material is selected from carbon black, activated carbon, CNT, carbon fiber, stone At least one of ink.
Carbon black includes but are not limited to section's qin carbon black (KB), acetylene black.KB has very big specific surface area and very strong suction Attached ability, can be such that active ion is deposited on negative pole 20 more uniform, and KB very strong conductive capabilities can improve whole The chemical property during high current charge-discharge of individual battery.
Carbon-based material can be the mixture of activated carbon and binding agent, and the weight range that activated carbon accounts for porous layer 30 is 20- 99%.The specific surface area scope of activated carbon is 200-3000m2/g.Specifically, will commercialization activated carbon powder (particle size range 1- 200mm) uniformly mixed with Kynoar (PVDF), add 1-METHYLPYRROLIDONE (NMP) and be dissolved into pasty state, be coated on negative pole The surface of collector 22.The thickness range of porous layer 30 is 0.1-0.2mm, and the weight range that NMP accounts for porous layer mixture is 50- 70%.
The form of activated carbon includes but are not limited to activated carbon powder, active carbon particle, activated carbon-fiber felt or activated carbon fiber The specific surface area scope of cloth, activated carbon-fiber felt or activated carbon fiber cloth is 100-2200m2/g。
Specifically, active carbon particle is mixed with electrically conductive graphite, then uniformly mixed with PVDF, NMP, be coated in negative pole currect collecting The surface of body 22.The thickness of porous layer 30 is between 0.1-0.2mm.The effect of electrically conductive graphite is to increase negative pole porous layer 30 Electronic conduction ability.Wherein, the weight range that activated carbon accounts for porous layer 30 is 20-80%, and electrically conductive graphite accounts for the weight of porous layer 30 Amount scope is 5-20%, and the weight range that bonding agent PVDF accounts for porous layer 30 is 5-15%.Active carbon material has loose structure And larger specific surface area, carbon-based material of the price also with respect to CNT class be cheap.Moreover, specific make contains porous layer Negative pole technique it is also relatively easy, easy industrialization.
It is preferred that, the surface of negative pole 20 is formed with graphene layer.Graphene has the heat conductivility and mechanical property of protrusion, reason 2600m is up to by specific surface area2/ g, and the electron mobility of high speed at room temperature, therefore, are formed at the graphite on the surface of negative pole 20 Alkene layer can not only provide bigger surface area for the deposition of active ion 28, while conduction of negative pole 20 can also be improved further Ability, so as to improve the chemical property of battery high current.
In the first embodiment, because negative pole 20 only includes negative current collector 22, therefore, porous layer or graphene layer are It is formed at the surface of negative current collector 22.
Electrolyte include it is at least one can dissolve electrolyte and make electrolyte ionize solvent, solvent include the aqueous solution or At least one of person's alcoholic solution, alcoholic solution includes but are not limited to ethanol or methanol.
Electrolyte can be ionized out at least one charge and discharge process in the generation reduction-deposition of negative pole 20 and oxidation-dissolving Active ion 28.
The concentration range of active ion 28 is 0.5-15mol/L.In a particular embodiment, active ion 28 includes gold Belong to ion, metal is selected from least one of Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Metal ion is present in electrolyte in forms such as chlorate, sulfate, nitrate, acetate, formates, phosphate In.It is preferred that, metal ion is present in electrolyte in the form of the mixture of sulfate, acetate or sulfate and acetate In.
It is preferred that, a kind of electrolyte is also included in electrolyte, electrolyte can be ionized out at least one charge and discharge process Positive pole 10 can it is reversible deviate from-ion 16 that is embedded in, so as to improve positive active material 14 and the ion exchange in electrolyte Speed, improves the high rate charge-discharge performance of battery.Specifically, positive active material 14 for can it is reversible deviate from-be embedded in lithium from The compound of son, electrolyte is corresponding can also to ionize out lithium ion.The ion 16 of reversible abjection-insertion includes lithium ion or sodium Ion or magnesium ion or zinc ion, the concentration range of the ion 16 of reversible abjection-insertion in the electrolytic solution are 0.1-30mol/L.
In order to ensure that the concentration of the active ion 28 in battery capacity, electrolyte must reach certain limit, work as electrolyte When crossing alkali, the solubility of active ion 28 in electrolyte can be influenceed；When electrolyte peracid, then occur electrode material corrosion and The problems such as proton is embedded in altogether in charge and discharge process, therefore, the pH value range of electrolyte is 3-7 in the present invention.
It refer to shown in Fig. 2, the charge-discharge principle of battery is：During charging, deviate from positive active material 14 it is reversible abjection- Embedded ion 16, while be oxidized with variable valency metal in positive active material 14, and ejected electron；Electronics is via external circuit GND 20 is reached, while the active ion 28 in electrolyte obtains electronics in negative pole 20 and is reduced, and negative pole collection is deposited on The surface of fluid 22, forms active ion sedimentary 26.The inverse process of discharge process then for charging, as shown in Figure 3.
In the first embodiment, working first for battery is to deviate from reversible abjection-insertion in positive active material 14 Ion 16, active ion 28 reduce-are deposited as the charging process of active ion sedimentary 26 in negative pole 20.The capacity of battery Depending on the capacity of positive active material 14, therefore, during battery initial charge, need to include enough in positive active material 14 The ion 16 of reversible abjection-insertion.User's battery before without charging process cannot function as power supply and use, therefore protect Demonstrate,proved the capacity of battery before not by any type of loss.
Second embodiment
It refer to shown in Fig. 4, second embodiment of the invention provides a kind of battery, with disclosing in first embodiment The difference of battery is：Negative pole 20 also includes the negative electrode active material for being formed at the surface of negative current collector 22 in second embodiment 24, negative electrode active material 24 can aoxidize-be dissolved as active ion 28 in discharge process.
The carrier that negative current collector 22 only conducts and collected as electronics, is not involved in negative pole 20 and reacts, negative electrode active material 24 are formed at 22 on negative current collector by the method for coating, plating or sputtering, and sputtering method includes but are not limited to magnetic control and splashed Penetrate.Specifically, negative current collector 22 is copper foil, negative electrode active material 24 is zinc, and zinc is formed at copper foil table by electric plating method Face.
It is preferred that, negative electrode active material 24 is formed on the negative current collector 22 by surface preparation, surface preparation Method include at least one of mechanical treatment, chemical treatment or electrochemical treatments.Specifically, when negative current collector 22 is Cu When, the method pre-processed to Cu can be manual/mechanical grinding, remove the dim part in its surface while having its surface Certain roughness, but can not thoroughly remove due to hand sand the impurity on Cu surfaces, such as CuO, thus Cu is needed into The chemical treatment of one step, chemically treated method can prepare different sour mixed liquors to soak it, such as sulfuric acid, nitre Acid and hydrochloric acid.The specific method of pretreatment depends on the selection of negative current collector 22, is typically machinery, chemistry, three kinds of electrochemistry Method is combined.
In present embodiment, negative pole 20 includes negative current collector 22 and negative electrode active material 24, therefore, porous layer or graphite Alkene layer is formed at the surface of negative current collector 22.Negative electrode active material is formed at many by modes such as coating, plating or sputterings Aperture layer or graphene layer surface.
