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WO2014041800A1 - ÉLÉMENT MÉTALLIQUE NA METAL Na CELL - Google Patents

ÉLÉMENT MÉTALLIQUE NA METAL Na CELL Download PDF

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WO2014041800A1
WO2014041800A1 PCT/JP2013/005378 JP2013005378W WO2014041800A1 WO 2014041800 A1 WO2014041800 A1 WO 2014041800A1 JP 2013005378 W JP2013005378 W JP 2013005378W WO 2014041800 A1 WO2014041800 A1 WO 2014041800A1
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battery
metal
negative electrode
positive electrode
water
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Japanese (ja)
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林　克郎
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Tokyo Institute of Technology NUC
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Tokyo Institute of Technology NUC
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid 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

Definitions

  • the present invention relates to a metal Na battery.
  • Li + ion battery has attracted attention as one of such batteries.
  • Li + ion battery it is difficult to provide an electric vehicle using a lithium ion battery as a storage battery with the same range as a conventional internal combustion engine.
  • commercial Li-ion batteries have only an energy density of about 100 to 200 Wh / kg.
  • an Li-ion battery requires an energy density four or more times the current level. Such a significant improvement in energy density is difficult only with the technology in the extension of the conventional Li-ion battery. Therefore, new energy conversion devices have been required.
  • Li-air batteries As one of the means for achieving high energy density, there is known a technology in which a light alkali metal itself having a large change in reaction free energy due to an oxidation reaction is used as the active material of the negative electrode.
  • so-called Li-air batteries have been mainly studied.
  • a lithium-air battery using a carbon composite electrode positive electrode, a polymer membrane separator, and an organic electrolytic solution that transmits oxygen by using a Li metal foil as a negative electrode Non-patent Document 1).
  • This Li-air battery has been considered as the basic type of Li-air battery developed later.
  • the Li-air battery is a battery reaction of 4Li + O 2 ⁇ 2Li 2 O, and the calculated value including O 2 in the battery reaction weight is 5,200 Wh / kg, calculated without O 2. It has a high theoretical energy density of 11,140 Wh / kg. Therefore, it is supposed that an experimentally higher energy density can be obtained as compared to a Li-ion battery having a theoretical energy density of 250 to 350 Wh / kg.
  • Li-air batteries (referred to herein as "Li-water-air batteries") having a different structure have also been developed.
  • This Li-water-air battery is said to be capable of completely performing a battery reaction because the reaction product at the time of discharge is LiOH which is dissolved in a water-soluble electrolyte.
  • the theoretical energy density of this Li-water-air cell is about 5,700 Wh / kg excluding the weight of oxygen required for the reaction.
  • a discharge of about 800 Wh / kg has been demonstrated in the experiment (Non-Patent Document 2).
  • ⁇ -alumina As another means for providing high energy density to the battery, a technology using ⁇ -alumina as a solid electrolyte of a sodium-sulfur (Na-S) battery is known.
  • the ⁇ -alumina is a crystal having a layered structure in which a structural layer called a spinel block sandwiches a layer composed of Na + ions (hereinafter also referred to as sodium ions, Na ions or simply Na + ).
  • ⁇ -alumina has two structures in which the layers of hexagonal ⁇ -phase and cyclohedral ⁇ ′-phase overlap slightly differently.
  • the orientation-controlled polycrystal is a solid electrolyte exhibiting high-speed Na + ion conductivity of 0.1 S ⁇ cm ⁇ 1 or more at about 350 ° C. because Na + ions in the layer can diffuse at high speed.
  • Na-S batteries were initially developed as secondary batteries for electric vehicles, which can achieve high energy density four to five times that of lead acid batteries.
  • Na-S batteries are currently commercialized for stationary use because they operate at a high temperature of about 350.degree.
  • metal Na for the negative electrode
  • graphite wool for the current collector of the molten molten salt are respectively used.
  • Typical operating temperatures are 300-350 ° C., where the sodium sulfide melts and the conductivity of the electrolyte is sufficiently high.
  • Na-S batteries are characterized by high charge and discharge energy efficiency.
  • NASICON is known as a solid electrolyte having high Na + ion conductivity and ion conductivity close to ⁇ or ⁇ ′ ′ alumina.
  • Nasacon is AMM ′ P 3 O 12 (A is an alkali ion It is a series of rhombohedral or monoclinic crystals represented by the general formula of various cations including M, M ', which are divalent to pentavalent cations.
  • Conducting Na + ions typical chemical composition of NASICON to, Na l + x Si x Zr 2 P 3-x O 12 (0 ⁇ x ⁇ 3) is expressed by.
  • a technology using ⁇ or ⁇ ′ ′ alumina electrolyte and metal Na as a negative electrode active material is also known.
