WO2021166655A1 - Ｍｇ基合金負極材及びその製造方法、並びにこれを用いたＭｇ二次電池 - Google Patents

Ｍｇ基合金負極材及びその製造方法、並びにこれを用いたＭｇ二次電池 Download PDF

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WO2021166655A1
WO2021166655A1 PCT/JP2021/004058 JP2021004058W WO2021166655A1 WO 2021166655 A1 WO2021166655 A1 WO 2021166655A1 JP 2021004058 W JP2021004058 W JP 2021004058W WO 2021166655 A1 WO2021166655 A1 WO 2021166655A1
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negative electrode
based alloy
electrode material
alloy negative
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PCT/JP2021/004058
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English (en)
French (fr)
Japanese (ja)
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英俊 染川
俊彦 万代
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国立研究開発法人物質・材料研究機構
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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 an Mg-based alloy negative electrode material and a method for producing the same.
  • the present invention also relates to an Mg secondary battery using an Mg-based alloy negative electrode material.
  • Mg (magnesium) metal When used as the negative electrode of a storage battery, Mg (magnesium) metal exhibits the highest theoretical capacity density among the metals in practical use and does not form a dendride-like precipitation part during electrodeposition, so that it is a high energy density storage battery. It is attracting attention as a negative electrode material for this purpose. However, unlike the Li (lithium) metal negative electrode and the Na (sodium) metal negative electrode, the Mg metal negative electrode is difficult to form an ionic conductive film at the interface with the electrolytic solution and is easily passivated, so that the dissolution and precipitation behavior is reversible. The problem is that it is unlikely to occur.
  • a storage battery such as a secondary battery includes a positive electrode active material and an electrolytic solution in addition to the negative electrode material. Therefore, as one means for solving the above-mentioned problems, the components other than the negative electrode material have been improved.
  • a positive electrode active material and an electrolytic solution effective for Mg secondary batteries have been developed, respectively.
  • the constituent materials can be roughly classified into two types: Mg metal negative electrode material (and Mg-based alloy negative electrode material) and Mg-containing intermetallic compounds.
  • Patent Documents 3 and 4 the above-mentioned problems are solved by utilizing the Mg-Bi intermetallic compound (Mg 3 Bi 2 ) and the Mg-Sn intermetallic compound (Mg 2 Sn) as the negative electrode material.
  • the intermetallic compound negative electrode has a problem that the potential is higher and the capacitance density is lower than that of the Mg metal negative electrode (and the Mg base alloy negative electrode).
  • Bi bismuth
  • Sn titanium
  • Patent Document 5 discloses an Mg metal negative electrode and an Mg-based alloy negative electrode using an Mg metal as a negative electrode without utilizing an intermetallic compound.
  • Patent Document 5 lists Mg—Al alloys, Mg—Zn alloys, and Mg—Mn alloys as Mg-based alloys constituting the negative electrode, but Mg— is shown in Examples. Only 6 mass% Al alloy. In this alloy, from the viewpoint of thermal equilibrium and metallographic structure, a large number of intermetallic compounds represented by Mg 17 Al 12 are dispersed in the Mg matrix at high density due to the high concentration of Al added. Will be done. Of course, since Al is spent on the formation of intermetallic compounds, it is obvious that solute element segregation does not occur at the grain boundaries.
  • Patent Document 6 discloses an Mg metal negative electrode and an Mg-based alloy negative electrode suitable for an Mg secondary battery containing 90% or more of Mg in terms of mass ratio.
  • a subcomponent that can be contained any one of Al (aluminum), Zn (zinc), Mn (manganese), Si (silicon), Ca (calcium), Fe (iron), Cu (copper), and Ni (nickel).
  • Al aluminum
  • Zn zinc
  • Mn manganese
  • Si silicon
  • Ca calcium
  • Fe iron
  • Cu copper
  • Ni nickel
  • Si, Fe, Cu, and Ni have a maximum solid solution amount of 0.01 mol% or less with respect to Mg, which is not a solid solution amount that affects mechanical properties and functional characteristics, and therefore are usually unavoidable impurity elements. Be treated.
  • Patent Document 7 discloses an Mg alloy containing 0.03 to 0.54 mol% of a solute atom having an atomic radius larger than that of Mg and having excellent strength and ductility.
