WO2024128128A1 - Oxyde ainsi que procédé de fabrication de celui-ci, électrolyte solide, et dispositif d'accumulation d'électricité - Google Patents

Oxyde ainsi que procédé de fabrication de celui-ci, électrolyte solide, et dispositif d'accumulation d'électricité Download PDF

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Publication number
WO2024128128A1
WO2024128128A1 PCT/JP2023/043840 JP2023043840W WO2024128128A1 WO 2024128128 A1 WO2024128128 A1 WO 2024128128A1 JP 2023043840 W JP2023043840 W JP 2023043840W WO 2024128128 A1 WO2024128128 A1 WO 2024128128A1
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oxide
solid electrolyte
solid
formula
ion conductivity
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PCT/JP2023/043840
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English (en)
Japanese (ja)
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孝章 名取
裕飛 山野
朋子 仲野
直彦 斎藤
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東亞合成株式会社
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Publication of WO2024128128A1 publication Critical patent/WO2024128128A1/fr

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    • 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 oxides and their manufacturing methods, solid electrolytes, and electricity storage devices.
  • the present invention is as follows.
  • M1 contains an element that becomes a divalent cation
  • M2 contains an element that becomes a trivalent cation containing Al
  • M3 contains an element that becomes a tetravalent cation (excluding Zr and Si)
  • x, y, z, and ⁇ satisfy x ⁇ 0, 0 ⁇ y ⁇ 0.1, z ⁇ 0, and ⁇ >0.
  • M1 is an element that can form a divalent cation, such as Group 2 elements, Group 12 elements, transition elements (Groups 3 to 11 elements) that can form a divalent cation, Sn, Pd, etc.
  • M2 includes Al. That is, M2 may include an element other than Al that becomes a trivalent cation. Examples of such elements include Group 3 elements, Group 13 elements, transition elements (Groups 3 to 11 elements) that become trivalent cations, Sb, Bi, etc.
  • x, y, z, and ⁇ may satisfy x ⁇ 0, 0 ⁇ y ⁇ 0.1, z ⁇ 0, and ⁇ >0. However, it is preferable that x ⁇ 0.3 is further satisfied, and better Na ion conductivity can be obtained compared to the case where x>0.3. This is believed to be because the segregation of M1 can be suppressed by satisfying x ⁇ 0.3. As the content of M1 increases, the solid solubility limit in the Zr site is approached, and an impurity phase containing a large amount of M1 begins to form, which inhibits Na ion conduction.
  • the condition y ⁇ 0.1 contributes to this.
  • the upper limit of y is preferably y ⁇ 0.09, more preferably y ⁇ 0.08, even more preferably y ⁇ 0.07, and even more preferably y ⁇ 0.06.
  • the lower limit of y is preferably 0.01 ⁇ y, more preferably 0.02 ⁇ y, even more preferably 0.03 ⁇ y, even more preferably 0.04 ⁇ y, and even more preferably 0.05 ⁇ y.
  • M2 has a smaller valence than Zr, the electrostatic repulsion force between M2 and a Na ion, which is a monovalent cation, is smaller than that between M2 and Zr. Therefore, it is considered that the substitution of Zr with M2 facilitates the diffusion of Na ions in the vicinity of M2.
  • z ⁇ 0.3 be satisfied, and better Na ion conductivity can be obtained as compared with the case where z>0.3. This is believed to be because the segregation of M3 can be suppressed by satisfying z ⁇ 0.3.
  • the content of M3 increases, the solid solubility limit in the Zr site is approached, and an impurity phase containing a large amount of M3 begins to form, which inhibits Na ion conduction. Therefore, a composition in which the impurity phase is unlikely to form is preferable, and from this perspective, the condition z ⁇ 0.3 is believed to contribute.
  • the presence or absence of segregation of M3 can be detected by measuring the distribution of M3 using energy dispersive X-ray spectroscopy.
  • the condition z ⁇ 0.3 contributes to this.
  • the upper limit of z is preferably z ⁇ 0.2, and more preferably z ⁇ 0.1.
  • the lower limit of z is preferably z ⁇ 0.01, and more preferably z ⁇ 0.03, and more preferably z ⁇ 0.05.
  • Si has a smaller valence than P, the electrostatic repulsion with Na ions, which are monovalent cations, is smaller than that of P. Therefore, it is considered that by substituting Si for P, diffusion of Na ions in the vicinity of Si is likely to occur.
  • the amount of Si substitution increases, the effect of inhibiting Na ion conduction due to the capture of Na ions in the vicinity of Si becomes significant. For this reason, it is considered that the ion conductivity deteriorates when the amount of Si substitution is large. From this perspective, it is considered that the condition ⁇ 1.0 contributes.
  • the upper limit of ⁇ is preferably ⁇ 0.9, more preferably ⁇ 0.8, even more preferably ⁇ 0.7, even more preferably ⁇ 0.6, and even more preferably ⁇ 0.5.
  • the lower limit of ⁇ is preferably ⁇ 0.1, more preferably ⁇ 0.15, even more preferably ⁇ 0.2, even more preferably ⁇ 0.25, and even more preferably ⁇ 0.3.
  • the oxide represented by formula (1) is described as having a stoichiometric ratio of O of 12. However, in reality, it is sufficient to maintain the charge neutrality of the oxide as a whole, and the value may be less than 12 or more than 12.