  • the primary battery is operated in the region, so that the negative electrode is amalgam of Na-Hg, the separator is a ⁇ alumina electrolyte, the positive electrode active material is contained in a water-soluble electrolytic solution or an organic solvent such as propylene carbonate Br 2 , I 2 , H 2 O and O 2 (Non-Patent Document 4) Since metal Na is solid at room temperature, when only solid metal Na is used as the negative electrode, Na chemical species can not be sufficiently diffused and the discharge characteristics are extremely low.
  • Hg has been used to solve this problem Hg improves diffusion by forming a liquid phase at room temperature with Na.
  • the theoretical energy density of this cell The degree of energy is in the range of 500 to 1,550 Wh / kg, and the actual energy density by the battery test is 1/2 to 1/3 of them, and the energy density is practically higher than that of the Li ion battery.
  • the present invention has been made in view of these problems, and an object thereof is to reduce the cost by using only common materials for the main members while reducing the energy density per weight or volume significantly. It is to provide.
  • the metal Na battery Na + ion conductivity and Na + ion conductor having a substantially metal disposed on one side of the Na + ion conductor
  • the metal Na with light and active metal Na and water, and oxygen which can be taken in from the outside if necessary, is used as the active material, and thus the metal Na with significantly improved energy density per weight or volume A battery can be provided.
  • metallic Na is used for the negative electrode, decomposition of the ceramic separator used as the organic electrolytic solution, the current collector, and the Na + ion conductor is made in comparison with the conventional metal Li-water-air battery or Li ion battery. It is hard to cause.
  • the ion conductivity of the Na + ion conductive solid electrolyte itself is also good, it does not serve as a barrier for improving the power density of the battery.
  • metal Na batteries use only common materials and elements for main components, they can be manufactured inexpensively and do not hinder large-scale use.
  • Na which is responsible for charge transfer in the battery, does not have the problems of abundance and uneven distribution of resources as compared with Li used in Li-ion batteries.
  • Al aluminum
  • the negative electrode holding metal Na it is not necessary to use copper which is often required when using Li, and cheaper aluminum (Al) can be suitably used.
  • the elements and raw materials that make up the ⁇ -alumina based and Nasicon ceramics used as the Na + ion conductor are also inexpensive and touched.
  • the present invention it is possible to provide a metallic Na battery in which the energy density per weight or volume is significantly improved while suppressing the cost by using only common materials for the main members.
  • FIG. 1 (A) is a schematic view showing a sodium-water-air battery of Embodiment 1.
  • FIG. 1 (B) is a schematic view showing a sodium-water battery of Embodiment 2. It is the schematic which shows the outline
  • the current-voltage characteristics obtained at 50 ° C. are shown for the metal Na battery using the Nashicon separator of Example 1.
  • the discharge characteristics obtained at 50 ° C. are shown for the metal Na battery using the Nashicon separator of Example 1.
  • the current-voltage obtained at 50 ° C. is shown for a metallic Na battery using the Nashicon separator of Example 2.
  • the current-voltage characteristics obtained at 30 ° C., 40 ° C., and 50 ° C. are shown for the metal Na battery using the ⁇ -alumina-based separator of Example 3.
  • the current-voltage characteristics measured at 25 ° C. in air for the metal Na battery using the gas-permeable positive electrode of Example 4 are shown.
  • the evaluation of the charge / discharge characteristic with respect to the metal Na battery using the gas-permeable positive electrode of Example 4 is shown.
  • the present inventors are Na + ion conductors (hereinafter also referred to as separators), which are Na + ion conductive solid electrolytes, ⁇ and ⁇ ′ ′ alumina, and Na—Zr—Si—P—O-based Nasacon ceramics.
  • separators Na + ion conductors
  • a battery metal Na battery
  • Na + ion conductive Indicates that Na + ions can be selectively conducted. Selectively conductive does not necessarily mean that only Na + ions are conducted and other substances are not conducted at all. That is, the case in which Na + ions can be conducted at a significantly higher frequency than other substances is also included in the case where they can be conducted selectively.
  • Na of the negative electrode active material When the metal Na battery is discharged, Na of the negative electrode active material is ionized to be Na + ions and dissolved in the organic electrolytic solution to supply electrons to the negative electrode. Na + ions diffuse through the Na + ion conductor into the aqueous electrolyte. That is, the partial reaction at the negative electrode is Na ⁇ Na + + e ⁇ .
  • the partial reaction at the positive electrode is 1 / 2H 2 O + e ⁇ + 1 ⁇ 4O 2 ⁇ OH ⁇ .
  • the total reaction in the metal Na battery is Na + 1/2 H 2 O + e ⁇ + 1 ⁇ 4 O 2 ⁇ NaOH (aq). That is, as the discharge progresses, the concentration of NaOH in the water-soluble electrolyte increases. However, hydrogen gas is not generated from the surface of the positive electrode.
  • This operating condition of the metal Na battery 20 is referred to as "sodium-water-air battery".
  • a sodium-water-air battery will be described as Embodiment 1 with reference to FIG. 1 (A).