Likewise, positive pole 10 includes plus plate current-collecting body 12 and positive active material 14.Plus plate current-collecting body 12 is not involved in electrification Learn reaction, positive active material 14 can it is reversible deviate from-embedded ion, such as lithium ion, sodium ion, zinc ion or magnesium ion, But in this second embodiment, when preparing battery without limit positive active material 14 itself whether contain lithium ion, sodium from Son, zinc ion or magnesium ion, specifically, positive active material 14 can have four kinds of states：Reversible abjection-insertion is not contained Ion 16, contain and can also further be embedded in reversible abjection-insertion ion 16, containing reversible abjection-insertion from Son 16 and reversible abjection-insertion ion 16 reach saturation state, the ion 16 containing reversible abjection-insertion and it is reversible take off The ion 16 for going out-being embedded in reaches hypersaturated state.
Electrolyte include it is at least one can dissolve electrolyte and make electrolyte ionize solvent, solvent include the aqueous solution or Alcoholic solution, alcoholic solution includes but are not limited to ethanol and methanol.
Now, electrolyte can ionize out at least one charge and discharge process negative pole 20 occur reduction-deposition and oxidation- In the active ion 28 or at least one charge and discharge process of dissolving positive pole 10 can it is reversible deviate from-ion 16 that is embedded in or simultaneously Ion 16 containing active ion 28 and reversible abjection-insertion.
Second embodiment disclose battery, positive active material 14 in charge and discharge process can it is reversible deviate from-be embedded in Ion, but, the ion 16 of reversible abjection-insertion can not included, can be included for positive active material 14 itself There can also be the hole for the ion 16 for receiving reversible abjection-insertion in the ion 16 and internal structure of reversible abjection-insertion, may be used also To be itself ion 16 comprising reversible abjection-insertion and reach saturation state even hypersaturated state, therefore, battery is just Pole active material 14 has very big selection space in selection, further, can be comprising active ion 28 and/or can in electrolyte The ion 16 of inverse abjection-insertion so that the battery in the present invention can select different battery works according to different application scenarios Operation mode, battery strong adaptability.The battery that the positive active material 14 and electrolyte of different conditions are constituted is further elucidated below Mode of operation.
A kind of battery, including positive pole 10, negative pole 20, electrolyte (not shown).Positive pole 10 is including plus plate current-collecting body 12 and just Pole active material 14, positive active material 14 can it is reversible deviate from-embedded ion.Negative pole 20 includes negative current collector 22 and participated in The negative electrode active material 24 of electrochemical reaction.Electrolyte include it is at least one can dissolve electrolyte and make electrolyte ionize it is molten Agent.Electrolyte, which can be ionized out, at least one the ion 16 of reversible abjection-insertion can occur in positive pole 10；Positive active material 14 do not contain the ion 16 of reversible abjection-insertion；Battery work first be reversible abjection-insertion in electrolyte ion 16 it is embedding Enter to positive active material 14, negative electrode active material 24 to aoxidize-be dissolved as the discharge process of active ion 28.
Specifically, positive active material 14 is Mn2O4, negative electrode active material 24 is metal Zn, and LiAc is included in electrolyte. Due to being free of lithium in positive active material 14, and lithium ion is included in electrolyte, therefore, battery works as lithium in electrolyte first Ion is embedded into positive active material 14, and the metal Zn of negative electrode active material 24 aoxidizes-it is dissolved as Zn2+Discharge process.
It is preferred that, also include that the electrolyte of active ion 28 can be ionized out in electrolyte, active ion 28 is in the energy of negative pole 20 It is enough to occur reduction-deposition and oxidation-dissolving, so, in battery discharge, negative pole 20 can be accelerated and exchanged with electrolyte intermediate ion Speed.
As long as positive active material 14 meet in charge and discharge process can it is reversible deviate from-embedded ion this condition Work, and must contain the ion 16 of reversible abjection-insertion without limiting positive active material 14.Although positive active material 14 Not comprising can it is reversible deviate from-ion 16 that is embedded in, need to be discharge process when battery works first, but user is buying During battery in the present invention, it can equally be used directly as power supply, while battery is very long.
A kind of battery, including positive pole 10, negative pole 20, electrolyte.Positive pole 10 includes plus plate current-collecting body 12 and positive electrode active material Matter 14, negative pole 20 includes negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction, and electrolyte includes at least one The solvent that can be dissolved electrolyte and ionize electrolyte is planted, electrolyte can ionize out at least one to be occurred also in negative pole 20 Original-deposition and the active ion of oxidation-dissolving 28 and at least one the ion of reversible abjection-insertion can occur in positive pole 10 16；The ion 16 of reversible abjection-insertion can be deviate from and be embedded in positive active material 14；Working first for battery is reversible de- The charging process that the ion 16 for going out-being embedded in is deviate from from positive active material 14, active ion 28 is reduced and deposited in negative pole 20 The insertion of ion 16 positive active material 14, the negative electrode active material 24 of either reversible abjection-insertion aoxidize and are dissolved as activity The discharge process of ion 28.
Specifically, positive active material 14 contains Li1-xMn2O4, negative electrode active material 24 is metal Zn, is included in electrolyte Zinc acetate and lithium acetate.Positive active material 14 can deviate from Li+, meanwhile, in the spinel structure of positive active material 14 also There is hole to be available for Li in electrolyte+Embedded, therefore, mode of operation can be electric discharge to battery first：Li in electrolyte+It is embedded into Li1-xMn2O4, the metal Zn of negative electrode active material 24 aoxidizes and is dissolved as Zn2+；Mode of operation can be charging to battery first：I.e. Li1-xMn2O4Middle abjection Li+, the Zn in electrolyte2+Reduce and deposit to form active ion sedimentary 26 in negative pole 20.
Therefore, it both can be charging process or discharge process that battery works first.User is buying this hair During battery in bright, without considering it is that battery is charged or battery is discharged before use, you can use, and this The battery of invention is very long.
It is preferred that, battery works first to be deviate from for the ion 16 of reversible abjection-insertion from positive active material 14, activity The charging process of reduction-deposition occurs in negative pole 20 for ion 28.
A kind of battery, including positive pole 10, negative pole 20, electrolyte, positive pole 10 include plus plate current-collecting body 12 and positive electrode active material Matter 14, negative pole 20 includes negative current collector 22 and participates in the negative electrode active material 24 of electrochemical reaction；Electrolyte includes at least one Plant the solvent that can be dissolved electrolyte and ionize electrolyte；Electrolyte can ionize out at least one can occur in positive pole 10 The ion 16 of reversible abjection-insertion；The ion 16 of reversible abjection-insertion can be deviate from and be embedded in positive active material 14；Battery To work first be reversible abjection that-insertion of ion 16 positive active material 14, the negative electrode active material 24 of insertion are aoxidized-is dissolved as The discharge process of active ion 28.
Specifically, positive active material 14 contains Li1-xMn2O4, negative electrode active material 24 is metal Zn, is included in electrolyte Lithium acetate.Positive active material 14 can deviate from Li+, can also be embedded in Li+, contain Li in electrolyte+, therefore, battery works first It is Li+It is embedded into Li1-xMn2O4, metal Zn aoxidize-be dissolved as Zn2+Discharge process.
