WO2012097456A1 - Batterie échangeuse d'ions à configuration plate - Google Patents

Batterie échangeuse d'ions à configuration plate Download PDF

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Publication number
WO2012097456A1
WO2012097456A1 PCT/CA2012/050032 CA2012050032W WO2012097456A1 WO 2012097456 A1 WO2012097456 A1 WO 2012097456A1 CA 2012050032 W CA2012050032 W CA 2012050032W WO 2012097456 A1 WO2012097456 A1 WO 2012097456A1
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WO
WIPO (PCT)
Prior art keywords
rechargeable battery
battery according
anode
electrolyte
cathode
Prior art date
Application number
PCT/CA2012/050032
Other languages
English (en)
Inventor
Pu Chen
Original Assignee
Liu, Hao
YAN, Jing
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Liu, Hao, YAN, Jing filed Critical Liu, Hao
Priority to AU2012208932A priority Critical patent/AU2012208932A1/en
Publication of WO2012097456A1 publication Critical patent/WO2012097456A1/fr

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Classifications

    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
    • H01M4/50—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0472—Vertically superposed cells with vertically disposed plates
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a secondary battery.
  • the invention relates to an ion exchange secondary battery having a plate configuration.
  • a “secondary battery”, also referred to as a rechargeable battery, is a battery wherein the internal electrochemical reactions are reversible.
  • Various kinds of secondary batteries are applied in different fields depending on their specific requirements. For example, portable electronic devices require a battery with a high energy density as in lithium ion (Li-ion) batteries, electric tools require a high power output as in Li-ion, Ni-MH, and Ni-Cd batteries, and large energy storage applications (such as a UPS), motor start-up batteries, wind power/solar energy storage devices all require batteries with low cost and long service life.
  • Li-ion batteries lithium ion
  • electric tools require a high power output as in Li-ion, Ni-MH, and Ni-Cd batteries
  • large energy storage applications such as a UPS
  • motor start-up batteries wind power/solar energy storage devices all require batteries with low cost and long service life.
  • Lead-acid batteries have been occupying the majority of the battery market share, especially among energy storage fields for several decades.
  • LiMn 2 0 4 /V0 2 LiNi 0 8 iCoo i 9 0 2 /LiV 3 0 8 , LiM ⁇ O ⁇ TiP ⁇ , LiMn 2 0 4 /LiTi 2 (P0 4 )3, and
  • the invention provides a rechargeable battery consisting of a cathode electrode, an anode electrode and an electrolyte.
  • the invention provides a rechargeable battery comprising a shell and a cover, the shell containing: [0009] - at least one cathode plate, comprising a current collector, a cathode active material, a binder and a conductive agent; [0010] - at least one anode plate comprising an electrically conductive and electrochemically inert material; [0011] - an electrolyte comprising a solution of at least one metal salt, wherein the metal is capable of being reduced and deposited onto the surface of the anode during charging of the battery and oxidized and dissolved into the electrolyte during discharging of the battery.
  • Figure 1 shows a schematic of a cathode electrode according to one aspect of the invention.
  • Figure 2 shows a schematic of an anode electrode according to one aspect of the invention.
  • Figure 3 shows a schematic of a cover of the battery according to one aspect of the invention.
  • Figure 4 shows a schematic of a cathode electrode according to the embodiment illustrated in Example 1 .
  • Figure 5 shows a schematic of the anode electrode according to the embodiment illustrated in Example 1 .
  • Figure 6 shows a schematic of the battery structure according to the embodiment illustrated in Example 1 .
  • Figure 7 shows the charge and discharge curve of the battery of Example 1 .
  • Figure 8 shows the cyclability curve of the battery in Example 1 .
  • the terms “comprise”, “comprises”, “comprised” or “comprising” may be used in the present description. As used herein (including the specification and/or the claims), these terms are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not as precluding the presence of one or more other feature, integer, step, component or a group thereof as would be apparent to persons having ordinary skill in the relevant art.
