WO2014017461A1 - Composé au magnésium, procédé de fabrication de celui-ci, matériau actif d'électrode positive, électrode positive, et batterie secondaire au magnésium-ion - Google Patents

Composé au magnésium, procédé de fabrication de celui-ci, matériau actif d'électrode positive, électrode positive, et batterie secondaire au magnésium-ion Download PDF

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WO2014017461A1
WO2014017461A1 PCT/JP2013/069854 JP2013069854W WO2014017461A1 WO 2014017461 A1 WO2014017461 A1 WO 2014017461A1 JP 2013069854 W JP2013069854 W JP 2013069854W WO 2014017461 A1 WO2014017461 A1 WO 2014017461A1
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magnesium
lithium
positive electrode
active material
electrode active
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PCT/JP2013/069854
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English (en)
Japanese (ja)
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喜晴 内本
有基 折笠
徹也 大門
タイタス マセセ
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国立大学法人京都大学
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Priority to JP2014526920A priority Critical patent/JPWO2014017461A1/ja
Publication of WO2014017461A1 publication Critical patent/WO2014017461A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • 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
    • H01M4/58—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
    • 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 magnesium compound, a method for producing the same, a positive electrode active material, a positive electrode, and a magnesium ion secondary battery.
  • lithium ion secondary batteries have been used as power sources for mobile phones and the like.
  • the lithium ion secondary battery has a problem in terms of resources and safety, and has a concern about an increase in size.
  • the lithium ion secondary battery does not have as high energy density as a conventional gasoline vehicle. Therefore, development of a new secondary battery that replaces the lithium ion secondary battery is required.
  • a magnesium ion secondary battery as disclosed in Patent Document 1 As a new secondary battery replacing the lithium ion secondary battery, for example, a magnesium ion secondary battery as disclosed in Patent Document 1 can be cited.
  • the magnesium ion secondary battery has a high energy density when metallic magnesium or the like is used for the negative electrode. Magnesium is a safe and abundant resource. Therefore, the magnesium ion secondary battery has attracted attention as a new secondary battery that replaces the lithium ion secondary battery.
  • the development of a positive electrode active material capable of extracting a high energy density is insufficient, and the development of a compound suitable as the positive electrode active material of the magnesium ion secondary battery is desired.
  • the main object of the present invention is to provide a novel magnesium compound suitable as a positive electrode active material of a magnesium ion secondary battery.
  • the magnesium compound according to the present invention is represented by the general formula: MgMSiO 4 (1).
  • M is at least one of Fe, Cr, Mn, Co, and Ni.
  • the magnesium compound has a 2 ⁇ value of at least 7.00 ° to 7.75 °, 10.50 ° to 10.90 °, and 11.00 as measured by powder X-ray diffraction using X-rays having a wavelength of 0.5 mm. It has major diffraction peaks in the range of ° to 11.80 °, 14.00 ° to 14.50 °, and 15.50 ° to 15.90 °.
  • M in the general formula (1) preferably contains Fe.
  • M is preferably Fe in the general formula (1).
  • the positive electrode active material of the magnesium ion secondary battery according to the present invention contains the above magnesium compound.
  • the positive electrode of the magnesium ion secondary battery according to the present invention includes the above positive electrode active material.
  • a magnesium ion secondary battery according to the present invention includes the positive electrode, the negative electrode, an electrolyte, and a separator.
  • a first method for producing a magnesium compound according to the present invention includes a lithium salt-containing electrolyte having a general formula: Li 2 MSiO 4 (2) [wherein M is Fe, Cr, Mn, Co, and Ni. At least one of them.
  • a second method for producing a magnesium compound according to the present invention is the following: In an electrolyte containing a magnesium salt, a general formula: Li 2 MSiO 4 (2) [wherein M is Fe, Cr, Mn, Co, and Ni. At least one of them. ] After the lithium is desorbed from the lithium compound represented by formula (I), magnesium is inserted into the lithium compound from which the lithium has been desorbed.
  • a novel magnesium compound suitable as a positive electrode active material for a magnesium ion secondary battery can be provided.
  • the magnesium compound according to the present invention has the general formula: MgMSiO 4 (1) [Wherein, M is at least one of Fe, Cr, Mn, Co, and Ni. ] It is represented by
  • the magnesium compound according to the present invention has a 2 ⁇ value of at least 7.00 ° to 7.75 °, 10.50 ° to 10.5, as measured by powder X-ray diffraction using an X-ray having a wavelength of 0.5 mm. It has major diffraction peaks in the ranges of 90 °, 11.00 ° to 11.80 °, 14.00 ° to 14.50 °, and 15.50 ° to 15.90 °. More specifically, the 2 ⁇ value has a plurality of main diffraction peaks in the range of 11.00 ° to 11.80 °.