  • FIG. 1 (A) is a schematic view showing the structure of a metal Na battery 20 (sodium-water-air battery) according to the first embodiment. First, an outline of the structure of the metal Na battery 20 is described, and then each configuration is described in detail.
  • the negative active material and Na + ion conductor 1 having a Na + ion-conducting, substantially consisting of metallic Na, which is arranged on one side of the Na + ion conductor 1 4 and at least a portion of the negative electrode active material 4 being in contact with the negative electrode 5 capable of conducting electrons generated when metal Na is ionized and in contact with one surface of the negative electrode 5 and the Na + ion conductor 1 water to the pooled organic electrolyte 2, stored as a positive electrode 8 disposed on the other side of the Na + ion conductor 1, in contact with the other surface of the positive electrode 8 and the Na + ion conductor 1 as And a water-soluble electrolyte 3 and having a base resistance and a positive electrode side housing portion 13.
  • the housing 7 accommodates the main components of the metal Na battery 20.
  • the housing 7 includes a negative electrode side housing portion 12 and a positive electrode side housing portion 13.
  • the negative electrode side accommodation portion 12 accommodates the negative electrode 5, the negative electrode active material 4 and the organic electrolytic solution 2 which are members on the negative electrode side of the metal Na battery 20.
  • the negative electrode side housing portion 12 has a structure for keeping the inside airtight after housing these. In this state, the negative electrode external terminal 6 extends from the inside to the outside of the negative electrode side housing portion 12.
  • the positive electrode side accommodation portion 13 accommodates the positive electrode 8 and the water-soluble electrolyte 3 which are members on the positive electrode side of the metal Na battery 20. Further, the positive electrode external terminal 10 extends from the inside of the positive electrode side accommodation portion 13 to the outside. Furthermore, the gas introduction pipe 11 may be inserted into the positive electrode side accommodation portion 13 from the outside as needed.
  • the concentration of NaOH (sodium hydroxide) in the aqueous electrolyte solution 3 increases as the reaction proceeds.
  • the pH of the water-soluble electrolyte 3 may exceed 13. Therefore, at least a portion of the positive electrode side accommodating portion 13 of the housing 7 in contact with the water-soluble electrolytic solution 3 is formed of a basic resistant material, preferably a strongly basic resistant material that can withstand pH 14 or more.
  • a positive electrode side housing portion 13 for example, a container such as Pyrex (registered trademark) glass, nylon, polyvinylidene chloride, peak (polyether ether ketone) resin (manufactured by VICTREX), etc. can be suitably used.
  • the negative electrode side accommodation portion 12 and the positive electrode side accommodation portion 13 of the housing 7 may be integrally formed or may be separately formed.
  • the Na + ion conductor 1 separates the organic electrolyte solution 2 contained in the negative electrode side housing portion 12 from the water-soluble electrolyte solution 3 contained in the positive electrode side housing portion 13.
  • the Na + ion conductor 1 is made of a compact Na + ion conductive solid electrolyte ceramic.
  • materials suitable for the Na + ion conductor 1 the following two materials are mainly considered.
  • the first material suitable for the Na + ion conductor 1 is rhombohedral ⁇ -alumina and hexagonal ⁇ ′ ′-alumina ceramics. These are combined to form a polycrystalline “ ⁇ -alumina based ceramic”. It is called. ⁇ ′ ′-alumina is preferable to ⁇ -alumina because higher Na + ion conductivity improves cell performance, but there is no significant performance difference even in the presence of two phases, and the ⁇ alumina produced actually The ceramics often contain both ⁇ -alumina and ⁇ ′ ′-alumina as main phases.
  • the metal Na battery 20 can be operated in the range of 0 to 100 ° C.
  • the ion conductivity of these ⁇ -alumina based ceramics is typically in the range of 10 ⁇ 3 to 0.1 S ⁇ cm ⁇ 1 . This ionic conductivity is very high as a solid electrolyte, about 1/10 of 1 M HCl aqueous solution.
  • ⁇ alumina-based ceramics have high stability without decomposition even in direct contact with metal Na, as demonstrated for application to Na-S batteries. Therefore, ⁇ -alumina-based ceramics play an important role in securing safety while incorporating metallic Na having high activity into a battery structure.
  • the second suitable material for the Na + ion conductor 1 is monoclinic or rhombohedral (polycrystalline) Nasicon ceramics.
  • the feature of the crystal structure is that Na + ions embedded in a network of oxide ions tetrahedrally and hexahedrally coordinated to cations have a structure capable of easily moving.
  • an electric conduction of 0-100 ° C, typically 10 -4 to 0.1 S ⁇ cm -1 is exhibited. Since Nasicon ceramics are stable even when immersed in an aqueous solution for a long time (J.J. Auborn & D. W. Johnson., Solid State Ionics, Vol. 5, p. 315, 1981), the water-soluble electrolyte 3 Show excellent characteristics for separating the organic electrolyte 2.