  • the present invention relates to a structure design of a novel secondary battery, based on the principle of ion-exchange in the electrolyte.
  • Such battery is referred to herein as an Ion-Exchange Battery (IEB).
  • IEB Ion-Exchange Battery
  • a battery 300 having a plate structure comprising a positive electrode or cathode 310, a negative electrode or anode 320, an electrolyte 340 and separator 330.
  • the positive electrode 310 comprises a current collector 31 1 , cathode active materials 312, at least one binder 313 and at least one conductive agent or material 314.
  • the cathode active materials 312 comprise lithium (Li) and/or sodium (Na) intercalation cathode materials.
  • a negative electrode 320 according to an aspect of the invention is illustrated in Figure 2. As shown, the negative electrode 320 generally comprises an electrically conductive and electrochemically inert plate 321 with a plating or coating layer 322.
  • the electrolyte according to one aspect of the invention comprises a solution, preferably an aqueous solution, of metal salts.
  • the solvent may comprise water, ethanol, methanol or mixtures thereof.
  • the metal salts comprise at least one sort of metal ion, which can be reduced and deposited onto the surface of the anode plate 322 during charging, and oxidized and dissolved into the electrolyte during discharging.
  • the electrodes 310, 320 of the invention preferably have a generally plate shape, and are preferably electrically separated from each other by a separator 330.
  • the separator 330 comprises a generally porous membrane.
  • the electrodes 310, 320 and separator 330 are packed in a shell 380, casing or other such container as will be known to persons skilled in the art.
  • the shell 380 may, for example, be formed of a plastic or metal material.
  • a cover 360 is preferably provided on the shell 380, in order to separate the internal components of the battery from the external environment.
  • the cover 360 may be insulative.
  • the cathode current collector 31 1 and the negative (anode) electrode 320 are connected through the cover 360 with the output circuit, 316 and 326.
  • the cathode current collector 31 1 may penetrate through the cover 360.
  • a cap 31 16 may be provided over the exposed ends of the collectors 31 1 .
  • the cap 31 16 may be formed from graphite, conductive plastics, Pb, Sn or an alloy of such metals.
  • the battery may be provided with a pressure limiting, or pressure relief means, as known in the art, which serves to prevent a pressure buildup inside the battery 300.
  • the pressure relief means comprises a pressure relief valve 370.
  • the valve 370 may be provided at any location on the battery as would be apparent to persons skilled in the art.
  • the valve 370 may be located on the cover 360 as shown in Figure 6.
  • the lithium ion intercalation compounds of the cathode active material may comprise layered structure compounds, spinel structure compounds or olivine structure compounds.
  • the layered structure compounds may be represented by the compositional formula Li 1+x M y M' z M" c 0 2+ n, where each of M, M', M" represents an element selected from Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, and where x, y, z, c, n individually satisfy the following relationships: 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 1 , 0 ⁇ z ⁇ 1 , 0 ⁇ c ⁇ 1 , and -0.2 ⁇ n ⁇ 0.2.
  • the spinel structure compounds may be represented by the compositional formula Li 1+x Mn y M z O k , where M is at least one element selected from Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, and where x, y, z, k individually satisfy the following relationships: 0 ⁇ x ⁇ 0.5, 1 ⁇ y ⁇ 2.5, 0 ⁇ z ⁇ 0.5, and 3 ⁇ k ⁇ 6.
  • the olivine structure compounds may be represented by the compositional formula Li x M-
  • the invention comprises a LiMn 2 0 4 /Zn battery with LiMn 2 0 4 as the cathode active material, tin plated copper film/foil as the anode, and 5 mol/L ZnCI 2 as the electrolyte.
  • Li + ions deintercalate from the spinel crystal lattice of LiMn 2 0 4 , while trivalent manganese is oxidized to tetravalent manganese with an accompanying electron output.