  • the solute elements are unevenly distributed at the grain boundaries, but the average crystal grain size is 1.5 ⁇ m or less because the main purpose is to achieve high strength and high ductility of the bulk material.
  • Patent Document 8 discloses an Mg alloy containing 0.77 to 2 mass% of Mn
  • Patent Document 9 discloses an Mg alloy containing 0.25 to 9 mass% of Bi, both of which are excellent in room temperature ductility. It is said to be a Mg alloy.
  • Mg alloys are characterized in that the average crystal grain size is 10 ⁇ m or less, the elongation at break is about 100%, and the m value, which is an index of the contribution ratio of grain boundary slip to deformation, is 0.1 or more. There is.
  • the Mg alloys disclosed by the present inventors are intended to improve mechanical properties such as strength and ductility, and the electrochemical properties are unknown. As far as the present inventor knows, there is no literature or disclosure example related to the electrochemical properties of Mg-based binary alloys.
  • the first aspect of the present invention for solving the above-mentioned problems is to use at least one element (solute element) selected from Al, Ag, Bi, Ca, Sn, Mn, Li, RE (rare earth) and Zn.
  • This is an Mg-based alloy negative electrode material containing 0.02 mol% or more and 10 mol% or less in total, the balance of which is formed of an Mg-based alloy composed of Mg and an unavoidable component, and a thickness of 1 mm or less.
  • the Mg-based alloy negative electrode material may have an average particle size of 1000 ⁇ m or less as the Mg base material.
  • At least one of the solute elements may be segregated at the grain boundaries.
  • the Mg-based alloy negative electrode material may exhibit cycle characteristics of 5 times or more in cycle measurement using a tripolar cell.
  • the Mg-based alloy negative electrode material may exhibit characteristics of an overvoltage of 50 mV or less in an electrochemical precipitation / dissolution test of Mg metal.
  • the Mg-based alloy negative electrode material may exhibit a current density of ⁇ 10 mAcm ⁇ 2 or more when the electrode potential with respect to the Mg metal is ⁇ 0.5 V in the electrochemical precipitation / dissolution test of the Mg metal.
  • the second aspect of the present invention for solving the above-mentioned problems is to melt and cast a raw material to obtain an Mg-based alloy cast material, and to obtain an Mg-based alloy cast material at 400 ° C. or higher and 650 ° C. with respect to the Mg-based alloy cast material.
  • the solution treatment is performed at the following temperature for 0.5 hours or more and 48 hours or less, and the Mg-based alloy cast material after the solution treatment is subjected to plastic strain of 50 ° C. or higher and 550 ° C.
  • This is a method for producing an Mg-based alloy negative electrode material according to the first aspect, which comprises performing a spreading process having a cross-sectional reduction rate of 10% or more at the following temperature.
  • a third aspect of the present invention for solving the above problems is an Mg secondary battery composed of an Mg-based alloy negative electrode material according to the first aspect, an electrolyte and a positive electrode.
  • the Mg secondary battery may exhibit a cycle characteristic of 10 times or more by cycle measurement.
  • FIG. 1 It is a schematic diagram which shows the schematic structure of the Mg secondary battery which uses the Mg-based alloy negative electrode material which concerns on one aspect of this invention.
  • An example of an external photograph of the Mg-based alloy negative electrode material according to each embodiment of the present invention shows an external photograph after rolling.
  • An electron backscatter diffraction image is shown in an example of observing the microstructure of the Mg—Ca alloy according to an embodiment of the present invention.
  • a Z contrast image by high resolution electron microscopy is shown.
  • the electrochemical precipitation dissolution test example of the Mg—Ca alloy according to one embodiment of the present invention the relationship between the potential and the current density in each cycle is shown.
  • An electrochemical precipitation / dissolution test example of an Mg—Ag alloy according to an embodiment of the present invention shows the relationship between the potential and the current density in each cycle. It is an electrochemical precipitation dissolution curve of the Mg-based binary alloy which concerns on each Example of this invention.
  • the relationship between the potential and the current density at the time of two cycles is shown in the electrochemical precipitation dissolution test examples of Mg—Ca alloys having various Ca amounts according to one embodiment of the present invention.
  • the relationship between the potential and the current density at 10 cycles is shown in the electrochemical precipitation and dissolution test examples of Mg—Ca alloys having various Ca amounts according to one embodiment of the present invention.