  • the composition of the ion conductive species in the ⁇ -alumina based ceramics and the NASICON ceramics be adjusted so as to be limited to Na + ions. That is, it is desirable to minimize the amount of chemical species to be monovalent cations other than Na, such as K (potassium).
  • K potassium
  • the amount of monovalent cations other than Na + ions increases, the ion conductivity decreases and, in addition, the exchange of monovalent cations occurs during the operation of the battery, which causes the volume change in these ceramics, thereby making the ceramics Makes it easy to cause damage.
  • These ceramics are molded into a dense diaphragm. In order to reduce the internal resistance of the battery, the thinner the thickness, the better.
  • the thickness of the Na + ion conductor 1 be 0.1 to 2 mm from the viewpoint of strength.
  • a structure in which a dense ⁇ -alumina-based or NASICON film is formed on a base material made of a material that does not deteriorate with the insulating electrolyte 3 such as porous alumina as the Na + ion conductor 1. May be used. In this case, the resistance can be further reduced.
  • the material of the negative electrode 5 is solid (having a melting point of over 100 ° C.) at the operating temperature (0 to 100 ° C.) of the metal Na battery 20 and has a good conductivity to the extent that electrons generated by dissolving metal Na can be conducted. Any material may be used as long as it is a material that does not react significantly with metal Na. As such a material, for example, Al, Cu, Fe, Cr, Ni, Ti, an alloy containing these as main components, and the like can be suitably used. From the viewpoint of cost and weight, metals having Al as a main component are preferable. Forming the negative electrode 5 as a porous metal is more advantageous because the diffusion of sodium is promoted.
  • the negative electrode active material 4 is accommodated in the negative electrode side accommodation portion 12 so as to be in contact with at least a part of the negative electrode 5.
  • the negative electrode active material 4 contains metal Na as a main component. It is desirable that the negative electrode active material 4 be substantially made of metal Na. “Consisting essentially of metal Na” means that the content of metal Na in the negative electrode active material 4 is 90% by mass or more.
  • the negative electrode active material 4 is electrically connected to the negative electrode 5 and the negative electrode external terminal 6 connected to the negative electrode 5.
  • the metal Na which is the main component of the negative electrode active material 4 may be held by a flat metal plate including the negative electrode 5, a metal wire, a wire mesh or the like. Alternatively, when the negative electrode 5 is formed of a porous metal, Na may be impregnated into the pores to integrate the negative electrode active material 4 and the negative electrode 5.
  • the negative electrode active material 4 preferably contains substantially no amalgam, which is a liquid alloy of mercury and Na.
  • the content of mercury in the negative electrode active material 4 is desirably less than 1.0% by mass, and more desirably less than 0.1% by mass.
  • the energy density per weight of the metal Na battery 20 can be improved, the load on the environment can be reduced, and the safety can be improved.
  • the organic electrolytic solution 2 is a substance having Na + ion conductivity.
  • the organic electrolytic solution 2 propylene carbonate (PC), ethylene carbonate (EC), or a mixed solution of ethylene carbonate and dimethyl carbonate (EC: DMC) is preferable.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • Na has a smaller absolute value of the standard redox potential than Li, it does not require the stability as in the organic electrolyte of the conventional Li-ion battery or Li-water-air battery. Therefore, it is thought that the electrolyte solution considered unsuitable for Li ion batteries can be utilized. Even if the organic electrolyte solution 2 is omitted and the Na + ion conductor 1 and the negative electrode active material 4 are brought into direct contact, an electromotive force is generated in principle.
  • the organic electrolyte solution 2 plays an important role in order to sufficiently diffuse sodium between the Na + ion conductor 1 and the negative electrode active material 4.
  • sodium salt such as NaPF 6 , NaClO 4 , NaBO 4 or the like, or, if necessary, an electric current at the interface between the negative electrode active material 4 and the organic electrolytic solution Additives are added to improve the properties. Concentration of sodium salts such as NaPF 6 is more than 0.5M are preferred, more preferably at least 0.8 M, more preferably at least 0.95 M, more 1.0M is more preferable.
  • FEC fluoroethylene carbonate
  • the positive electrode 8 may have any shape of a plate or a wire mesh.
  • a material for example, carbon can be suitably used.
  • the positive electrode 8 may be a carbon plate, a metal electrode mainly composed of nickel (Ni), platinum (Pt) or palladium
  • an electrode made of a noble metal such as (Pd) or an electrode in which a noble metal is coated on a stainless steel mesh or the like (for example, carbon plates can be purchased from Tokai Carbon Co., and metal materials can be purchased from Niraco Co., Ltd.).
  • a carbon plate as the positive electrode 8.
  • a metal electrode mainly composed of nickel is particularly preferable.
  • oxygen or air may be supplied using a compressed gas cylinder.
  • the atmosphere may be supplied by using a pump or the like as needed.
  • the water-soluble electrolyte 3 is accommodated in the positive electrode side accommodation portion 13.
  • a sodium salt is added to the water-soluble electrolyte solution 3 to impart Na + ion conductivity.