  • LiMn 2 0 4 turns to Li-
  • x Mn 2 0 4 and Zn 2 + ions in the electrolyte are reduced to a metallic state and are deposited on the anode surface.
  • the reaction at the cathode is LiMn 2 0 4 -xe ⁇ ⁇ Li + + Li-
  • the cathode active material comprises a material that can reversibly intercalate-deintercalate. Such compounds include those that are able to intercalate-deintercalate lithium, sodium and other ions.
  • the cathode active material is a lithium ion intercalation-deintercalation compound
  • it can preferably be selected from, for example, LiMn 2 0 4 , LiFeP0 4 , LiCo0 2 , LiM x P0 4 , LiM x SiO y (where M is a metal with a variable valence, x) and other compounds.
  • the cathode active material is a sodium ion intercalation-deintercalation compounds, it can be, for example, NaVP0 4 F.
  • the cathode current collector of the invention may be selected from a stainless steel mesh or foil, graphite plate or foil, carbon fiber or a combination thereof.
  • the thickness of the collector is between 0.01 mm and 50 mm.
  • the anode electrode 320 of the invention may comprise a flat or porous plate with a thickness between 0.001 mm and 5 mm.
  • the plate may comprise a material selected from carbon based materials, stainless steel, and metals or metal combinations, alloys etc., and combinations thereof.
  • the plate forming the anode is preferably electroplated or coated by one of C, Sn, In, Ag, Pb, Co, and Zn.
  • the separator 330 is preferably a porous membrane having a pore size between 0.01 and 1000 microns and a porosity of 20 - 95%.
  • the electrolyte of the present ion-exchange battery contains at least one sort of metal ion chosen from: Zn, Ni, Fe, Cr, Cu and Mn and combinations thereof.
  • the metal ion of the electrolyte is reduced and deposited onto the surface of the anode during the charging phase.
  • the above reaction/process is reversed. That is, during discharge, the metal deposited on the surface of the anode is oxidized and returned to its ionic state in the electrolyte solution.
  • the solvent of the electrolyte is preferably water or an aqueous solution.
  • the solvent may comprise water, ethanol, methanol, or any mixture thereof.
  • the concentration of the metal dissolved in the solvent may be 0.5-15 mol/L.
  • the electrolyte comprises an aqueous solution comprising LiCI, Li 2 S0 4 , LiN0 3 , ZnCI 2 , ZnS0 4 , Zn(N0 3 ) 2 or any combination thereof.
  • the electrolyte comprises a solution containing 1 mol/L LiCI, or Li 2 S0 4 , LiN0 3 , and 4 mol/L ZnCI 2 , or ZnS0 4 , or Zn(N0 3 ) 2 .
  • additional Li or Na salts may be added to the electrolyte.
  • these salts may be added to any desired concentration, such as 1 -15 mol/L.
  • the working principle of the present ion-exchange battery is described below: during the charging process, Li/Na ions within the cathode deintercalate into the electrolyte while, simultaneously, the metal ions contained in the electrolyte are reduced and deposited onto the surface of the anode. The discharging process reverses these reactions.
  • an ion exchange process takes place in the electrolyte. For this reason, the battery is termed an ion-exchange battery (IEB).
  • the principle of the battery of the invention is: when charging, the cathode active material reacts, where Li (HOST)- e " ⁇ Li + + (HOST), and the anode presents M x+ + xe " ⁇ M.
  • Li (HOST) is a lithium ion intercalation compound; M is a metal; M x+ is the ionic state of M.
  • the cathode active material is a sodium ion intercalation compound, the cathode active material reacts with Na (HOST)-e " ⁇ Na + + (HOST), and the anode presents M x + + xe ⁇ ⁇ M when charging.
  • the present invention also provides a battery pack, comprising a number of plate ion-exchange battery units 300 connected in parallel. For example, 2 to 10 such units may be connected. However, the invention is not intended to be limited to any specific number of units.