Although it to be discharge process that battery works first, user is in the battery in buying the present invention, equally Can be used directly as power supply, without influence battery performance, and battery work first after can normally discharge and recharge, simultaneously Battery is very long.
A kind of battery, including positive pole 10, negative pole 20, electrolyte, positive pole 10 include plus plate current-collecting body 12 and positive electrode active material Matter 14, positive active material 14 can it is reversible deviate from-embedded ion；Negative pole 20 includes negative current collector 22 and participation electrochemistry is anti- The negative electrode active material 24 answered；Electrolyte includes at least one solvent that can be dissolved electrolyte and ionize electrolyte；Electrolysis Matter can ionize out at least one in the generation reduction-deposition of negative pole 20 and the active ion 28 of oxidation-dissolving；The work first of battery The charging deposited that work is reversible abjection-embedded ion is deviate from from positive active material 14, active ion 28 is reduced in negative pole 20- Journey.
Specifically, positive active material 14 contains Li1-xMn2O4, negative electrode active material 24 is metal Zn, is contained in electrolyte Zinc acetate, positive active material 14 can deviate from Li+, can also be embedded in Li+, therefore, it is Li that battery works first+From Li1-xMn2O4 Zn in middle abjection, electrolyte2+Occurs the charging process of reduction-deposition in negative pole 20.
A kind of battery, including positive pole 10, negative pole 20, electrolyte, positive pole 10 include plus plate current-collecting body 12 and positive electrode active material Matter 14, positive active material 14 can it is reversible deviate from-embedded ion；Negative pole 20 includes negative current collector 22 and participation electrochemistry is anti- The negative electrode active material 24 answered；Electrolyte includes at least one solvent that can be dissolved electrolyte and ionize electrolyte；Electrolysis Matter can ionize out at least one active ion 28 in the generation reduction-deposition of negative pole 20；It is reversible de- in positive active material 14 The ion 16 for going out-being embedded in reaches saturation state；Battery work first be reversible abjection-insertion ion 16 it is de- from positive pole 10 Go out, the charging process that active ion 28 is reduced-deposited in negative pole 20.
As well known to those skilled in the art, the ion 16 of reversible abjection-insertion is in saturation state in positive active material 14, The ion 16 of i.e. reversible abjection-insertion has occupied the VOID POSITIONS in the structure of positive active material 14, and positive-active substantially The Stability Analysis of Structures of material 14, being capable of steady operation in battery charge and discharge process.
It need to be charging process that battery works first, you can the ion 16 of inverse abjection-insertion takes off from positive active material 14 Go out, in negative pole 20 reduction-deposition occurs for the active ion 28 in electrolyte.Although user's need pair when buying this battery It carries out charging operations, but just because of this, battery capacity before first use will not be by any type of loss, so as to protect The performance that battery is used in the later stage is demonstrate,proved.
It is preferred that, also including the ion 16 that can occur reversible abjection-insertion in positive pole 10 can be ionized out in electrolyte Electrolyte, so, in battery discharge, can accelerate the exchange velocity of positive pole 10 and electrolyte intermediate ion, improve big times of battery Rate charge-discharge performance.
Therefore, as long as electrolyte in negative pole 20 comprising can occur the active ion 28 of reduction-deposition and oxidation-dissolving Battery can be allowed to work, that is to say, that in the electrolyte of this battery, it is only necessary to add active ion 28, without Qiang ZhiyaoQiung Need containing can it is reversible deviate from-ion 16 that is embedded in, you can make normal battery operation.The bath composition of battery is simple, system Cause low, battery has wider application.
A kind of battery, including positive pole 10, negative pole 20, electrolyte, positive pole 10 include plus plate current-collecting body 12 and positive electrode active material Matter 14, positive active material 14 can it is reversible deviate from-embedded ion；Negative pole 20 includes negative current collector 22 and participation electrochemistry is anti- The negative electrode active material 24 answered；Electrolyte includes at least one solvent that can be dissolved electrolyte and ionize electrolyte；Electrolysis Matter can ionize out at least one active ion 28 in the generation reduction-deposition of negative pole 20；It is reversible de- in positive active material 14 The ion 16 for going out-being embedded in is in hypersaturated state；Battery work first be reversible abjection-insertion ion 16 it is de- from positive pole 10 Go out, active ion 28 reduces-be deposited as the charging process of negative electrode active material 24 in negative pole 20.
As well known to those skilled in the art, the ion 16 of reversible abjection-insertion is in supersaturated shape in positive active material 14 State, that is, when preparing positive active material 14, on the basis of positive active material 14 is in saturation, further to positive electrode active material Matter 14 carries out embedding ion processing, to improve the capacity of positive active material 14, in order to ensure that the structure of positive active material 14 is steady Fixed, the surface of positive active material 14 is modified or coated by metal or metal oxide.Specifically, metal is included but not only It is limited to Al, metal oxide includes but are not limited to Al2O3。
Specifically, positive active material 14 is Al2O3The Li of cladding1+xMn2O4(0<x<0.5), negative electrode active material 24 is Zinc acetate is included in metal Zn, electrolyte.Li in positive active material 14+Content reached hypersaturated state, therefore, battery Work first is Li+From Li1+xMn2O4Zn in middle abjection, electrolyte2+Active ion is reduced-is deposited as in negative pole 20 to sink The charging process of lamination 26.
It is preferred that, also including the ion 16 that can occur reversible abjection-insertion in positive pole 10 can be ionized out in electrolyte Electrolyte, so, when battery charges, can accelerate positive pole 10 and electrolyte intermediate ion exchange velocity, improve battery charging and discharging Performance.
Because the negative pole 20 of battery in second embodiment includes negative current collector 22 and participates in the negative pole of electrochemical reaction Active material 24, so the mode of operation first of battery has more selections, thus, what the producer can be according to user should With occasion, the collocation of positive pole 10, negative pole 20 and electrolyte in battery is selected, the electricity with different charge and discharge modes is produced Pond.
3rd embodiment
Third embodiment of the invention further discloses a kind of battery, and the difference of the battery disclosed with second embodiment is： Negative pole 20 only includes negative current collector 22 in 3rd embodiment, but negative current collector 22 serves not only as electronics conduction and collected Carrier, react, can be aoxidized in battery discharge procedure-molten while also corresponding to negative electrode active material and can participate in negative pole 20 Solve for active ion 28, the i.e. material of negative current collector 22 it is identical with the pure metals of active ion 28, for example：Active ion 28 For zinc ion, corresponding negative current collector 22 is metallic zinc.
In the third embodiment, negative pole 20 include participate in electrochemical reaction negative current collector 22, therefore, porous layer or Graphene layer is formed at the surface of negative current collector 22.Specific in the 3rd embodiment, the positive electrode active material of anode 10 Matter 14 is LiMn2O4, plus plate current-collecting body 12 is stainless (steel) wire, and negative current collector 22 is metallic zinc, and electrolyte is the water containing zinc salt Solution.It is preferred that, electrolyte is the aqueous solution containing zinc salt and lithium salts.Metallic zinc can participate in negative pole 20 and react.