  • NaOH is suitable.
  • the positive electrode 8 is in electrical contact with the positive electrode external terminal 10.
  • FIG. 1A shows the case where a platinum wire mesh (Pt wire mesh) is used as the positive electrode 8.
  • the positive electrode 8 is immersed in the water-soluble electrolyte 3.
  • a gas introduction pipe 11 for supplying a gas containing oxygen may be further provided.
  • a Na salt is added to the water-soluble electrolyte solution 3 in order to impart Na + ion conductivity.
  • the H 3 O + ion concentration in the water-soluble electrolyte 3 increases, and the H 3 O + diffuses into the Na + ion conductor 1 and reduces when reaching the organic electrolyte 2 and the negative electrode active material 4 It may be decomposed to form an ion diffusion barrier layer of oxide accompanied by generation of hydrogen gas.
  • the H 3 O + ions move from the organic electrolyte 2 into the water-soluble electrolyte 3 with the discharge of the metal Na battery 20, the NaOH concentration becomes high. However, there is no particular problem even if the depth of discharge is further increased.
  • the concentration of monovalent cations other than Na + ions such as K + be lower. Specifically, it is desirable that the Na + ion concentration ratio is less than 5%.
  • the energy density per weight or volume is significantly large.
  • An improved metal Na battery 20 can be provided.
  • metallic Na is used for the negative electrode, decomposition of the ceramic separator used as the organic electrolytic solution, the current collector, and the Na + ion conductor 1 as compared with the conventional metal Li-water-air battery or Li ion battery Hard to cause
  • the ion conductivity of the Na + ion conductive solid electrolyte itself is also good, it does not serve as a barrier for improving the power density of the battery.
  • the metal Na battery 20 can be manufactured inexpensively and does not hinder large-scale use.
  • Na which is responsible for charge transfer in the battery, does not have the problems of abundance and uneven distribution of resources as compared with Li used in Li-ion batteries.
  • the negative electrode 5 holding metal Na it is not necessary to use copper which is often required when using Li, and cheaper Al can be suitably used.
  • the elements and raw materials constituting the ⁇ -alumina system and the NASICON ceramics used as the Na + ion conductor 1 are also inexpensive and touched.
  • amalgam which is a liquid alloy of mercury and sodium
  • the energy density of the metal Na battery 20 can be improved.
  • the metal Na battery 20 is excellent not only in manufacture but also in terms of disposal.
  • the organic electrolytic solution 2 in which solid metal Na and Na salt are dissolved on the negative electrode 5 side through the Na + ion conductor 1 is dissolved on the positive electrode 8 side.
  • No. 3 enables stable operation at room temperature to 80 ° C.
  • ⁇ and ⁇ ′ ′ alumina and Nasicon ceramics are used as Na + ion conductor 1, good conduction of Na + ions does not become a main resistance component for discharge, and it is a main factor that inhibits the cell reaction.
  • FIG. 1 (B) is a schematic view showing the structure of a metal Na battery 20 (sodium-water battery) according to the second embodiment. Here, only differences from the sodium-water-air battery of Embodiment 1 will be described.
  • the water-soluble electrolyte 3 is accommodated in the positive electrode side accommodating portion 13 by forming the positive electrode 8 on one side of the positive electrode side accommodating portion 13.
  • the positive electrode 8 has gas permeability that directly takes in oxygen from the outside during discharge and releases the oxygen generated on the electrode during charge to the outside.
  • the positive electrode 8 is appropriately infiltrated by the water-soluble electrolyte 3, it does not allow the water-soluble electrolyte 3 to pass through. That is, the positive electrode 8 has gas permeability, and the other surface opposite to the one surface facing the Na + ion conductor 1 is at least partially in contact with air.
  • the gas-permeable positive electrode 8 is water-repellent on the air side and porous and permeable to air, good for oxygen reduction and water oxidation reaction on the aqueous solution side, and excellent in electric conductivity and durability.
  • a positive electrode 8 a gas diffusion layer, a catalyst layer, and a nickel metal mesh are laminated in this order, and a laminated board obtained by hot pressing them at about 200 ° C., for example, can be suitably used.
  • the gas diffusion layer can be obtained by mixing highly conductive carbon (Ketjen black) and a binder (PTEF emulsion) and hot pressing the mixture at, for example, about 200 ° C.
  • the catalyst layer can be obtained by mixing activated carbon on which a catalyst consisting of a Mn 3 O 4 phase is supported with a binder (PTEF emulsion) and hot-pressing the mixture at, for example, about 200 ° C.
  • Table 1 shows theoretical electromotive force (V) at 25 ° C. and theoretical energy density (Wh / kg) at 25 ° C. of sodium-water-air battery (embodiment 1) and sodium-water battery (embodiment 2). In the case where O 2 is not included and when included.
  • “s” “l” “aq” “g” respectively represent solid, liquid, aqueous solution and gas.
  • an energy density of about 3 to 15 times that of a typical Li ion battery can be obtained.