  • the invention provides plate shaped ion- exchange batteries having a number of suitable combinations of the cathodes, anodes and electrolytes.
  • the present invention comprises new battery system, wherein the cathode active material comprises ion intercalation/deintercalation compounds.
  • the electrochemical reversibility of the cathode relies on the intercalation (during charging of the battery) and deintercalation (during discharging of the battery) of ions to/from the cathode active material.
  • the electrochemical reversibility of the anode relies on a metal ion being reduced (during charging of the battery) and oxidized (during discharging of the battery) on the surface of the anode plate.
  • the electrolyte of the invention contains both the deintercalated ions of the cathode active material and the ion that deposits/dissolves to/from the anode surface.
  • the cathode of the invention comprises at least a cathode current collector, one or more cathode active materials, one or more binders, and one or more conductive agents.
  • the cathode current collector preferably comprises a composite material that may use carbon based conductive materials. Different carbon or carbon composite materials have different electrical properties. For example, graphite and conductive carbon fibre are both good electronic conductors, and also have excellent structural strength. As such, these materials can be used as a cathode current collector in the present invention.
  • the conductive carbon black and a binder, such as PVDF (polyvinylidene fluoride), polyethylene, polypropylene, uniformly and heat treating, the conductive material can be made with both good electronic conductivity and flexibility.
  • a conductive material is found to have suitable properties for use as a cathode collector for the invention.
  • the cathode active material are mixed with the cathode conductive agent and binder uniformly, and are then coated onto the current collector.
  • the current collector should not be too thick; the preferred range of the thickness is between 0.01 mm - 5 mm.
  • the anode structure consists mainly of an anode plate.
  • any material that has good conductivity and sufficient chemical stability can be used as the anode plate.
  • Al, Fe, Ni, Cu, Ag, Cd, W, Au, Pb, Sn, stainless steel and graphite, and combinations of same can be used for making an anode plate according to the invention.
  • the preferred thickness of the anode plate should be between 0.005 - 1 mm.
  • the anode surface is preferably covered with a layer of metal or metal oxide by a process such as plating, coating, etc.
  • the material for the plating or coating is selected from at least one of Sn, Ag, Pb, Co, Zn, and their oxide powders.
  • the thickness of the plating or coating is preferably between 0 - 0.1 mm.
  • the cathode of the battery is preferably porous, made of powder, and has a high- current discharge capability.
  • the anode which comprises a plate or foil of carbon or of the aforementioned metals, is flat, and its specific area may be limited. For example, if the surface of the anode is porous, the specific area will be high and, as such, the anode would have better electrochemical properties and a higher current discharge capability.
  • the present inventor has found that using metal foam as the anode substrate, and further plating suitable material thereon, can improve the discharge performance of the anode. For example, an anode comprised of a nickel foam material with silver plated thereon was found to have better discharge performance than nickel foam itself.
  • the electrolyte of the invention preferably includes at least one kind of metal ion that proceeds with reduction-oxidation reactions on the surface of the anode during charge and discharge, respectively.
  • the electrolyte preferably contains Zn 2+ ions, and the zinc salt may be chosen from the sulfate or chloride.
  • the preferred concentration of Zn 2+ in the electrolyte is about 4 - 6 mol/L.
  • the cathode and anode need to be connected to an external circuit, to provide an electron conducting channel.
  • the current collectors 31 1 of the cathodes extend externally of the shell 380 and run across the battery cover 360. It will be understood that the apertures in the cover 360 through with the current collectors 31 1 extend are preferably sealed in a suitable manner.
  • the anodes 320 also extend through the cover 360 and run across same to connect with the external circuit. As shown in Figure 3, the anode plate can be connected to the external circuit wires by welding or other methods inside or outside the battery.
  • the portions of the cathode current collectors 31 1 extending through the battery cover 360 are preferably sealed with a protective cover or cap 31 16 that has good electrical conductivity and is chemically stable.