When battery in the present invention is as that need to use barrier film, barrier film can be the porous material of organic or inorganic, the hole of barrier film Gap rate scope is 20-95%, and pore diameter range is 0.001-100 μm.
The battery that the present invention is provided, high (up to the 60%-80% of lithium ion battery) with energy density, power density is big (being expected to reach the 200% of lithium ion battery, even more high), it is easy to manufacture, totally nontoxic, environmental protection is easily reclaimed and cost is low Honest and clean (battery of same capacity, it is expected to reach the 60% of lead-acid battery, the 20% of lithium ion battery, even lower) the features such as, and And with good cycle performance, in a specific embodiment, battery capacity after circulating 4000 weeks is still maintained at more than 90%. Therefore, the present invention in battery as a new generation green energy resource, be highly suitable as the energy storage system in large-scale energy storage field with And the substitute of lead-acid battery.
The unit in weight, percent by volume in the present invention is well-known to those skilled in the art, such as volume hundred Divide the weight than referring to the solute in 100 milliliters of solution.Unless otherwise defined, all specialties used in text are used with science Language is identical with meaning known to one skilled in the art.In addition, any method similar or impartial to described content and material Material all can be applied in the inventive method.Preferable implementation described in text only presents a demonstration with material to be used.
With reference to embodiment, present disclosure is further illustrated.It should be appreciated that the implementation of the present invention is not limited to In the following examples, any formal accommodation and/or change made to the present invention fall within the scope of the present invention. In the present invention, if not refering in particular to, all part, percentage are unit of weight, and all equipment and raw material etc. can be from markets Buy or the industry is conventional.
By cyclic voltammetry (CV), build three-electrode system to test the stability of different collectors in the electrolytic solution.
Embodiment 1-1
Using stainless steel as working electrode, stainless steel model 304, zinc electrode is to electrode and reference electrode, in sulfate Electrolyte 2mol/L ZnSO4With 2mol/L Li2SO4In the electrochemical behavior of stainless steel, voltage are studied by cyclic voltammetry Scope is 1.0-2.4V.Stainless steel does not pass through Passivation Treatment.
Fig. 5 is the cyclic voltammetry curve of the stainless steel 304 of unpassivated processing in embodiment 1-1.As can be seen from the figure Stainless steel first anodic scan when, 1.9V (Vs.Zn) place occur a wide oxidation peak, then occur in that obvious O2Separate out Peak, increases along with electric current.In subsequent cathodic scan, relatively small reduction peak is occurred in that at 1.4V.Circulation 1 is taken second place The oxidation peak at 1.9V afterwards is hindered, it is meant that forms oxide layer in stainless steel surfaces in being circulated in first time, aoxidizes Layer inhibits the further oxidation of stainless steel surfaces internal layer.But perhaps oxide layer can trigger O2Precipitation.Therefore oxygen is caused Peak is separated out to migrate to low potential and become increasing.
Embodiment 1-2
Using the stainless steel of passivation as working electrode, stainless steel model 316, zinc electrode be to electrode and reference electrode, Stannous sulphate electrolyte 2mol/L ZnSO4With 2mol/L Li2SO4In studied by cyclic voltammetry passivation stainless steel electricity Chemical behavior, voltage range is 1.0-2.4V.
The method for being passivated stainless steel is chemical passivation, and detailed process is：At 50 DEG C, Stainless steel 316 is inserted 20% Concentrated nitric acid solution, maintains 0.5h, makes stainless steel surfaces formation passivating film, finally takes out stainless steel and is cleaned and dried with water.
Fig. 6 is the cyclic voltammetry curve of the stainless steel Jing Guo Passivation Treatment in embodiment 1-2.
Experimental result is shown in for example dense HNO of the solution containing oxidant3After being passivated in solution, stainless steel becomes more stable, And O2Precipitation peak favorable reproducibility, in different cycle period O2Precipitation peak shape do not distinguish significantly.On the other hand, O2 Evolution or deposition potential is migrated slightly towards high potential, and the precipitation of obvious oxygen does not occur before 2.0V.This result is to water system electricity Pond is extremely important, because the stainless steel through transpassivation is highly stable in the range of water system battery operating voltage.
Embodiment 1-3
Using the stainless steel of passivation as working electrode, stainless steel model 316P, zinc electrode be to electrode and reference electrode, Nitric acid salt electrolyte 3mol/L Zn (NO3)2With 6mol/L LiNO3In study by cyclic voltammetry the stainless steel of passivation Electrochemical behavior, voltage range is 1.0-2.4V.
It is passivated the method be the same as Example 1-2 of stainless steel.
Fig. 7 is Stainless steel 316 P by the Passivation Treatment CV curves in nitric acid salt electrolyte.
Embodiment 1-4
Using aluminium alloy as working electrode, zinc electrode is to electrode and reference electrode, in acetic acid salt electrolyte 1.5mol/L Zn (Ac)2With the electrochemical behavior for studying aluminium alloy in 3mol/L LiAc by cyclic voltammetry, voltage range is 1.0- 2.4V, aluminium alloy is passivated in 2.4V lower surfaces.
Embodiment 1-5
Using aluminium alloy as working electrode, zinc electrode is to electrode and reference electrode, in stannous sulphate electrolyte 2mol/L ZnSO4With 2mol/L Li2SO4In the electrochemical behavior of aluminium alloy is studied by cyclic voltammetry, voltage range is 1.0- 2.4V, aluminium alloy is passivated in 2.4V lower surfaces.
Fig. 8 and Fig. 9 are respectively CV curve of the aluminium alloy in acetate and stannous sulphate electrolyte in embodiment 1-4 and 1-5. In fig. 8, first anodic scan when occur in that significant oxidation peak, electric current is slightly fluctuated, and this phenomenon may be attributed to Nonfaradaic current or other processes that the oxidation of aluminum alloy surface or ionic adsorption are produced.Aluminium alloy surface in 2.4V is electric Chemical oxidation, is formed after passivating film, first time anodic scan, at 1.0-2.1V not any peaks, and O2Evolution or deposition potential to High potential is migrated, and analysis oxygen electric current diminishes.Show the aluminium alloy after electrochemical passivation in the range of water system battery operating voltage It is highly stable.
Embodiment 1-6
Using graphite foil as working electrode, zinc electrode is to electrode and reference electrode, in hydrochloric acid salt electrolyte 4mol/L ZnCl2With the electrochemical behavior for studying graphite foil in 3mol/L LiCl by cyclic voltammetry.
Embodiment 1-7
Using the stainless steel of unpassivated processing as working electrode, zinc electrode is to electrode and reference electrode, in hydrochloride electricity Solve liquid 4mol/L ZnCl2With the electrification for the stainless steel for studying unpassivated processing in 3mol/L LiCl by cyclic voltammetry Scholarship and moral conduct is.
Figure 10 and Figure 11 are respectively embodiment 1-6 and 1-7 CV curves.It can be seen that graphite foil in chloric acid by CV curves Stablize relatively in salting liquid, it is bright without occurring under whole electrochemical window in addition to the precipitation of oxygen occurs under high potential Aobvious oxidation or reduction peak, this phenomenon demonstrate carbon-based material and are adapted to as collector in solution of chlorate, and without blunt The stainless steel for changing processing is poorly suited for solution of chlorate.