  • the charge / discharge rate (current density) of the metal Na battery 20 is about 0.1 mA / cm 2 , more preferably about 0.5 mA / cm 2 , and still more preferably about 1 mA / cm 2 .
  • Example 1 Metallic Na battery using Nashikon separator
  • Na 3 Zr 2 Si 2 so as to have the composition of the PO 12, Na 3 PO 4, ZrO 2, SiO 2 raw material is weighed and mixed, and 12 hours calcined at 1100 ° C..
  • the powder is pulverized by a ball mill, then subjected to uniaxial pressing and cold isostatic pressing and sintered at 1275 ° C. for 15 hours to form a disc having a Nasicon phase purity of 98% or more and a diameter of about 16 mm.
  • a sintered body having a relative density of 98% or more and no gas permeability was obtained.
  • Nashicon separator Na + ion conductor 1
  • the temperature characteristics of the sum of the resistance components in the crystal grains and grain boundaries of the above-described Nashicon ceramic were evaluated by the AC impedance method.
  • the activation energy of the electrical conductivity showed a typical value of 0.27 eV.
  • the direct current resistance as the separator was 53 ⁇ ⁇ cm ⁇ 2 at 50 ° C.
  • FIG. 2 is a schematic view showing an outline of a battery test.
  • the metal Na battery 20 used in the present example was configured as follows.
  • the housing 7 is configured by the O-ring 14, the jig 15, the glove box 16, the negative electrode side housing portion 12 including the lid portion 17, and the positive electrode side housing portion 13.
  • the obtained Na + ion conductor 1 was attached to a jig 15 made of peak resin (polyether ether ketone) designed to have an effective area of 1.1 cm 2 .
  • the jig 15 has a structure in which the inside of the negative electrode 5 side and the outside of the positive electrode 8 are airtightly separated by a rubber O-ring 14.
  • a glove box 16 providing a purified atmosphere from which oxygen and water were removed, 20 mg of metal Na pieces were bound to a platinum wire and stored in the jig 15 described above. Furthermore, after pouring the organic electrolyte solution 2 in which 0.5 M NaPF 6 and 0.05 M fluoroethylene carbonate were dissolved in propylene carbonate so that all metal Na was immersed, O-ring 14 and lid 17 Airtight sealing was performed to form the negative electrode side accommodation portion 12. The platinum wire was drawn out from the negative electrode side accommodation portion 12 so as to maintain the airtightness, and was used as a negative electrode external terminal 6.
  • the water-soluble electrolyte 3 0.1 M NaOH aqueous solution was used.
  • the water-soluble electrolyte solution 3 was accommodated in the positive electrode side accommodation portion 13 made of Pyrex (registered trademark) glass.
  • the negative electrode side housing portion 12 in which the above-described Na was sealed in the water-soluble electrolyte 3 was placed so that all the Na + ion conductors 1 were immersed in the water-soluble electrolyte 3.
  • 4 cm 2 of 250 mesh Pt wire netting (a metal material purchased from Nyako Co., Ltd.) was set as a positive electrode 8.
  • the platinum wire welded to the positive electrode 8 was drawn out from the positive electrode side accommodation portion 13 to form a positive electrode external terminal 10.
  • FIG. 3 shows the current-voltage characteristics obtained at 50 ° C. for the metal Na battery using the Nashicon separator of Example 1.
  • the voltage (V) at current 0 corresponds to the open electromotive force.
  • the metal Na battery of this example operated as a Na-water-air battery.
  • the obtained open electromotive force (V) almost matches the theoretical electromotive force.
  • the measured value was slightly smaller than the theoretical electromotive force. It is considered that this is because 0.1 M NaOH was previously dissolved in the aqueous electrolyte.
  • 5% H 2 -95% Ar was supplied through the gas introduction pipe, the metal Na battery of this example operated as a Na-water battery.
  • the obtained open electromotive force (V) showed a value close to the theoretical electromotive force.
  • the measured value was larger than the theoretical electromotive force. It is considered that this is because the dissolved oxygen in the water-soluble electrolyte could not be completely removed.
  • Current - the internal resistance of the battery was estimated from the slope of the voltage characteristic, Na- water - about 200 [Omega / cm 2 in the air battery, the Na- water cell was about 400 ⁇ / cm 2. This was a value several times larger than the resistance value of the separator of Nashicon ceramics. Therefore, it was judged that Nashicon ceramic itself is not a main component of internal resistance, and works effectively as the Na + ion conductor without impairing the battery performance itself.
  • FIG. 4 shows the discharge characteristics obtained at 50 ° C. for the metal Na battery using the Nashicon separator of Example 1.
  • the electromotive force voltage / V
  • the integrated current value discharge amount / mAh
  • the metal Na battery of the present Example operated stably for 2 days or more in the state which the positive electrode side accommodating part was immersed in the strongly-basic (pH> 13) water-soluble electrolyte solution.
