Proton-conductive solid electrolyte, electrolyte layer, and battery

Abstract

Provided are: a proton-conducting solid electrolyte which is capable of exhibiting high proton conductivity and stability in a low-temperature and medium-temperature range; an electrolyte layer which uses the proton-conducting solid electrolyte; and a battery. As an example, a proton-conducting solid electrolyte, an electrolyte layer, and a battery are represented by the general formula Ba1-alphaSc1-xMoxO3-[delta] Hy (where alpha is-0.2-0.2, x is 0.1-0.3, y is 0-1-3x, and [delta] is 0-1 / 2-3x / 2), or are represented by the general formula BaSc1-xMoxO3-[delta] Hy (where x is 0.15-0.25, y is 0-1-3x, and [delta] is 0-1 / 2-3x / 2), etc.

Description

Technical Field

[0001] The present invention relates to a proton conductive solid electrolyte used in a proton conductive solid electrolyte layer of a fuel cell, a sensor, etc., and an electrolyte layer and a battery using the proton conductive solid electrolyte.

[0002] This application claims priority based on Japanese Patent Application No. 2022-140685, filed on September 5, 2022, the contents of which are incorporated herein by reference. Background Art

[0003] Various fuel cells are attracting attention as a key to realizing the next generation clean energy society and solving environmental problems. Various ion conductors are known as materials that can be used in fuel cells and sensors, such as proton conductors of metal oxides and oxide ion conductors.

[0004] As a conventionally known ion conductor, oxide ions (O 2- ) Conductive ceramics include yttria-stabilized zirconia (ZrO2-Y2O3) (hereinafter referred to as "YSZ"). YSZ is known to be used in solid oxide fuel cells (hereinafter referred to as "SOFC"), which have the advantages of particularly high power generation efficiency, no need for a fuel reformer, and excellent long-term stability.

[0005] On the other hand, as a proton conductor, perovskite-type oxides such as BaZr0.8Y0.2O2.9 in which oxygen vacancies are introduced by chemical substitution are known.

[0006] Patent Document 1 discloses a crystalline inorganic compound capable of conducting at least one carrier selected from the group consisting of anions, cations, protons, electrons, and holes. A compound having high electrical conductivity, such as a conductive oxide ion (O 2- ), proton (H + ) compounds that exhibit high ion conductivity such as ions can be used as solid electrolytes for fuel cells, etc.

[0007] The present inventors disclosed in Patent Document 2 a solid electrolyte, an electrolyte layer using the solid electrolyte, and a battery. The solid electrolyte is a solid electrolyte containing a hexagonal perovskite-related compound, and the compound is a compound of the general formula: Ba 7-α Nb( 4-x-y )Mo (1+x) M y O (20+z) The solid electrolyte, the electrolyte layer using the solid electrolyte, and the battery have higher electrical conductivity than YSZ even in a low temperature range and are suitable for SOFC.

[0008] Patent document 3 discloses a solid electrolyte comprising a general formula: BaZr 1-x Sc x O 3-δ H y The invention indicates that scandium-doped barium zirconate has x greater than 0.20 and less than 0.65, y is 0.7x to x, and δ is 0 to 0.15x. The purpose of this technology is to provide a solid electrolyte that can exhibit a certain level of proton conductivity and chemical stability in a medium temperature range.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent No. 6448020

[0012] Patent Document 2: International Publication No. 2020 / 153485

[0013] Patent Document 3: International Publication No. 2021 / 085366 Summary of the invention

[0014] Technical problem to be solved by the invention

[0015] Currently, in addition to the above-mentioned conventionally known ion conductors, oxide ion conductors having high oxide ion conductivity and high oxygen mobility and proton conductors having high proton conductivity and high proton mobility are required.

[0016] In addition, an ion conductor having stable properties regardless of the surrounding environment is required. Examples of the surrounding environment include dependence on temperature conditions and oxygen partial pressure.

[0017] Regarding temperature conditions, the existing YSZ requires a high temperature of about 700°C or more to ensure the oxide ion conductivity required by the battery. In order to operate the battery at a high temperature of 700°C or more, the fuel cell itself needs to be preheated before operation, and most of the fuel cell constituent materials require thermal durability. In addition, it is necessary to have an environment and space for operation, and other devices for blocking or cooling that keep the battery at a high temperature while other environments do not become high temperatures. Therefore, an ion conductor that exhibits high ion conductivity under a wide range of temperature conditions is required.