By Tafel curves, build three-electrode system to test corrosion speed of the different collectors in acetic acid salt electrolyte Rate.
Embodiment 2-1
Using aluminium foil as working electrode, zinc is to electrode and reference electrode, in acetic acid salt electrolyte 1.5mol/L Zn (Ac)2 In 3mol/L LiAc, the corrosion behavior of aluminium foil is studied by Tafel curves.
Embodiment 2-2
Using stainless steel 304 rod as working electrode, its excess-three electrode group into test condition be the same as Example 2-1.
Embodiment 2-3
Using graphite rod as working electrode, its excess-three electrode group into test condition be the same as Example 2-1.
Embodiment 2-4
Using aluminium alloy as working electrode, its excess-three electrode group into test condition be the same as Example 2-1.
Embodiment 2-5
Using the stainless steel 304 of passivation as working electrode, its excess-three electrode group into test condition be the same as Example 2-1.Tool Body stainless steel is handled by chemical passivation.
Embodiment 2-6
Using the aluminium alloy of passivation as working electrode, its excess-three electrode group into test condition be the same as Example 2-1.Aluminium alloy is Handled by electrochemical passivation, discharge and recharge, charge and discharge cycles 1 time are carried out to aluminium alloy.
Embodiment 2-7
Using the aluminium alloy of passivation as working electrode, its excess-three electrode group into test condition be the same as Example 2-1.Specific aluminium Alloy is handled by electrochemical passivation, and discharge and recharge, electrochemical passivation charge and discharge cycles 50 times are carried out to aluminium alloy.
Corrosion current can be obtained from Tafel curves and formula 1.Area, density and possible corruption based on working electrode Mechanism (quantity of electron transfer in corrosion process) is lost, the corrosion speed of several different plus plate current-collecting bodies as shown in table 1 is obtained Rate, wherein.R is corrosion resistance, IcorrFor corrosion current.
Formula 1：
Table 1
As can be seen from Table 1：The corrosion rate highest of aluminium foil, the corrosion speed of stainless steel and aluminium alloy in Acetate Solution Rate is small compared to aluminium foil 10 times.Respectively through the stainless steel and the corrosion speed of aluminium alloy after chemical passivation and electrochemical passivation processing Rate declines 6-12 times.Also, the corrosion rate after the further electrochemical oxidation of aluminium alloy can also further decline, electrochemical oxidation 50 post-etching speed of processing cycle decline 150 times.This result is coincide with CV results, and CV results show that oxygen is analysed in circulation afterwards for several times Curve dies down.
Further, the chemical property of battery is studied by specific embodiment.
Embodiment 3-1
With LiMn2O4For positive active material, by positive active material, conductive agent acetylene black (AB), binding agent polyvinylidene fluoride Alkene (PVDF) is according to 83：10：7 part by weight, which is mixed and is dissolved in 1-METHYLPYRROLIDONE (NMP), is made anode sizing agent. Plus plate current-collecting body is graphite foil, and anode sizing agent is evenly applied on plus plate current-collecting body, is dried 24 hours at 110 DEG C in atmosphere Positive pole is made.GND collector is stainless steel.It containing concentration is 4mol/L zinc chloride and 3mol/L chlorinations that electrolyte, which is, The aqueous solution of lithium, by the way that the pH value of electrolyte is adjusted into 4 toward titration 0.1mol/L lithium hydroxides in electrolyte.Barrier film is glass felt Cloth.Positive pole, negative pole are assembled into battery, centre is separated with barrier film, injects electrolyte.Treat that battery stands 12 hours after assembling Then begin to be charged and discharged with 4C multiplying powers.Charging/discharging voltage interval is 1.4-2.15V.
Figure 12 is the voltage of 3-1 of the embodiment of the present invention batteries provided and the relation curve of discharge capacity, the coulomb of battery Efficiency is about 97%, at the same also indicate that battery excellent electrochemical performance and cyclic process in almost there is no side reaction.
Figure 13 is the discharge capacity of 3-1 of the embodiment of the present invention batteries provided and the relation curve of cycle-index, from figure As can be seen that battery initial capacity is 0.35mAh, the specific capacity based on positive electrode is 117mAhg-1, and circulating battery Volumetric efficiency after 1000 weeks still has 90%, shows that the cycle performance of battery is very good.
Embodiment 3-2
Battery positive electrode active material is Li in embodiment 3-61.08Co0.03Al0.03Mn1.94O4, remaining battery constitute and assemble Method is identical with embodiment 3-1.
Figure 14 is the discharge capacity of the embodiment 3-2 batteries provided and the relation curve of cycle-index, can from figure Go out, volumetric efficiency of the circulating battery after 4000 weeks still has 95%, show the LiMn treated using doping vario-property2O4Positive-active The cycle life of the battery of material is further improved.
Embodiment 3-3
With Li1.05Mn1.89Co0.03Al0.03O4For positive active material, by positive active material, binding agent PVDF, super- P carbon blacks are according to 83：10：7 part by weight, which is mixed and is dissolved in 1-METHYLPYRROLIDONE (NMP), is made anode sizing agent, just Pole collector is thickness 1mm graphite cake.Charging/discharging voltage interval is 1.5-2.1V.Remaining composition of battery and method of testing are same Embodiment 3-1.
Figure 15 is the discharge capacity and the relation curve of cycle-index for the battery that embodiment 3-3 is provided, can be clear from figure Clear to find out, the discharge capacity that circulating battery is 4000 times and discharge capacity first are almost equal, and not only cycle performance is very steady for battery It is fixed, and have extended cycle life.
Figure 16 is the coulombic efficiency and the relation curve of cycle-index for the battery that embodiment 3-3 is provided, can from figure Go out after circulating battery 4000 times, coulombic efficiency shows that the charge-discharge performance of battery in the present invention is very steady still close to 100% It is fixed.
Embodiment 3-4
With LiMn2O4For positive active material, by positive active material, polyfluortetraethylene of binding element (PTFE), super-p Carbon black is according to 83:10:7 ratio, which is mixed and is dissolved in 1-METHYLPYRROLIDONE (NMP), is made anode sizing agent.Anode collection Body is the stainless (steel) wire of 30 μm of thickness, and anode sizing agent is evenly applied on plus plate current-collecting body by stainless steel without transpassivation, in sky Positive pole is made in 24 hours in drying at 110 DEG C in gas.GND collector is 10 μm of copper foils of thickness.Electrolyte is is containing concentration The aqueous solution of 1mol/L lithium acetates and 1.5mol/L zinc acetates, by toward titration 0.1mol/L lithium hydroxides in electrolyte and The pH value of electrolyte is adjusted to 4 by 0.1mol/LHAc.Barrier film is glass felt-cloth.Positive pole, negative pole are assembled into battery, it is middle with every Film is separated, and injects electrolyte.Treat that battery is stood after assembling to then begin within 12 hours be charged and discharged with 0.5C multiplying powers.Charge and discharge Piezoelectric voltage interval is 1.5-2.1V.