  • the magnesium compound according to the present invention has a 2 ⁇ value of at least 7.10 ° to 7.40 °, 10.65 ° as measured by powder X-ray diffraction using an X-ray having a wavelength of 0.5 mm. It has diffraction peaks in the range of ⁇ 10.80 °, 11.50 ° to 11.60 °, 14.20 ° to 14.35 °, and 15.65 ° to 15.80 °.
  • an olivine structure belonging to the space group Pnma is known.
  • the magnesium compound according to the present invention has an X-ray diffraction peak different from the conventionally known olivine structure.
  • the range of the diffraction peak of powder X-ray diffraction of the magnesium compound according to the present invention is selected from the range of the main diffraction peak, and the crystal structure of the magnesium compound according to the present invention is not necessarily limited only by these peaks. Is not to be done. That is, the magnesium compound according to the present invention may have a diffraction peak in a range other than these ranges.
  • a is about 10.22 to 10.26 mm
  • b is about 6.50 to 6.60 mm
  • c is about 4.91 to 4.97 mm.
  • M preferably contains Fe, and more preferably Fe.
  • the magnesium compound represented by the general formula (1) having a conventional olivine structure has random site occupation of Mg and M. For this reason, when a magnesium compound is used as a positive electrode active material of a magnesium ion secondary battery, it is thought that one-dimensional diffusion of magnesium ions is inhibited by cation mixing. Therefore, when the magnesium compound represented by the general formula (1) having a conventional olivine structure is used as a positive electrode active material of a magnesium ion secondary battery, it is difficult to draw out a high energy density of magnesium.
  • the magnesium compound according to the present invention has a general formula: Li 2 MSiO 4 (2) [In formula, M is the same as M of General formula (1). ] Is obtained by ion-exchange of Li and Mg using a lithium compound represented by In the lithium compound represented by the general formula (2), the site occupancy of Li and M is determined. Therefore, the magnesium compound according to the present invention is different from the conventional olivine type magnesium compound in X-ray diffraction. It has a peak and the site occupation of Mg and M is considered to be fixed. Therefore, in the magnesium compound according to the present invention, diffusion of one-dimensional magnesium ions is hardly inhibited, and a high energy density of magnesium can be extracted. Therefore, the magnesium compound according to the present invention is useful as a positive electrode active material for a magnesium ion secondary battery.
  • the magnesium compound according to the present invention can be produced, for example, by the following first production method.
  • a lithium desorption step is performed in which lithium is desorbed from the lithium compound represented by the general formula (2) in an electrolyte containing a lithium salt.
  • the lithium desorption step includes, for example, a positive electrode using a lithium compound represented by the general formula (2) as a positive electrode active material, a negative electrode using carbon or the like as a negative electrode active material, an electrolyte containing a lithium salt, and a separator. This can be done by assembling and charging the battery. By such a method, lithium can be electrochemically desorbed from the lithium compound represented by the general formula (2).
  • Lithium salts include LiPF 6 , LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2) 3, LiC ( C 2 F 5 SO 2) 3, or the like can be used LiClO 4.
  • Lithium salt may be comprised by 1 type and may be comprised by 2 or more types.
  • the electrolyte may contain a solvent such as cyclic carbonate, chain carbonate, cyclic ester, cyclic ether, or chain ether.
  • the solvent may be composed of one type or may be composed of two or more types.
  • Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and the like.
  • Examples of chain carbonates include dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
  • Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
  • Examples of the cyclic ether include tetrahydrofuran and 2-methyltetrahydrofuran.
  • Examples of chain ethers include dimethoxyethane and ethylene glycol dimethyl ether. Further, acetonitrile or the like may be used as a solvent.
  • the charging temperature is preferably in the range of about 20 ° C to 60 ° C.
  • the charge rate is preferably in the range of about 0.01 C to 0.1 C.
  • a magnesium insertion step is performed in which magnesium is inserted into a lithium compound from which lithium has been desorbed in an electrolyte containing a magnesium salt.
  • the magnesium insertion step includes, for example, a positive electrode from which lithium has been removed, a negative electrode using metallic magnesium or the like as a negative electrode active material, an electrolyte containing a magnesium salt, and a separator obtained in the above lithium desorption step. This can be done by assembling and discharging the battery. By such a method, magnesium can be electrochemically inserted into the lithium compound from which lithium has been eliminated.