  • Example 2 Metallic Na Battery Using Nashicon Separator
  • the present embodiment is different from the first embodiment in that a sintered body having the same composition as that of the first embodiment is polished to a thickness of 0.5 mm to obtain a separator made of Nashicon ceramics.
  • the battery test shown in FIG. 2 was performed in the same manner as in Example 1 for the metal Na battery 20 using the obtained Nashicon separator. Point metal Na pieces tied to the platinum wire was 23 mg, that was used NaPF 6 of 1.0 M, a point used as a positive electrode 8 12cm 2 carbon plate (Tokai Carbon Co., Ltd. isotropic graphite) And a battery test was conducted in the same manner as Example 1 except that only 100% O 2 gas was supplied to the positive electrode 8.
  • FIG. 5 shows the current-voltage obtained at 50 ° C. for the metal Na battery using the Nashicon separator of Example 2.
  • the open electromotive force (V) was almost in agreement with the theoretical electromotive force. Therefore, it was confirmed that the metal Na battery of this example operated as a Na-water-air battery.
  • the maximum value of the power density (W / kg) is a total of 4.1 mg of the enclosed metal sodium weight of 23 mg and 18 mg of water required for the complete reaction, and 200 W / kg in terms of the effective area of the Nashicon separator.
  • the current density at that time was 6 mA / cm 2 .
  • FIG. 5 in the present example, the unstable behavior seen in Example 1 (FIG. 3) was not confirmed.
  • Example 2 From this, it is considered that the main reason that the current density was further increased than in Example 1 was that the positive electrode was replaced from a Pt wire mesh to a carbon plate. In addition, it is considered that the increase in the concentration of NaPF 6 in the organic electrolyte is also a factor.
  • Table 2 shows the open electromotive force (V), the energy density (Wh / kg) at 50 ° C., and the power density (W / kg) obtained by the metal Na battery using the Nasicon separators of Examples 1 and 2. .
  • the energy and the power density were calculated from the value at the maximum power in the current-voltage characteristics and the mass of the negative electrode and the positive electrode active material excluding oxygen gas involved in the battery reaction.
  • a conventional Li-ion battery requires a battery of about 1200 kg. Therefore, the conventional Li-ion battery is impractical for practical use.
  • the weight of the battery is about 200 kg. This is a realistic weight comparable to current electric vehicles. In a general-purpose automobile, it is only necessary to constantly obtain a maximum output of about 80 kW for about 1 minute and a steady output of about 20 kW.
  • the metal Na battery of the present embodiment has a high energy density, that is, the feature of lightness is not necessarily limited to a mobile object such as an automobile, and is also suitable as a battery for home electric appliances.
  • Example 3 ⁇ -alumina based metal Na battery using separator
  • a raw material was mixed with Na 2 CO 3 , g-Al 2 O 3 and MgO as a raw material, and calcined at 1600 ° C. for 2 hours. This is subjected to ball milling, uniaxial pressing, and cold isostatic pressing followed by sintering at 1650 ° C. for 24 hours to obtain a diameter of about 6: 4 in weight ratio of ⁇ alumina and ⁇ ′ ′ alumina phase.
  • a sintered body with 16 mm disk shape and relative density of 98% or more without gas permeability was obtained and polished to a thickness of 1.5 mm to obtain a separator (Na + ion conductor of ⁇ alumina ceramic)
  • the temperature characteristics of the sum of the resistance components within the crystal grains and grain boundaries of the above-mentioned ⁇ -alumina-based ceramics were evaluated by the alternating current impedance method.
  • the activation energy of the electrical conductivity was a typical value.
  • the direct current resistance as a Na + ion conductor was 40 ⁇ ⁇ cm ⁇ 2 at 50 ° C.
  • Example 2 a battery test shown in FIG. 2 was performed.
  • a separator of ⁇ -alumina based ceramic was used as Na + ion conductor 1, 10 mg of metal Na pieces bound to a platinum wire, and 0.5 M sodium perchlorate (NaClO instead of NaPF 6)
  • a battery test was conducted in the same manner as in Example 1 except that 4 ) was used.
  • FIG. 6 shows the current-voltage characteristics obtained at 30 ° C., 40 ° C., and 50 ° C. for the metal Na battery using the ⁇ -alumina-based separator of Example 3.
  • the open circuit electromotive force (V) almost agrees with the theoretical electromotive force as the Na-water-air battery. From this, it was confirmed that the metal Na battery of this example operated as desired.
  • the internal resistance of the cell estimated from the slope of the current-voltage characteristics at 50 ° C. was about 900 ⁇ / cm 2 . This was a value 10 or more times larger than the resistance value of the ⁇ -alumina-based ceramic separator. Therefore, it was determined that the ⁇ -alumina ceramic itself was not a main component of the internal resistance. Further, even if the Pt wire mesh was changed to a 1 cm 2 Ni plate, no change in current-voltage characteristics was observed.