Figure 17 is the discharge capacity and the relation curve of cycle-index for the battery that embodiment 3-4 is provided.Can be clear from figure It is clear to see：Discharge capacity is battery first, and the discharge capacity after circulating 250 times is with discharge capacity first almost without difference, table The cycle performance of bright battery is highly stable, and the battery that the present invention is provided has excellent chemical property.
Embodiment 4-1
With LiMn2O4For positive active material, according to positive active material 90%, conductive carbon black 6%, bonding agent SBR (fourths Benzene latex rubber) 2%, thickener CMC (sodium carboxymethylcellulose) 2% ratio, first CMC is well mixed with a certain amount of water, then Positive active material and conductive carbon black are added, is stirred 2 hours, SBR stirrings is eventually adding and obtains anode sizing agent in 10 minutes.Positive pole collection Fluid is thickness 0.1mm graphite foil, and anode sizing agent is coated uniformly on plus plate current-collecting body, thickness 0.3mm, 120 degree of drying Positive plate is made within 12 hours.GND collector is thickness 0.1mm graphite foil.By activated carbon powder, (coconut husk is fired, and compares table Area 1500m2/ g), conductive carbon black, PVDF is with 90:5:5 ratio is well mixed, and is added NMP and is dissolved, is coated uniformly on Porous layer is made in negative current collector graphite foil, thickness is 0.1mm.Electrolyte be containing concentration be 4mol/L zinc chloride and The aqueous solution of 3mol/L lithium chlorides, barrier film is nonwoven cloth diaphragm.By positive plate, negative plate is assembled into battery, it is middle with barrier film every Open.Electrolyte is injected, electrolyte is largely stored in porous layer, the Zn in charge and discharge process in electrolyte2+/ Zn is sent out in negative pole Original-deposition of surviving and oxidation-dissolving reaction, the especially interface inside porous layer and between porous layer and negative current collector Upper generation reduction-deposition and oxidation-dissolving reaction.Figure 18 is that the structure that negative current collector surface of the present invention is formed with porous layer is shown It is intended to.In charge and discharge process, zinc is in cathode deposition/dissolving.Micron-sized hole can effectively adsorb a large amount of electrolysis in activated carbon Liquid and offer zinc deposition basic point.Figure 19 is the partial enlarged drawing of porous layer in Figure 18, it is apparent that be deposited on inside porous layer Active ion sedimentary 26.Treat that battery is stood after assembling to then begin within 12 hours be charged and discharged with 1C multiplying powers.Charge and discharge For 1.4-2.15V, (i.e. with 100mAh electric current constant-current charge to 2.15V, then constant-current discharge is to 1.4V, so in piezoelectric voltage interval Circulate operation).Figure 20 is 4-1 of embodiment of the present invention LiMn2O4/ Zn battery first charge-discharge voltage-capacity curve maps.
Embodiment 4-2
Battery is manufactured with embodiment 4-1 identical modes, the difference is that being used as GND collector so that copper foil is tin plating.Phase For graphite foil, more preferably, mechanical strength is higher, also thinner for copper foil electric conductivity.Be conducive to improving the negative of battery using copper foil Pole discharge performance, while can also reduce battery volume, improves the volume energy density of battery.But simple copper foil can not conduct The negative pole of ion exchange battery, because in copper foil surface, the efficiency of zinc deposition is very low.It therefore, it can plate one layer in copper foil surface Tin, to improve deposition efficiency.
Because negative current collector can not largely effect on the performance of battery in itself, the charge and discharge of battery is done with the embodiment Electric curve is substantially similar to embodiment one.
Embodiment 4-3
Battery is manufactured with embodiment 4-1 identical modes, the difference is that porous using commercially available activated carbon fiber cloth as battery Layer.The microstructure of the active carbon cloth is similar with activated carbon, and (uncompressed) thickness is 0.5mm or so, in 0.1-0.2mm after compression Between.The specific surface area of the activated carbon fiber cloth is 800m2/g.Activated carbon fiber cloth and negative current collector are cut into same big It is small, it is overlapping successively according to negative current collector-activated carbon fiber cloth-nonwoven cloth diaphragm-anode electrode.With the knot of this battery formed Structure is identical with the battery structure shown in Figure 15, and simply the material of porous layer includes activated carbon fiber cloth.It is obvious that above method The battery of manufacture it is simple in construction, industrialized production can be carried out at faster speed.With embodiment one and embodiment two In the porous layer being made up of activated carbon mentioned it is the same, activated carbon fiber cloth can also provide sufficiently large negative pole specific surface area.
Embodiment 5-1
With LiMn2O4For positive active material, compare 8 according to positive active material, active carbon black, bonding agent PVDF weight:1: 1 is well mixed, and is cut into diameter 12mm, thickness 0.1-0.2mm disk, is compressed on aluminium alloy collector, makes positive pole.It is negative Extremely diameter 12mm, thickness 1mm metallic zinc, metallic zinc double as negative electrode active material and negative current collector.Between between positive and negative electrode Every 5mm, barrier film is filter paper.Electrolyte is the mixing of the lithium sulfate containing 4mol/L lithium ions and 2mol/L zinc ions and zinc sulfate The aqueous solution, the pH that 0.1mol/L LiOH regulation electrolyte is added by titrating is 5.
Discharge and recharge is carried out to battery, voltage range is 1.4-2.4V, and sweep speed is 0.5mV/s.Plus plate current-collecting body aluminium is closed Gold surface in high voltage 2.4V forms passivating film.
Embodiment 5-2
In embodiment 5-2, plus plate current-collecting body is the alloy foil of 50 μm of thickness, and negative pole is the metallic zinc paper tinsel of 50 μm of thickness, Electrolyte is 1.5mol/L Zn (Ac)2With 2mol/L LiAc, barrier film is glass felt-cloth, remaining battery composition and method of testing Be the same as Example 5-1.
Figure 21 and Figure 22 are respectively the CV curve maps for the battery that embodiment 5-1 and 5-2 are provided.It can be seen that every Anode and cathodic scan to should have two significant oxidation peaks (1.95V and 1.85V) and two reduction peaks (1.85V and 1.7V), this abjection/insertion mechanism with lithium ion in organic bath is consistent.Except the two obvious redox Electricity have also appeared less oxidation peak to outside, after circulation primary, and peak current appears in 1.6V, and the cause of this oxidation peak may It is abjection-insertion of proton.This result further demonstrates the stability of battery of the present invention very well, and filled with excellent Discharge cycle performance.
In addition, coulombic efficiency of the battery after circulating 600 times in embodiment 5-2 shows filling for battery still close to 90% Discharging efficiency is very high.
Embodiment 5-3
In embodiment 5-3, plus plate current-collecting body is the stainless steel 304 through transpassivation, and the thickness of stainless steel 304 is 50 μm, electricity Solution liquid is 2mol/L ZnSO4With 2mol/L Li2SO4, barrier film is glass felt-cloth, remaining battery composition be the same as Example 5-1, charge and discharge Piezoelectric voltage interval is 1.4-2.1V.Specifically the method for passivation stainless steel is：At 50 DEG C, stainless steel is inserted to 20% concentrated nitric acid Up to half an hour, make stainless steel surfaces one layer of passivating film of formation.