  • the Mg-based alloy negative electrode material according to the first aspect of the present invention (hereinafter, may be simply referred to as “first aspect”) is substantially made of Mg—Amol% X as the Mg-based alloy material. That is, the balance of Amol% other than the X element is composed of Mg and an unavoidable component.
  • X is at least one element selected from Al, Ag, Bi, Ca, Sn, Mn, Li, RE (rare earths) and Zn.
  • these elements may be collectively referred to as "solute elements”.
  • Rare earths among solute elements include lanthanoids such as Sc (scandium) and Y (yttrium), and Gd (gadolinium) and Ce (cerium).
  • the value of A is not more than the maximum solid solution value with respect to Mg, preferably 0.02 mol% or more and 10 mol% or less, more preferably 0.02 mol% or more and 5 mol% or less, still more preferably 0.02 mol%.
  • the above is 1 mol% or less.
  • the added solute element does not affect the mechanical properties and the electrochemical properties, and only acts in the same manner as the impurity element. From the viewpoint of sufficiently exerting a positive effect on the mechanical properties and electrochemical properties of the added solute element, it is preferable that each lower limit value in the range of A described above is 0.05 mol%.
  • the solid solution amount A is preferably 0.02 mol% or more and 0.2 mol% or less. It is more preferably 02 mol% or more and 0.1 mol% or less.
  • the thickness of the first side surface is 1 mm or less.
  • the thickness is preferably 0.5 mm or less, more preferably 0.3 mm or less.
  • the crystal grain size of the Mg matrix is preferably 1000 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 50 ⁇ m or less. In the dissolution of Mg by the negative electrode reaction, the grain boundaries tend to become sites.
  • the crystal grain size is measured by the section method based on the JIS standard (also referred to as a cutting method. See JIS H0501 and G0551). However, when the crystal grain size is fine or the grain boundaries are unclear, it is difficult to apply the section method. Therefore, a bright field image or an electron backscatter diffraction image obtained by a transmission electron microscope is used. The result of the measurement is taken as the crystal grain size.
  • the added solute element segregates at the grain boundaries and its concentration is 1.5 times or more higher than the concentration of the solute element present in the Mg matrix.
  • the presence or absence of grain boundary segregation is preferably identified by using the analysis result by the energy dispersive X-ray spectroscopy (EDX) apparatus attached to the transmission electron microscope (TEM), but it is preferable to use a method such as a three-dimensional atom probe. You may evaluate it.
  • EDX energy dispersive X-ray spectroscopy
  • TEM transmission electron microscope
  • the first aspect exhibits cycle characteristics of preferably 5 times or more, more preferably 25 times or more, still more preferably 50 times or more in cycle measurement using a tripolar cell.
  • the cycle characteristic is 5 times or more, the problem of side reaction with the electrolytic solution does not become apparent, so that it can be suitably used as a negative electrode.
  • the overvoltage obtained in the electrochemical precipitation / dissolution test using a tripolar cell is preferably 50 mV or less, more preferably 30 mV or less, still more preferably 20 mV or less. When the overvoltage is 50 mV or less, the loss of the battery voltage is small, so that it can be suitably used as a negative electrode.
  • the current density when the electrode potential with respect to Mg metal is ⁇ 0.5 V is preferably ⁇ 10 mAcm -2 or more, more preferably ⁇ 20 mA cm -2 or more. , More preferably ⁇ 25 mAcm -2 or more.
  • the current density is ⁇ 10 mAcm -2 or more, the electrochemical reaction is less likely to be rate-determined by the negative electrode, and it can be suitably used as the negative electrode.
  • the electrolytic solution used in the cycle measurement test and the electrochemical precipitation / dissolution test uses a fluoroalkoxyborate magnesium salt or a fluoroalkoxyaluminate magnesium salt of 0.1 mol / L or more and 1.5 mol / L or less as a solute, and the solute is organic. It shall be mixed with ethers. However, when the solute cannot be used, other magnesium compounds such as alkylmagnesium chloride, magnesium chloride, magnesium bistrifluoromethanesulfonylimide salt and magnesium hexamethyldisilazide salt may be substituted as the solute.
  • Mg and solute metal which are raw materials, are melted and cast to obtain an Mg-based alloy cast material.