  • Magnesium salts include Mg [N (SO 2 CF 3 ) 2 ] 2 , Mg (BF 4 ) 2 , Mg (PF 6 ) 2 , Mg (ClO 4 ) 2 , Mg (CF 3 SO 3 ) 2 , Mg ( AsF 6 ) 2 , Mg (TFSI) 2 , MgCl 2 , N-methylanilylmagnesium bromide, pyrrylmagnesium bromide, Grignard reagent (general formula: RMX) , Ethyl group, butyl group and the like, and X represents Cl, Br, etc.), magnesium boride and the like can be used.
  • the magnesium salt may be composed of one type or may be composed of two or more types. In the magnesium insertion step, the electrolyte may contain the same solvent as in the lithium desorption step.
  • the discharge temperature is preferably in the range of about 20 ° C to 60 ° C.
  • the discharge rate is preferably in the range of about 0.01 C to 0.1 C.
  • lithium is desorbed from the lithium compound represented by the general formula (2) as the positive electrode active material by a lithium desorption process, and further lithium is desorbed.
  • the magnesium compound of the present invention can be produced.
  • the magnesium compound according to the present invention can be produced, for example, by the following second production method. That is, in the electrolyte containing the magnesium salt, after lithium is desorbed from the lithium compound represented by the general formula (2), magnesium is inserted into the lithium compound from which lithium is desorbed. Can be manufactured.
  • a battery including a positive electrode using a lithium compound represented by the general formula (2) as a positive electrode active material, a negative electrode using metal magnesium or the like as a negative electrode active material, an electrolyte containing a magnesium salt, and a separator is assembled and charged. By discharging, lithium can be electrochemically desorbed from the lithium compound, and magnesium can be electrochemically inserted.
  • the magnesium salt and the electrolyte those similar to those used in the first production method can be used.
  • the charging temperature, the discharging temperature, the charging rate, and the discharging rate can be the same as in the first manufacturing method.
  • lithium is desorbed from the lithium compound represented by the general formula (2), which is a positive electrode active material, in the presence of a magnesium salt by a lithium desorption process.
  • the magnesium compound of the present invention can be produced by inserting magnesium into the positive electrode active material from which lithium has been eliminated.
  • the positive electrode active material of the present invention contains the magnesium compound of the present invention.
  • the positive electrode active material of the present invention may contain a positive electrode active material other than the magnesium compound of the present invention.
  • Examples of the positive electrode active material other than the magnesium compound of the present invention include positive electrode active materials used in conventionally known magnesium ion secondary batteries.
  • the positive electrode active material of the present invention is preferably substantially composed of the magnesium compound of the present invention.
  • the positive electrode active material of the present invention may be one in which at least a part of the surface of the magnesium compound of the present invention is coated with carbon.
  • the overvoltage of a magnesium ion secondary battery can be reduced and cycling characteristics etc. can be improved more.
  • a method of carbon-covering at least a part of the surface of the magnesium compound of the present invention for example, in the first and second manufacturing methods described above, lithium is mixed with carbon and then lithium is desorbed. The method of doing is mentioned.
  • the shape of the positive electrode active material of the present invention is not particularly limited, but preferably includes a particulate shape. Moreover, although it does not restrict
  • the positive electrode of the present invention has a positive electrode active material layer and a positive electrode current collector.
  • the positive electrode active material layer contains the positive electrode active material of the present invention.
  • the positive electrode active material layer may contain a binder, a conductive agent, and the like in addition to the positive electrode active material.
  • the binder include polystyrene butadiene rubber.
  • the conductive agent include carbon materials such as ketjen black, carbon black, acetylene black, and graphite.
  • the positive electrode current collector can be made of, for example, aluminum, platinum, molybdenum, or the like.
  • the shape of the positive electrode current collector is not particularly limited, and can be, for example, a foil, a plate, or a mesh.
  • the magnesium ion secondary battery of the present invention includes the positive electrode of the present invention, a negative electrode, an electrolyte, and a separator.
  • the negative electrode has a negative electrode active material layer and a negative electrode current collector.
  • the negative electrode active material layer includes a negative electrode active material.
  • a negative electrode active material will not be specifically limited if it is a substance which can occlude / desorb magnesium reversibly.
  • Examples of preferable negative electrode active materials include metal magnesium and magnesium alloy.