Figure 23 is the CV curves of battery in embodiment 5-3.
Embodiment 5-4
In embodiment 5-4, plus plate current-collecting body is the stainless steel 304 through transpassivation, and electrolyte is 3mol/L Zn (NO3)2With 6mol/L LiNO3, remaining battery composition be the same as Example 5-1, charging/discharging voltage interval is 1.4-2.2V.Specific passivation stainless steel Method be the same as Example 5-3.
Figure 24 is the CV curves of battery in embodiment 5-4.
Embodiment 5-5
Battery is manufactured with embodiment 5-1 identical modes, except that the process Passivation Treatment by 1mm of thickness 304 type stainless steels replace graphite foil as plus plate current-collecting body, and specific Passivation Treatment process is：At 50 DEG C, stainless steel is inserted 20% nitric acid is up to half an hour, makes stainless steel surfaces one layer of passivating film of formation.It containing concentration is 1.5mol/L vinegar that electrolyte, which is, The aqueous solution of sour zinc and 3mol/L lithium acetate.GND is metallic zinc.Treat that battery stands 12 hours after assembling, then open Beginning is charged and discharged with 1mA constant currents to battery.Charging/discharging voltage interval is 1.4-2.2V.
Embodiment 5-6
Battery is manufactured with embodiment 5-1 identical modes, except that being replaced with 316 type stainless steels of Passivation Treatment 304 type stainless steels are as plus plate current-collecting body, specific Passivation Treatment process be the same as Example 5-5.Treat that battery stands 12 after assembling Hour, then begin to respectively charge and discharge battery with 1mA and 3mA constant current.Charging/discharging voltage interval is 1.4- 2.2V。
Figure 25 is the CV curves of battery in embodiment 5-6.
Embodiment 5-7
Battery is manufactured with embodiment 5-6 identical modes, except that it containing concentration is 3mol/L sulfuric acid that electrolyte, which is, The aqueous solution of zinc and 3mol/L lithium sulfates.Treat that battery stands 12 hours after assembling, then begin to respectively with 1mA, 2mA, 3mA Constant current battery is charged and discharged.Charging/discharging voltage interval is 1.4-2.2V.
Embodiment 5-8
Battery is manufactured with embodiment 5-7 identical modes, except that being used as positive pole collection using the metallic aluminium of Passivation Treatment Fluid.Process to metallic aluminium Passivation Treatment is：Treat that battery stands 12 hours after assembling, then begin to 1mA constant currents Battery is charged and discharged, voltage is charged to 2.4V during charging, i.e. charging/discharging voltage interval is 1.4-2.4V, makes metallic aluminium Surface forms one layer of passivating film.
Capability retention is tested
It is electrically operated by carrying out charge and discharge to the battery in embodiment 5-1 to 5-8, to detect the cycle performance of battery.
Table 2 is battery discharge and recharge under 1mA constant currents in embodiment 5-1 to 5-8, the battery performance that circulation is 80 times：
Table 2
From Table 2, it can be seen that stainless steel by Passivation Treatment as battery performance during plus plate current-collecting body from capacity Conservation rate and the aspect of efficiency for charge-discharge two are all more excellent.
Embodiment 5-6 is tested with 3mA constant current charge-discharge, capability retention is 94%, discharge and recharge after circulating 80 times Efficiency is 98%, and battery performance is better than with 1mA constant current charge-discharge test results, illustrates the battery in the present invention under high current With excellent battery performance.
Embodiment 5-7 is tested with 2mA, 3mA constant current charge-discharge, capability retention is respectively 92% after circulating 80 times With 72%, efficiency for charge-discharge is 99%, and the battery that embodiment 5-7 is provided is optimal with the battery performance of 2mA constant current charge-discharges.
Embodiment 5-9
With LiMn2O4For positive active material, compare 8 according to positive active material, active carbon black, bonding agent PVDF weight:1: 1 is well mixed, and is coated on the stainless steel collector of passivation, makes positive pole.Passivation for stainless steel method be the same as Example 5-3.Negative pole For 50 μm of metallic zinc paper tinsel of thickness, metallic zinc doubles as negative electrode active material and negative current collector.Barrier film is glass felt-cloth.Electrolyte For the mixed aqueous solution containing 2mol/L lithium acetates, 1.5mol/L zinc acetates and 1mol/L zinc sulfate, regulation electrolyte pH is 5.
Discharge and recharge is carried out to battery, voltage range is 1.4-2.1V, and sweep speed is 0.5mV/s.
Figure 26 is the CV curves of the embodiment 5-9 batteries provided, and experimental result shows, coulomb of the battery in circulation 200 times Efficiency shows there is stable charge-discharge performance using the battery of mixed electrolyte salt close to 100%.
Embodiment 6-1
With LiMn2O4For positive active material, by positive active material, super-p carbon blacks, bonding agent PVDF according to weight Ratio 83:10:7 are well mixed, using NMP as dispersant, and anode sizing agent is made, the anode collection of 80 μm of thickness is coated uniformly on In body graphite foil, it is subsequently dried, suppresses and obtain positive pole.Negative pole is the metallic zinc paper tinsel of 50 μm of thickness, and metallic zinc is both negative electrode active Material, while also also serving as negative current collector.Barrier film is glass felt-cloth.Electrolyte is to contain 3mol/L lithium chlorides and 4mol/L chlorinations The deionized water solution of zinc, the pH that electrolyte is adjusted by the way that 0.1mol/L LiOH solution is added dropwise into electrolyte is 4.Room temperature Under, discharge and recharge is carried out to battery with 4C multiplying powers in voltage range 1.5-2.1V.
Figure 27 is the battery first charge-discharge and the relation curve of voltage in embodiment 6-1, as can be seen from the figure battery Discharge capacity is about 0.35mAh first.
Figure 28 is discharge capacity of the cell and the relation curve of cycle-index, and the capacity of battery battery after circulating 1000 times is still More than 85% is maintained at, capacity attenuation very little shows that battery has extraordinary stability.
Figure 29 is battery coulombic efficiency and the relation curve of cycle-index, and as can be seen from the figure battery is in circulation 1000 times Coulombic efficiency afterwards is more than 80%.
Embodiment 6-2
With LiMn2O4For positive active material, by positive active material, super-p carbon blacks, bonding agent PVDF according to weight Ratio 83:10:7 are well mixed, using NMP as dispersant, and anode sizing agent is made, the anode collection of 80 μm of thickness is coated uniformly on In body graphite foil, it is subsequently dried, suppresses and obtain positive pole.Negative pole is the metallic zinc paper tinsel of 50 μm of thickness, and metallic zinc is both negative electrode active Material, while also also serving as negative current collector.Barrier film is non-woven fibre cloth.Electrolyte is to contain 3mol/L lithium chlorides and 4mol/L chlorine Change the aqueous solution of zinc, the pH that electrolyte is adjusted by the way that 0.1mol/L LiOH solution is added dropwise into electrolyte is 4.At room temperature, exist Voltage range 1.5-2.1V carries out discharge and recharge with 1C multiplying powers to battery.