  • the melting method is not limited as long as an alloy having the desired composition can be obtained, and atmospheric melting, vacuum melting, arc melting, plasma melting and the like can be adopted.
  • the casting method is not limited, and any method such as gravity casting, sand casting, die casting, etc. can be adopted as long as it can produce the desired Mg-based alloy casting material.
  • the molten Mg-based alloy cast material is subjected to a solution treatment at a temperature of 400 ° C.
  • the solution treatment time is preferably 0.5 hours or more and 48 hours or less. If the treatment time is less than 0.5 hours, the diffusion of the solute element in the matrix tends to be insufficient, so that segregation during casting remains and it becomes difficult to create a sound material. On the other hand, if the processing time exceeds 48 hours, the working time becomes long, which is not preferable from an industrial point of view.
  • the temperature of warm or hot working shall be 50 ° C or higher and 550 ° C or lower.
  • the temperature is preferably 75 ° C. or higher and 525 ° C. or lower, more preferably 100 ° C. or higher and 500 ° C. or lower.
  • the processing temperature is less than 50 ° C, many deformed twins that are the starting points of cracks and cracks are generated, and ear cracks and surface waviness occur at high density, so that a healthy foil material with a thickness of 1000 ⁇ m or less should be produced. Becomes difficult.
  • the amount of strain applied by warm or hot working is such that the cross-sectional reduction rate is 10% or more.
  • the cross-sectional reduction rate is preferably 20% or more, more preferably 50% or more.
  • strain cannot be uniformly applied to the inside of the work material, and it becomes difficult to control the crystal grain size and the grain boundary segregation.
  • the warm or hot working method is typically extrusion, forging, rolling, drawing, etc., but any working method can be used as long as it can apply strain and control the thickness. But it can be adopted.
  • the effect of the present invention cannot be obtained because the added solute element does not segregate at the grain boundaries only by solution-treating the cast material without executing warm or hot working.
  • the reason is that the grain boundary segregation phenomenon is caused by the interaction between the solute element and the strain introduced during warm or hot working.
  • FIG. 1 is a schematic view showing a schematic configuration of an Mg secondary battery in which the Mg-based alloy negative electrode material of the present invention is used.
  • the Mg secondary battery includes a positive electrode C, a negative electrode D, an electrolytic solution B, and a container A.
  • a positive electrode active material (not shown) is held by a positive electrode current collector (not shown).
  • the positive electrode current collector has a function of donating electrons to the positive electrode active material at the time of discharge.
  • the substance used as the positive electrode current collector nickel, iron, stainless steel, titanium, aluminum and the like are preferably used because they have relatively excellent corrosion resistance and are inexpensive.
  • the substance used as the positive electrode active material is not particularly limited as long as it can insert and remove Mg ions, but MgFeSiO 4 , MgMn 2 O 4 , or V 2 O 5 or the like is preferably used.
  • a specific configuration of the positive electrode C for example, a configuration in which V 2 O 5 is coated on stainless steel can be mentioned.
  • the Mg-based alloy negative electrode material As the negative electrode D, the Mg-based alloy negative electrode material according to the first side surface is used.
  • the electrolytic solution B is held by a separator (not shown) to generate ionic conductivity between the positive electrode C and the negative electrode D.
  • the electrolytic solution B contains Mg ions.
  • Mg ions cause a reduction reaction (for example, the reaction of the formula (1) described later) at the positive electrode C and an oxidation reaction (for example, the reaction of the formula (2) described later) at the negative electrode D.
  • Mg ions cause an oxidation reaction (for example, the reaction of the formula (3) described later) at the positive electrode C and a reduction reaction (for example, the reaction of the formula (4) described later) at the negative electrode D.
  • the electrolytic solution B in the third aspect may contain an organic solvent as a main solvent and a magnesium salt, or may be an inorganic solvent having Mg ion conductivity.
  • the magnesium salt dissolves in the organic solvent and dissociates to form a magnesium complex cation in which the organic solvent is coordinated. Since this complex cation is responsible for the activity in the electrochemical precipitation and dissolution of magnesium, good electrochemical properties tend to be obtained when a magnesium salt having higher dissociation is used.
  • the electrolytic solution exhibiting good electrochemical properties include an electrolytic solution in which a magnesium fluoroalkoxy borate salt or a magnesium fluoroalkoxyaluminate salt is mixed with organic ethers.