  • Examples of the magnesium alloy include Mg—Al alloys, Mg—Zn alloys, Mg—Mn alloys, Mg—Bi alloys, Mg—Ni alloys, Mg—Sb alloys, and the like.
  • the negative electrode current collector can be composed of, for example, metallic magnesium, a magnesium alloy, or the like.
  • the negative electrode active material layer and the negative electrode current collector may be composed of the same material.
  • the electrolyte contains magnesium serving as a carrier in an ionic state in the magnesium ion secondary battery.
  • the electrolyte is preferably, for example, a magnesium salt dissolved in a solvent.
  • magnesium salts include, for example, Mg [N (SO 2 CF 3 ) 2 ] 2 , Mg (BF 4 ) 2 , Mg (PF 6 ) 2 , Mg (ClO 4 ) 2 , Mg (CF 3 SO 3 ) 2 , Mg (AsF 6 ) 2 , Mg (TFSI) 2, MgCl 2 , N-methylanilylmagnesium bromide, pyrylmagnesium bromide, Grignard bromide General formula: RMgX, where R represents an ethyl group, a butyl group, etc., and X represents Cl, Br, etc.).
  • examples of the magnesium salt include Mg (OH) 2 , MgCl 2 , Mg (NO 3 ) 2 and the like.
  • the magnesium salt may be composed of one type or may be composed of two or more types.
  • examples of the solvent include cyclic carbonates, chain carbonates, cyclic esters, cyclic ethers, chain ethers, and the like.
  • the non-aqueous solvent may be composed of one type or may be composed of two or more types.
  • examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and the like.
  • Examples of chain carbonates include dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate.
  • Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
  • examples of the cyclic ether include tetrahydrofuran and 2-methyltetrahydrofuran.
  • Examples of the chain ether include dimethoxyethane, ethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. In addition, you may use acetonitrile etc. as a solvent.
  • the separator is not particularly limited as long as it can separate the positive electrode and the negative electrode and retain the electrolyte.
  • Examples of the separator include microporous membranes such as polyethylene and polypropylene.
  • the magnesium ion secondary battery of the present invention can be manufactured, for example, by making a positive electrode and a negative electrode face each other with a separator interposed between them and enclosing them in a battery container together with an electrolyte.
  • the shape of the magnesium ion secondary battery is not particularly limited, and may be rectangular, cylindrical, flat or the like.
  • the pellet was heated at 400 ° C./h in an Ar atmosphere and baked at 800 ° C. for 6 hours.
  • the fired powder was cooled to 300 ° C. at 100 ° C./h, and then allowed to cool to room temperature by natural cooling.
  • carbon was added so as to remain at 10% by mass in the final product, pulverized and mixed at 400 rpm for 24 hours using a ball mill, and refired at 800 ° C. in an Ar atmosphere.
  • the obtained powder was put into a ball mill container and wet mixed with acetone at 600 rpm for 1 hour. This was vaporized under reduced pressure to obtain Li 2 FeSiO 4 whose surface was coated with carbon.
  • a cell having a working electrode and a counter electrode was produced as follows, and the cell was charged and discharged.
  • Li 2 FeSiO 4 , Ketjen black (Mitsubishi Chemical Co., Ltd.) as a conductive additive, and polytetrafluoroethylene (PTFE) as a binder are mixed at a mass ratio of 35:55:10 and punched out at ⁇ 13 mm.
  • LiPF 6 / EC EMC (3: 7 v / v) in which LiPF 6 was dissolved in a mixed solution of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (volume ratio 3: 7) (3: 7 v / v) (Kishida Chemical Co., Ltd.).
  • EMC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the assembly of the cells was all performed in an Ar atmosphere in a glove box.
  • the cell was charged / discharged using a multi-channel charge / discharge device HD1001-SM8 (Hokuto Denko).
  • the cell was kept at a constant temperature in a constant temperature bath at 55 ° C.
  • the charge rate was 1 / 50C.
  • the lithium desorption process from Li 2 FeSiO 4 was performed as described above.
  • a cell having a working electrode and a counter electrode was produced and discharged as follows.
  • the cell charged as described above was disassembled in a glove box under an Ar atmosphere, and the working electrode was washed with ethyl methyl carbonate (manufactured by Kishida Chemical Co., Ltd.) and then vacuum-dried overnight.
  • the dried working electrode was punched out with a diameter of 6 mm, and a Pt mesh for current collection was sandwiched from both sides to obtain a working electrode.