Figure 30 is the discharge capacity of the embodiment 6-2 batteries provided and the relation curve of cycle-index, and battery is in circulation 30 Secondary rear capacity slightly has decay, but rate of decay is very slow.
Figure 31 is battery coulombic efficiency and the relation curve of cycle-index, and coulombic efficiency of the battery after circulating 30 times is nearly 90%.
Embodiment 6-3
With LiMn2O4For positive active material, by positive active material, super-p carbon blacks, bonding agent CMC-SBR according to weight Amount ratio 83:10:7 are well mixed, using NMP as dispersant, and anode sizing agent is made, the positive pole collection of 50 μm of thickness is coated uniformly on On fluid stainless steel foil, stainless steel is subsequently dried without transpassivation, suppresses and obtain positive pole.Negative pole is the metallic zinc of 40 μm of thickness Paper tinsel, metallic zinc is both negative electrode active material, while also also serving as negative current collector.Barrier film is glass felt-cloth.Electrolyte be containing The aqueous solution of 1mol/L lithium acetates and 1.5mol/L zinc acetates, by into electrolyte be added dropwise 0.1mol/L LiOH and The pH of 0.1mol/L HAc solution regulation electrolyte is 4.At room temperature, battery is entered with 0.5C multiplying powers in voltage range 1.5-2.1V Row discharge and recharge.
Cell Experimentation An result is shown in embodiment 6-3, discharge capacitance and coulombic efficiency that circulating battery is 320 times Close to 100%, show battery with very excellent cycle performance and life-span.
Embodiment 6-4
In embodiment 6-4, battery is placed at 55 DEG C and carries out discharge and recharge, it is electrical to study the charge and discharge of battery at high temperature Can, other compositions of battery and method of testing be the same as Example 6-3.
Figure 32 is the discharge capacity of the embodiment 6-4 batteries provided and the relation curve of cycle-index, can from figure Go out, battery is under 55 DEG C of high temperature, still with good discharge capacitance, circulating battery 160 times is almost without obvious Capacity attenuation.
Embodiment 6-5
With LiMn2O4For positive active material, by positive active material, super-p carbon blacks, bonding agent PVDF according to weight Ratio 83:10:7 are well mixed, using NMP as dispersant, and anode sizing agent is made, the anode collection of 30 μm of thickness is coated uniformly on On body stainless (steel) wire, stainless steel is subsequently dried without transpassivation, suppresses and obtain positive pole.Negative pole is the metallic zinc paper tinsel of 10 μm of thickness, Metallic zinc is both negative electrode active material, while also also serving as negative current collector.Barrier film is glass felt-cloth.Electrolyte is to contain 1mol/L The aqueous solution of lithium acetate and 1.5mol/L zinc acetates, by LiOH the and 0.1mol/L HAc that 0.1mol/L is added dropwise into electrolyte The pH of solution regulation electrolyte is 4.At room temperature, discharge and recharge is carried out to battery with 0.5C multiplying powers in voltage range 1.5-2.1V.
Figure 33 is the discharge capacity of the embodiment 6-5 batteries provided and the graph of relation of cycle-index, can be with from figure Find out, 30 discharge capacities of circulating battery almost do not decay, show that the battery charging and discharging stability that the present invention is provided is good.
Embodiment 7-1
With LiMn2O4For positive active material, by positive active material, super-p carbon blacks, bonding agent PVDF according to weight Ratio 8:1:It is well mixed, using NMP as dispersant, anode sizing agent is made, the plus plate current-collecting body of 80 μm of thickness is coated uniformly on In graphite foil, it is subsequently dried, suppresses and obtain positive pole.Negative current collector is the graphite foil of 50 μm of thickness, and metallic zinc is plated in graphite foil On be used as negative electrode active material.Barrier film is glass felt-cloth.Electrolyte is containing 2mol/L lithium acetates and 1.5mol/L zinc acetates The aqueous solution, the pH that electrolyte is adjusted by the way that 0.1mol/L LiOH solution is added dropwise into electrolyte is 4.At room temperature, in voltage model Enclose 1.5-2.1V and discharge and recharge is carried out to battery with 0.5C multiplying powers.
Embodiment 7-2
Battery is manufactured with embodiment 7-1 identical modes, except that 316 type stainless steels are used as negative pole instead of graphite foil Collector.
Embodiment 7-3
Battery is manufactured with embodiment 7-1 identical modes, except that copper foil is used as negative current collector instead of graphite foil.
The battery that embodiment 7-1 to 7-3 is provided, battery has good cycle performance.
Although inventor has done more detailed elaboration and enumerated to technical scheme, it will be appreciated that for For those skilled in the art, above-described embodiment is modified and/or the flexible or equivalent alternative solution of use is obvious , can not all depart from the essence of spirit of the present invention, the term occurred in the present invention be used for elaboration to technical solution of the present invention and Understand, can not be construed as limiting the invention.

Claims (10)

1. a kind of battery, including positive pole, negative pole, electrolyte, it is characterised in that：
The positive pole include positive active material, the positive active material can it is reversible deviate from-embedded ion；
The negative pole includes being not involved in the negative current collector of electrochemical reaction and is formed at the negative pole on the negative current collector surface Active material；
The electrolyte includes that electrolyte can be dissolved and makes the solvent of the electrolyte ionization；
The electrolyte can ionize out the activity in negative pole generation reduction-deposition and oxidation-dissolving in charge and discharge process Ion or/and the positive pole can it is reversible deviate from-ion that is embedded in；
The negative electrode active material can aoxidize-be dissolved as the active ion in discharge process.
2. battery according to claim 1, it is characterised in that：The negative electrode active material includes metal simple-substance, the gold Category is selected from least one of Zn, Fe, Cr, Cu, Mn, Ni.
3. battery according to claim 1, it is characterised in that：The material of the negative current collector be selected from W metal, Cu, One kind in Ag, Pb, Sn, Fe, Al or above-mentioned metal Jing Guo Passivation Treatment.
4. battery according to claim 1, it is characterised in that：The material of the negative current collector is selected from carbon-based material, no Become rusty steel, silicon or the metal with plating/coating, and the plating/coating contains C, Sn, In, Ag, Pb, Co simple substance, alloy or oxygen At least one of compound.
5. battery according to claim 4, it is characterised in that：The thickness range of the plating/coating is between 1-1000nm.
6. battery according to claim 1, it is characterised in that：The negative current collector is copper, the negative electrode active material For zinc.
7. battery according to claim 1, it is characterised in that：The negative electrode active material is formed at by surface preparation Negative current collector, the surface preparation is selected from least one of mechanical treatment, chemical treatment or electrochemical treatments.
8. battery according to claim 1, it is characterised in that：The active ion with chlorate, sulfate, nitrate, At least one of acetate, formates, phosphate form is present in the electrolyte.
9. battery according to claim 1, it is characterised in that：The positive active material can it is reversible deviate from-be embedded in lithium Ion, sodium ion, magnesium ion or zinc ion.
10. battery according to claim 1, it is characterised in that：The material of the plus plate current-collecting body is selected from graphite, stainless Steel, aluminium alloy, stainless steel or aluminium alloy through transpassivation.
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