  • magnesium salt used in the electrolytic solution examples include those having a fluoroalkoxyborate anion or a fluoroalkoxyaluminate anion as a counter anion.
  • the fluoroalkoxy group of the magnesium salt used here is not particularly limited.
  • Specific examples of the magnesium salt used in the third aspect include tetrakis (hexafluoroisopropoxy) magnesium borate salt and tetrakis (hexafluoroisopropoxy) aluminate magnesium salt.
  • the positive electrode C, the negative electrode D, and the electrolytic solution B are sealed in the container A.
  • the material of the container A is not particularly limited as long as it does not leak the electrolytic solution and has corrosion resistance, but it is formed by pressing a metal plate such as iron, and the entire inner and outer surfaces are for corrosion resistance. Those on which a plating layer such as nickel is formed are preferably used.
  • the third aspect may include technical matters that are obvious in the technical field of Mg secondary batteries, in place of or in addition to the above matters.
  • the cast material after the solution treatment was machined into a cylindrical extruded billet having a diameter of 40 mm and a length of 60 mm.
  • the processed billet is held in a container set at 275 ° C. for 30 minutes, and then hot strain is applied by extrusion at an extrusion ratio of 19: 1 to extrude a material having a length of 500 mm or more (hereinafter, simply "extruded material”). ”) was prepared.
  • the extruded material was cut to a length of 100 mm and rolled. Before rolling, the extruded material is held in an electric furnace (muffle furnace) set at 400 ° C for 15 minutes or more, and then a rolling mill with a roll temperature set at 200 ° C is used to set the rolling reduction ratio of one pass to 10% and thicken. Rolling was carried out until the diameter became 0.30 mm.
  • rolled material the material after rolling is simply referred to as "rolled material”.
  • a rolled material containing Ag, Al, Bi, Li, Mn, Sn, Y and Zn as solute elements instead of Ca was produced by the same method.
  • Mn or Y having a melting point significantly different from that of Mg is used as a solute element
  • the iron crucible containing the raw material is heated by a high-frequency heating device to melt the alloy casting material.
  • the conditions for producing rolled material from each molten casting include the temperature inside the container that holds the cylindrical extruded billet, the temperature of the muffle furnace that holds the extruded material before rolling, and the roll temperature during rolling. Except for the items shown in Table 1, they were the same as the rolled materials containing Ca as a solute element.
  • FIG. 2 is an external photograph of each rolled material (Mg-based alloy negative electrode material).
  • the thickness t of each rolled material is 300 ⁇ m for Mg—Ca alloy, 300 ⁇ m for Mg—Y alloy, 300 ⁇ m for Mg—Mn alloy, 290 ⁇ m for Mg—Sn alloy, 300 ⁇ m for Mg—Zn alloy, and 300 ⁇ m for Mg—Li alloy.
  • Mg—Al alloy was 300 ⁇ m.
  • a fine structure image was obtained for each of the obtained rolled materials by an electron backscatter diffraction technique.
  • the microstructure image of the rolled Mg—Ca alloy material is shown in FIG. 3, and the same fine structure was obtained for the other rolled materials.
  • the lumps having the same contrast in the figure are individual crystal grains, and one typical crystal grain is surrounded by a black line, and the size is 20 ⁇ m.
  • Table 1 summarizes the average grain size of the binary alloy used in the examples and the extrusion processing and rolling processing conditions. The average crystal grain size is 100 ⁇ m or less regardless of the type of added element.
  • Z-contrast image obtained by high-resolution electron microscopy (HREM) of a rolled Mg-Ag alloy material.
  • HREM high-resolution electron microscopy
  • a portion where an element having a large atomic number is present is displayed brightly (whitish). Since the contrast of the grain boundaries indicated by the arrows is clear, it can be confirmed that the solute element is segregated at the grain boundaries. The grain boundary segregation was confirmed even when the solute element was not Bi among the rolled materials produced in the examples.
  • FIG. 5 shows the cycle voltage / current test results of the cell using the rolled Mg—Ca alloy material as the working electrode. 0V vs.
  • the redox currents observed near Mg 2+ / Mg correspond to the dissolution and precipitation of magnesium, respectively.