  • Pt was used as the current collector of the working electrode
  • an Mg rod was used as the counter electrode
  • an Ag + / Ag electrode was used as the reference electrode.
  • the results of powder X-ray diffraction measurement (XRD) using CuK ⁇ rays with a wavelength of 0.5 mm are shown in FIG. 1 together with the calculation results of the powder X-ray diffraction measurement values of the olivine type MgFeSiO 4 . .
  • XRD powder X-ray diffraction measurement
  • the 2 ⁇ value is at least 7.00 ° to 7.75 °, 10.50 ° to 10.90 °, 11.00. It can be seen that it has major diffraction peaks in the ranges of ° to 11.80 °, 14.00 ° to 14.50 °, and 15.50 ° to 15.90 °. It can also be seen that the 2 ⁇ value has a plurality of main diffraction peaks in the range of 11.00 ° to 11.80 °.
  • the 2 ⁇ value is at least in the range of 9.0 ° to 9.35 °, 10.3 ° to 10.55 °, 13.7 ° to 14.0 °, and 17.5 ° to 17.8 °. It can also be seen that it has a diffraction peak.
  • FIG. 1 shows the result of the powder X-ray diffraction measurement of the calculated olivine type MgFeSiO 4 .
  • FIG. 2 a charge / discharge curve is shown in FIG. 2 for the charge of the cell in the lithium desorption process from Li 2 FeSiO 4 and the discharge of the cell in the subsequent magnesium insertion process.
  • a charge capacity of 334 mAh / g which is a theoretical capacity when MgFeSiO 4 is used as the positive electrode active material, is obtained, and 2Li is desorbed from Li 2 FeSiO 4 .
  • I was able to.
  • a cell using Li 2 FeSiO 4 coated with carbon exhibits a charge / discharge capacity of about 200 mAh / g at 30 ° C. and 1/20 C (D. Lv et al. , J. Mater.Chem. 21, 9506-9512 (2011)), compared with such a conventional cell, the cell manufactured in Example 1 has a very large charge capacity substantially equal to the theoretical capacity. It turns out that it has.
  • the cell using MgFeSiO 4 obtained in Example 1 as the positive electrode active material showed a good charge / discharge cycle even when charge / discharge was repeated five times. Further, this cell showed a reversible charge / discharge capacity as high as 330 mAh / g. From this, it can be seen that MgFeSiO 4 obtained in Example 1 does not easily inhibit the insertion and desorption of Mg due to the diffusion of Fe.
  • Example 2 A cell was prepared and charged / discharged as follows. Li 2 FeSiO 4 , Ketjen black (Mitsubishi Chemical Corporation) as a conductive additive, and polytetrafluoroethylene (PTFE) as a binder were mixed at a mass ratio of 35:55:10. This was punched out with a diameter of 6 mm, and a Pt mesh for collecting current was sandwiched from both sides to obtain a working electrode. Pt was used as the current collector of the working electrode, an Mg rod was used as the counter electrode, and an Ag + / Ag electrode was used as the reference electrode.
  • the potential range in charge and discharge is the upper limit potential of 1.0 V vs. Ag + / Ag, lower limit potential of ⁇ 0.9 V vs. Ag + / Ag (or 334 mAh / g was the maximum value).
  • the charge / discharge curve of the obtained cell is shown in FIG.
  • MgMnSiO 4 having a conventionally known olivine type structure was prepared as follows.
  • Mg source MgO manufactured by Wako Pure Chemical Industries, Ltd.,> 99.9%
  • Mn source MnCO 3 Pur Chemical Co.,> 99.9%
  • SiO 2 Kanto Chemical Co., Inc. in Si source Were used, and they were ball-milled with ZrO 2 balls in ethanol at a rotation speed of 300 rpm for 12 hours to form fine starting materials.
  • MgMnSiO 4 having a conventionally known olivine structure has an X-ray diffraction pattern similar to that of MgFeSiO 4 shown in FIG.
  • Example 1 Next, using the obtained MgMnSiO 4 , a cell was produced in the same manner as in Example 1. About the obtained cell, the charge / discharge curve in charge and the discharge of the cell in the subsequent magnesium insertion process is shown in FIG. As is apparent from FIG. 5, the cell produced in Comparative Example 1 had only a charge / discharge capacity of about 0.3 Mg compared to the theoretical capacity.