  • formula (1) when formula (1) is expressed as formula (2) as shown below (M1, M2, M3, x, y, z, and ⁇ are the same as formula (1)), Na 3 + 2x + y + ⁇ M1 x M2 y M3 z Zr 2-x-y-z Si 2 + ⁇ P 1- ⁇ O 12 + ⁇ ... (2) ⁇ can be set to, for example, 0 ⁇ 1.
  • the oxide of the present invention is not limited to a phase structure, and as a result, it is preferable that the oxide has high Na ion conductivity. Among them, it is preferable that the oxide exhibits a NASICON (Na Super Ionic Conductor) type. This is because the NASICON type is advantageous in use as a solid electrolyte. That is, unlike a layered structure, the NASICON type has a three-dimensionally expanded space for Na ion movement, and zirconium is stable even under high voltage, so it is useful as a solid electrolyte with a high operating voltage. Whether or not the oxide of the present invention exhibits a NASICON type can be determined from a diffraction profile obtained by powder X-ray diffraction measurement.
  • the oxide described above may be produced in any manner, and may be produced using a solid-phase method or a liquid-phase method, but in the present invention, it can be produced using a solid-phase method. More specifically, it can be produced by including a mixing step and a firing step.
  • a plurality of supply components including one or more elements selected from Na, M1, M2, M3, Zr, Si, and P are weighed so as to satisfy formula (1), i.e., so as to satisfy the stoichiometric ratio of the composition expressed by formula (1), and the weighed amounts are then mixed.
  • Mixing may be performed by dry mixing, but it is preferable to use a liquid for wet mixing. By performing wet mixing, the density of the sintered body after firing can be increased compared to the case of performing dry mixing, and the Na ion conductivity can also be relatively improved.
  • the liquid used for wet mixing water, various organic solvents, mixtures thereof, etc. can be appropriately used.
  • M1 is a divalent element
  • M2 is a trivalent element
  • M3 is a tetravalent element
  • x, y, z, and ⁇ satisfy x ⁇ 0, y ⁇ 0, z>0, and ⁇ >0.
  • the positive electrode 22 and the negative electrode 24 can be arranged to face each other with the solid electrolyte 23 interposed therebetween.
  • the positive electrode 22 and the negative electrode 24 are also arranged in contact with the solid electrolyte 23.
  • the all-solid-state battery 1 can include the solid electrolyte 23, the positive electrode 22, and the negative electrode 24 as an integrated sintered body.
  • the battery when the solid electrolyte 23 (solid electrolyte layer) has two main surfaces, i.e., when it is a plate, membrane, sheet, or film, the battery can be configured to include the positive electrode 22 on one main surface and the negative electrode 24 on the other main surface with the solid electrolyte 23 interposed therebetween.
  • the positive electrode usually contains a positive electrode active material and may contain one or more of, for example, a conductive material, a solid electrolyte, a binder, etc.
  • the negative electrode usually contains a negative electrode active material and may contain one or more of, for example, a conductive material, a solid electrolyte, a binder, etc.
  • Each electrode may be provided with a current collector.
  • the resulting mixture was dried at 100° C. for 3 hours, transferred to an alumina crucible (capacity 30 mL), heated to 1,100° C. over 5.5 hours, and held at that temperature for 5 hours to perform first pre-firing. Thereafter, the mixture was allowed to cool to room temperature to obtain a first pre-firing product.
  • the first calcined product was ground in an ethanol dispersion medium for 1 hour using a planetary ball mill with ⁇ 5 mm ZrO2 balls. The resulting dispersion was then passed through a 330 mesh sieve and dried at 80°C.
  • 0.3 g of the pulverized product of the first calcined product obtained was placed in a metal mold having a diameter of 1.2 cm, and molded into a coin shape by applying a load of 1 ton using a hydraulic press.
  • the molded product obtained was placed on a platinum plate, and the temperature was raised to 800°C over 30 minutes, and then the temperature was further raised to the main calcination temperature (1,200°C) described in Example 1 in Table 1 over 2 hours and maintained at that temperature for 4 hours to perform main calcination.
  • the product was then allowed to cool to room temperature, and the oxide of Example 1 was obtained.
  • Example 2 (2) Examples 2 to 17 and Comparative Examples 1 to 3
  • the respective samples were weighed so as to obtain the molar ratios shown in Examples 2 to 17 and Comparative Examples 1 to 3 in Table 1, and each sample was placed in a mortar, and 20 g of pure water was added thereto for wet mixing to obtain a mixture.
  • the obtained mixture was pre-fired and fired under the same conditions as in Example 1 to obtain the oxides of Examples 2 to 17 and Comparative Examples 1 to 3.
  • the first calcined product was molded into a coin shape in the same manner as in Example 1, and the resulting molded product was placed on a platinum plate and heated to 800° C.