  • the overvoltage of dissolution and precipitation was about ⁇ 20 mV in the initial cycle, but the overvoltage of dissolution and precipitation gradually decreased as the cycle increased, and became 10 mV or less after 10 cycles.
  • the electrode potential with respect to Mg metal was ⁇ 0.5 V, the current density showed a value of ⁇ 30 mAcm -2 or more.
  • FIG. 6 shows the cycle voltage / current test results of the cell using the rolled Mg—Ag alloy material as the working electrode. 0V vs.
  • the redox currents observed near Mg 2+ / Mg correspond to the dissolution and precipitation of magnesium, respectively.
  • the overvoltage of dissolution precipitation was stable at about ⁇ 15 mV from the initial cycle to 50 cycles, and the fluctuation of the overvoltage with the cycle was minute.
  • the current density when the electrode potential with respect to Mg metal was ⁇ 0.5 V showed a value of ⁇ 30 mAcm -2 or more.
  • FIG. 7 shows the voltage / current measurement results of each cell at 10 cycles.
  • the voltage-current characteristics are affected by the added elements, and as described above, the rolled Mg—Ca alloy exhibits a small overvoltage.
  • Table 2 summarizes the current and voltage during 10 cycles. Table 2 also shows the results of checking the surface condition after immersing various Mg-based alloy negative electrode materials in the electrolytic solution for 3 days. The formation of pitting corrosion could not be confirmed in the alloy to which Ca was added, but pitting corrosion was observed in the other added element species. Decomposition products due to the reaction with the electrolytic solution adhered to the surface of the alloy where pitting corrosion was observed.
  • a tripolar cell was produced.
  • the cell structure was the same as described above except that a solution of ethyl magnesium chloride (C 2 H 5 MgCl) in tetrahydrofuran (THF) (concentration 2 mol / L) was used as the electrolytic solution.
  • the obtained 3-pole cell was subjected to a cycle voltage / current test under the above-mentioned conditions.
  • the voltage / current measurement results at 2 cycles of each cell are shown in FIG. 8, and the voltage / current measurement results at 10 cycles are shown in FIG. 9, respectively. From FIGS. 8 and 9, it can be seen that a large current density can be obtained in the cell using the Mg—Ca alloy negative electrode material having a Ca content of 0.05 mol% and 0.1 mol%. From these results, it can be said that the Mg—Ca alloy negative electrode material exhibits particularly excellent electrochemical properties when the Ca content is very small.
  • the Mg-based alloy of the present invention exhibits excellent electrochemical properties, it can be used as an Mg-based alloy negative electrode material for Mg secondary batteries as well as Mg primary batteries.
  • the Mg-based alloy negative electrode material of the present invention can be used for an Mg secondary battery.
  • Mg has a low density and a thin material, it can be applied as a lightweight foil material that can replace an aluminum foil as an Mg-based alloy foil having the composition of the Mg-based alloy negative electrode material of the present invention.

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PCT/JP2021/004058 2020-02-21 2021-02-04 Ｍｇ基合金負極材及びその製造方法、並びにこれを用いたＭｇ二次電池 WO2021166655A1 (ja)

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JP2013168351A (ja) * 2012-01-16 2013-08-29 Dainippon Printing Co Ltd 電池パック
JP2014164901A (ja) * 2013-02-22 2014-09-08 Dainippon Printing Co Ltd マグネシウムイオン二次電池用負極板、及びマグネシウムイオン二次電池、および電池パック
WO2018168995A1 (ja) * 2017-03-16 2018-09-20 国立大学法人山口大学 マグネシウムとビスマスの合金層を備える電極及びマグネシウム二次電池

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KR101964895B1 (ko) * 2011-04-18 2019-04-02 고쿠리츠다이가쿠호진 도호쿠다이가쿠 마그네슘 연료전지
JP2021073635A (ja) * 2017-01-11 2021-05-13 幸信 森 ニッケル−マグネシウム電池

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JPS56102547A (en) * 1979-09-19 1981-08-17 Magnesium Elektron Ltd Magnesium alloy for anode
JP2013168351A (ja) * 2012-01-16 2013-08-29 Dainippon Printing Co Ltd 電池パック
JP2014164901A (ja) * 2013-02-22 2014-09-08 Dainippon Printing Co Ltd マグネシウムイオン二次電池用負極板、及びマグネシウムイオン二次電池、および電池パック
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