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Abstract

La présente invention vise à fournir un nouveau composé au magnésium qui est approprié en tant que matériau actif d'électrode positive pour des batteries secondaires au magnésium-ion. A cet effet, l'invention concerne un composé au magnésium qui est représenté par la formule générale (1) MgMSiO4. Dans la formule générale (1), M représente au moins un élément qui est choisi parmi Fe, Cr, Mn, Co et Ni. Ce composé au magnésium est caractérisé en ce que la valeur 2θ possède des pics de diffraction principaux au moins dans une plage de 7,00° à 7.75°, dans une plage de 10,50° à 10,90°, dans une plage de 11,00° à 11,80°, dans une plage de 14,00° à 14,50° et dans une plage de 15,50° à 15,90° en diffractométrie des rayons X sur poudre à l'aide d'un rayon X ayant une longueur d'onde de 0,5 Å.
PCT/JP2013/069854 2012-07-25 2013-07-23 Composé au magnésium, procédé de fabrication de celui-ci, matériau actif d'électrode positive, électrode positive, et batterie secondaire au magnésium-ion WO2014017461A1 (fr)

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Cited By (8)

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JP2014143183A (ja) * 2012-12-27 2014-08-07 Showa Denko Kk マグネシウムイオン二次電池用正極活物質及びその製造方法、マグネシウムイオン二次電池用正極並びにマグネシウムイオン二次電池
WO2014175255A1 (fr) * 2013-04-24 2014-10-30 国立大学法人京都大学 Composé du magnésium contenant du fluor
JP2015182945A (ja) * 2014-03-26 2015-10-22 太平洋セメント株式会社 オリビン型シリケート化合物の製造方法
WO2017119493A1 (fr) * 2016-01-06 2017-07-13 国立研究開発法人産業技術総合研究所 Matériau actif d'électrode positive pour batterie secondaire, procédé de production de celui-ci, et batterie secondaire
CN108172899A (zh) * 2016-12-07 2018-06-15 松下知识产权经营株式会社 固体电解质以及使用该固体电解质的二次电池
WO2018174087A1 (fr) * 2017-03-23 2018-09-27 国立大学法人静岡大学 Batterie secondaire au magnésium et électrode négative avec matériau inorganique pour batteries secondaires au magnésium
CN109659536A (zh) * 2018-12-18 2019-04-19 中科廊坊过程工程研究院 一种镁离子电池正极材料及其制备方法和应用
US11349154B2 (en) 2016-12-07 2022-05-31 Panasonic Intellectual Property Management Co., Ltd. Secondary battery using alkaline earth metal ion moving during charge and discharge

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WO2014175255A1 (fr) * 2013-04-24 2014-10-30 国立大学法人京都大学 Composé du magnésium contenant du fluor
JP2015182945A (ja) * 2014-03-26 2015-10-22 太平洋セメント株式会社 オリビン型シリケート化合物の製造方法
WO2017119493A1 (fr) * 2016-01-06 2017-07-13 国立研究開発法人産業技術総合研究所 Matériau actif d'électrode positive pour batterie secondaire, procédé de production de celui-ci, et batterie secondaire
JPWO2017119493A1 (ja) * 2016-01-06 2018-11-08 国立研究開発法人産業技術総合研究所 二次電池用正極活物質及びその製造方法、並びに二次電池
US11133526B2 (en) 2016-12-07 2021-09-28 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte having magnesium ion conductivity and magnesium secondary battery using the same
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JP2018107106A (ja) * 2016-12-07 2018-07-05 パナソニックＩｐマネジメント株式会社 固体電解質及びそれを用いた二次電池
US11349154B2 (en) 2016-12-07 2022-05-31 Panasonic Intellectual Property Management Co., Ltd. Secondary battery using alkaline earth metal ion moving during charge and discharge
CN108172899B (zh) * 2016-12-07 2022-05-24 松下知识产权经营株式会社 固体电解质以及使用该固体电解质的二次电池
WO2018174087A1 (fr) * 2017-03-23 2018-09-27 国立大学法人静岡大学 Batterie secondaire au magnésium et électrode négative avec matériau inorganique pour batteries secondaires au magnésium
JPWO2018174087A1 (ja) * 2017-03-23 2020-04-02 国立大学法人静岡大学 マグネシウム二次電池及び無機材料付きマグネシウム二次電池用負極
JP7111937B2 (ja) 2017-03-23 2022-08-03 国立大学法人静岡大学 マグネシウム二次電池及び無機材料付きマグネシウム二次電池用負極
CN109659536A (zh) * 2018-12-18 2019-04-19 中科廊坊过程工程研究院 一种镁离子电池正极材料及其制备方法和应用

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