  • the role of the protective cap 31 16 is to prevent water in the electrolyte of the battery from evaporating out through the opening through which the cathode current collectors extend.
  • the caps 3116 aid in preventing the corrosion of the external circuit wires and the cathode current collectors.
  • the preferred materials of the protective caps 31 16 are impermeable graphite, conductive plastics, lead alloy, etc. Various materials having the aforementioned properties will be apparent to persons skilled in the art. [0056] As will be understood by persons skilled in the art, all features described herein can be replaced by features that can provide the same, equal or similar purposes.
  • the features disclosed herein are only the general features of equal or similar examples. [0057] As will be understood by persons skilled in the art after having reviewed the present description, the main advantages offered by the present invention include one or more of: 1) desirable qualitative characteristics such a battery providing good
  • Example 1 The cathode active material LiMn 2 0 4 , conductive carbon black and SBR (styrene butadiene rubber milk) were mixed uniformly in accordance with the proportion of 85:10:5, and then the mixture was added into water to make slurry.
  • the cathode current collector comprised a graphite plate with a thickness of 1 mm; the slurry was coated onto the graphite plate and dried at 105 °C for 10 hours.
  • the active material coated on each graphite plate was 5 g, and the total amount of the cathode active material was 20 g, with a theoretical capacity of 2000 mAh.
  • the configuration of the cathode is shown in figure 4.
  • the anode of the battery comprised a copper foil with a thickness of 0.1 mm, and had the configuration as shown in Figure 5.
  • the size of the anode substrate was slightly larger than that of the cathode, so that the full capacity of the cathode could be used and the current distribution at the edge of the anode would be uniform.
  • the copper foil was covered by a certain thickness of plating/coating to enhance the adhesion properties of metal reduced from metal ions in the electrolyte.
  • the surface of the copper foil was coated with a layer of tin by plating, and the thickness of the tin plating was about 0.01 mm.
  • the separator membrane of the battery was a non-woven material with a thickness of 0.1 mm.
  • the battery was formed with five anode plates and four cathode plates in alternating fashion.
  • the adjacent anode and cathode electrodes were separated by a layer of the non-woven membrane.
  • the assembled electrodes were placed in a plastic battery shell, and then 20 ml of electrolyte was injected.
  • the cathode current collector and anode plate was allowed to extend through the battery cover, and were sealed by a binder.
  • the electrolyte comprised a water solution containing 4 mol/L LiCI and 4.5 mol/L ZnCI.
  • the amount of Zn 2+ in the electrolyte was chosen to be more than the amount of Zn on the anode plate after charging. In this example, 0.09 mol Zn 2+ was provided in the electrolyte. This amount was based on a calculation that, at 2 Ah, there would be 0.035 mol Zn 2+ consumed during charging.
  • the concentration of Zn 2+ in the electrolyte after charging is 2.75 mol/L.
  • Example 2 A battery was made according to a method similar to that of Example 1 .
  • the anode plate comprised a tin plated nickel foam, of the same size as the anode plate of Example 1 .
  • nickel foam as the skeleton for the anode provides an increased specific area than a metal plate/foil, and the tin plating provides a better interface for the electrodeposition of Zn.
  • the performance of the battery according to this example is shown in Table 1 .
  • Example 3 A battery was made according to a method similar to that of Example 1 .
  • the anode plate comprised 316L stainless steel.
  • the thickness of the stainless steel plate was 0.5 mm.
  • the surface of the stainless steel was passivated with concentrated sulfuric acid and then sanded rough with abrasive paper.
  • the performance of the battery according to this example is shown in Table 1 .