  • Example 4 Metallic Na Battery Using Gas Permeable Positive Electrode Corresponding to FIG. 1 (B), the metal Na battery using the gas-permeable positive electrode was created, and the discharge characteristic was evaluated.
  • a gas-permeable positive electrode was produced by the following procedure.
  • This was mixed with a binder (PTEF emulsion), and the mixture was hot pressed at about 200 ° C. to obtain a catalyst layer.
  • a highly conductive carbon Ketjen black
  • a binder PTEF emulsion
  • gas diffusion layer the catalyst layer, and the nickel wire netting described above were stacked in this order and hot pressed at about 200 ° C. to obtain a gas-permeable positive electrode.
  • the metal Na battery 20 shown in FIG. 1 (B) was configured using this gas permeable positive electrode.
  • the effective electrode area of this metal Na battery 20 was 0.79 cm 2 .
  • EC which dissolved 10 mg metal Na crimped on a SUS304 stainless steel plate on a negative electrode, 1M sodium perchlorate NaClO 4 as a sodium salt and 1 vol% fluoroethylene carbonate (FEC) as an additive to a negative electrode electrolyte:
  • An electrolyte of DMC mixture of ethylene carbonate and dimethyl carbonate in a 1: 1 ratio
  • a 0.6 mm thick Nashicon ceramic was used as a ceramic separator.
  • the positive electrode electrolyte was a 0.5 M aqueous solution of sodium hydroxide NaOH, and was in contact with one side of the above gas-permeable positive electrode.
  • FIG. 7 shows the current-voltage characteristics of the metal Na battery using the gas-permeable positive electrode of Example 4 measured at 25 ° C. in air.
  • the maximum output of the metal Na battery of this example was improved to 25 mW / cm 2 or more. It is believed that this property surpasses both conventional aqueous and non-aqueous lithium and sodium air batteries. That is, in the present embodiment, a highly conductive sodium ion conductive ceramic material, a non-aqueous electrolytic solution and a water-soluble electrolytic solution are selected as the electrolyte component. This shows that high output can be obtained in the form of an aqueous solution sodium-air battery equipped with a gas-permeable positive electrode.
  • Example 5 Evaluation of charge and discharge characteristics
  • the configuration of the battery and the measurement conditions are the same as in the fourth embodiment. Only the current control of the measurement system for charge and discharge (charge and discharge) differs from that of the fourth embodiment.
  • FIG. 8 shows the evaluation of charge and discharge characteristics of a metal Na battery using the gas-permeable positive electrode of Example 4.
  • the charge / discharge rate (current density) of the metal Na battery of this example was about 1 mA / cm 2 . This is greater than the charge and discharge rate of the previously reported battery.
  • the charge / discharge rate was about 30 times as fast. That is, in the present embodiment, by taking the form of the aqueous solution sodium-air battery, the merit that the material having high conductivity can be selected for the electrolyte component was exhibited.
  • the present invention relates to a metal Na battery.

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PCT/JP2013/005378 2012-09-11 2013-09-11 ÉLÉMENT MÉTALLIQUE NA METAL Na CELL Ceased WO2014041800A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113328177A (zh) * 2021-05-27 2021-08-31 中国科学技术大学 金属-氢气电池及其制备方法
US11427869B2 (en) 2015-02-26 2022-08-30 The Broad Institute, Inc. T cell balance gene expression, compositions of matters and methods of use thereof
WO2025097638A1 (fr) * 2023-11-09 2025-05-15 宁德时代新能源科技股份有限公司 Batterie secondaire au sodium et dispositif électrique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080268327A1 (en) * 2006-10-13 2008-10-30 John Howard Gordon Advanced Metal-Air Battery Having a Ceramic Membrane Electrolyte Background of the Invention
US20120183868A1 (en) * 2009-10-27 2012-07-19 Electricite De France Electrochemical device having a solid alkaline ion-conducting electrolyte and an aqueous electrolyte
JP2012227119A (ja) * 2011-04-20 2012-11-15 Samsung Electro-Mechanics Co Ltd 金属空気電池及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080268327A1 (en) * 2006-10-13 2008-10-30 John Howard Gordon Advanced Metal-Air Battery Having a Ceramic Membrane Electrolyte Background of the Invention
US20120183868A1 (en) * 2009-10-27 2012-07-19 Electricite De France Electrochemical device having a solid alkaline ion-conducting electrolyte and an aqueous electrolyte
JP2012227119A (ja) * 2011-04-20 2012-11-15 Samsung Electro-Mechanics Co Ltd 金属空気電池及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11427869B2 (en) 2015-02-26 2022-08-30 The Broad Institute, Inc. T cell balance gene expression, compositions of matters and methods of use thereof
CN113328177A (zh) * 2021-05-27 2021-08-31 中国科学技术大学 金属-氢气电池及其制备方法
WO2025097638A1 (fr) * 2023-11-09 2025-05-15 宁德时代新能源科技股份有限公司 Batterie secondaire au sodium et dispositif électrique

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