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  • Secondary Cells (AREA)

Abstract

L'invention fournit un nouvel oxyde à base de NASICON présentant une conductivité élevée des ions Na, et fournit également un procédé de fabrication de celui-ci. En outre, l'invention fournit un électrolyte solide et un dispositif d'accumulation d'électricité mettant en œuvre cet oxyde.　L'oxyde de l'invention satisfait la formule (1) ci-dessous.　Ｎａ３＋２ｘ＋ｙ＋αＭ１ｘＭ２ｙＭ３ｚＺｒ２－ｘ－ｙ－ｚＳｉ２＋αＰ１－αＯ１２・・・（１） (Dans la formule (1), M1 contient un élément qui constitue un ion positif divalent, M2 contient un élément qui constitue un ion positif trivalent à teneur en Al, et M3 contient un élément qui constitue un ion positif tétravalent (Zr et Si étant exclus), et ｘ, ｙ, ｚ et α satisfont ｘ≧０, ０＜ｙ＜０,１, ｚ≧０ et α＞０.)
PCT/JP2023/043840 2022-12-15 2023-12-07 Oxyde ainsi que procédé de fabrication de celui-ci, électrolyte solide, et dispositif d'accumulation d'électricité WO2024128128A1 (fr)

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JP2022-200262 2022-12-15
JP2022200262 2022-12-15

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WO2024128128A1 true WO2024128128A1 (fr) 2024-06-20

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000126556A (ja) * 1998-10-23 2000-05-09 Agency Of Ind Science & Technol リチウム同位体分離剤
CN113675463A (zh) * 2021-08-21 2021-11-19 西南石油大学 一种nasicon型无机固态电解质材料及其制备方法和应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000126556A (ja) * 1998-10-23 2000-05-09 Agency Of Ind Science & Technol リチウム同位体分離剤
CN113675463A (zh) * 2021-08-21 2021-11-19 西南石油大学 一种nasicon型无机固态电解质材料及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG ZHIZHEN, ZOU ZHEYI, KAUP KAVISH, XIAO RUIJUAN, SHI SIQI, AVDEEV MAXIM, HU YONG‐SHENG, WANG DA, HE BING, LI HONG, HUANG XUEJI: "Correlated Migration Invokes Higher Na + ‐Ion Conductivity in NaSICON‐Type Solid Electrolytes", ADVANCED ENERGY MATERIALS, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 9, no. 42, 1 November 2019 (2019-11-01), DE , pages 1902373, XP093180835, ISSN: 1614-6832, DOI: 10.1002/aenm.201902373 *

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