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

Une batterie rechargeable à structure plate comprend une électrode cathode, une électrode anode et un électrolyte. L'électrode cathode comprend un collecteur de courant, un matériau actif de cathode, un liant et un agent conducteur. Le matériau actif de cathode est choisi de préférence entre les composés d'intercalage à base de lithium et/ou de sodium. L'électrode anode comprend une plaque électrode qui est conductrice d'électricité et électrochimiquement inerte. L'électrolyte est constitué d'une solution de sels métalliques. La solution peut être constituée d'eau, d'éthanol, de méthanol et de leur mélange. Les sels métalliques sont constitués d'au moins un ion métallique qui peut être réduit et déposé à la surface d'une autre plaque d'anode pendant le chargement et oxydé et dissous dans l'électrolyte pendant le déchargement.
PCT/CA2012/050032 2011-01-21 2012-01-20 Batterie échangeuse d'ions à configuration plate WO2012097456A1 (fr)

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AU2012208932A AU2012208932A1 (en) 2011-01-21 2012-01-20 Ion-exchange battery with a plate configuration

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US201161434959P 2011-01-21 2011-01-21
US61/434,959 2011-01-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104659372A (zh) * 2015-02-15 2015-05-27 天能集团江苏科技有限公司 无酸铅锂二次电池负极板及其制备方法
US20210313634A1 (en) * 2020-04-01 2021-10-07 Global Graphene Group, Inc. Graphene-enabled battery fast-charging and cooling system and method of operating same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1468416A (en) * 1973-09-10 1977-03-23 Exxon Research Engineering Co Chalcogenide battery
US5800939A (en) * 1994-08-23 1998-09-01 Canon Kabushiki Kaisha Battery and method for the manufacture of such a battery
US6187475B1 (en) * 1998-08-31 2001-02-13 Finecell Co., Ltd. Aqueous zinc sulfate (II) rechargeable cell containing manganese (II) salt and carbon powder
US6645667B1 (en) * 1999-08-06 2003-11-11 Matsushita Electric Industrial Co., Ltd. Lithium secondary cell
CN101299476A (zh) * 2008-06-16 2008-11-05 中南大学 一种锌镍静态单液流电池
JP2010113963A (ja) * 2008-11-06 2010-05-20 Toyota Central R&D Labs Inc 水系リチウムイオン二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1468416A (en) * 1973-09-10 1977-03-23 Exxon Research Engineering Co Chalcogenide battery
US5800939A (en) * 1994-08-23 1998-09-01 Canon Kabushiki Kaisha Battery and method for the manufacture of such a battery
US6187475B1 (en) * 1998-08-31 2001-02-13 Finecell Co., Ltd. Aqueous zinc sulfate (II) rechargeable cell containing manganese (II) salt and carbon powder
US6645667B1 (en) * 1999-08-06 2003-11-11 Matsushita Electric Industrial Co., Ltd. Lithium secondary cell
CN101299476A (zh) * 2008-06-16 2008-11-05 中南大学 一种锌镍静态单液流电池
JP2010113963A (ja) * 2008-11-06 2010-05-20 Toyota Central R&D Labs Inc 水系リチウムイオン二次電池

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LI ET AL.: "Rechargeable Lithium Batteries with Aqueous Electrolytes", SCIENCE, vol. 264, no. 5162, 20 May 1994 (1994-05-20), pages 1115 - 1118, XP002699783, DOI: doi:10.1126/science.264.5162.1115 *
LINDEN, HANDBOOK OF BATTERIES AND FUEL CELLS, 1984, pages 19-1 - 19-8 *
LUO ET AL.: "Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte", NATURE CHENZISTRY, vol. 2, August 2010 (2010-08-01), pages 760 - 765, XP008127000, DOI: doi:10.1038/nchem.763 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104659372A (zh) * 2015-02-15 2015-05-27 天能集团江苏科技有限公司 无酸铅锂二次电池负极板及其制备方法
US20210313634A1 (en) * 2020-04-01 2021-10-07 Global Graphene Group, Inc. Graphene-enabled battery fast-charging and cooling system and method of operating same
US11958382B2 (en) * 2020-04-01 2024-04-16 Honeycomb Battery Company Graphene-enabled battery fast-charging and cooling system and method of operating same

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