[0018] Here, it is known that proton ceramic fuel cells (PCFCs) using a proton conductor in a solid electrolyte have a certain degree of ion conductivity even at relatively low temperatures because protons as conductive species have high mobility, and have ion conductivity that is independent of oxygen partial pressure.

[0019] In recent years, as a material that exhibits sufficient proton conductivity in the medium temperature range, the use of the aforementioned BaZr0.8Y0.2O2.9, BaZr 1-x Sc x O 3-δ H y Research on barium zirconate.

[0020] However, there is a strong demand for obtaining sufficient proton conductivity in a lower temperature range. However, in order to obtain such characteristics, it is necessary to explore a composition different from barium zirconate.

[0021] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a solid electrolyte capable of exhibiting excellent proton conductivity in low and medium temperature ranges, and an electrolyte layer and a battery using the proton conductive solid electrolyte.

[0022] Technical solutions for solving technical problems

[0023] In order to solve the above-mentioned technical problems, the present invention has the following aspects.

[0024] [1](1) A proton conductive solid electrolyte having the general formula: Ba 1-α Sc 1-x Mo x O 3-δ H y It means that α is -0.2~0.2, x is 0.1~0.3, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0025] [2] A proton conductive solid electrolyte,

[0026] By the general formula: BaA 1-x M x O 3-δ H y Indicates that A is the ionic radius of all ions except Ce, In, Zr and Zn. M is an element other than A, Zr, Ce and Zn whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A and Zn whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1,

[0027] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0028] When M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1),

[0029] y is 0~1, δ is 0~1 / 2.

[0030] [3] The proton conductive solid electrolyte according to [2],

[0031] A is Sc, M is Mo, Ge, Nb, Ta, V, W or Sb,

[0032] When M is Mo or W, x is greater than 0 and less than 1 / 3; when M is Ge, x is greater than 0 and less than 1 / 2; when M is Nb, Ta, V or Sb, x is greater than 0 and less than 1 / 2.

[0033] The proton conductive solid electrolyte according to [2] or [3],

[0034] Any one of the following (2) to (8).

[0035] (2) From the general formula: BaSc 1-x Ge x O 3-δ H y It means that x is 0.25 to 0.35, y is 0 to 1-x, and δ is 0 to 1 / 2-x / 2.

[0036] (3) From the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0037] (4) From the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0038] (5) From the general formula: BaSc 1-x V x O 3-δ H y It means that x is 0.2~0.25, y is 0~1-2x, and δ is 0~1 / 2-x.

[0039] (6) From the general formula: BaSc 1-x W x O 3-δ H y It means that x is 0.15~0.25, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0040] (7) From the general formula: BaSc0.6 Ce 0.4 O 3-δ express.

[0041] (8) From the general formula: BaSc 1-x Sb x O 3-δ H y It means that x is 0.35~0.45, y is 0~1-2x, and δ is 0~1 / 2-x.

[0042] [5] A proton conductive solid electrolyte,

[0043] By the general formula: BaSc 1-x M x O 3-δ H y represents, M represents a mixed composition of multiple elements other than Sc, Zr, Ce and Zn, the average ion radius of M is 70 to 130% of the ion radius of Sc, x is greater than 0 and less than 1,

[0044] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0045] When M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1)

[0046] y is 0~1, δ is 0~1 / 2.

[0047] [6] A proton conductive solid electrolyte,

[0048] By the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y express,

[0049] M is Mo, Ge, Nb, Ta, V, W or Sb,

[0050] y is 0 to 1, ε is 0 to 0.7, δ is 0 to 1 / 2,

[0051] In the case where M is Ge, x is greater than 0 and less than 1 / 2,

[0052] When M is Nb, Ta, V or Sb, x is greater than 0 and less than 1 / 2,

[0053] When M is Mo or W, x is greater than 0 and less than 1 / 3.

[0054] [7] A proton conductive solid electrolyte,

[0055] By the general formula: Ba 1-ε Sc 1-x Ce x O 3-δ H y It means that x is greater than 0 and less than 1, y is 0 to 1, ε is greater than 0.05 to 0.7 (when 0.05<ε<0.2, 0<x<0.5), and δ is 0 to 1 / 2.

[0056] [8] A proton conductive solid electrolyte,

[0057] By the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y It indicates that M is an element other than Sc and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixed composition of multiple elements other than Sc and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc, and x is greater than 0 and less than 1,

[0058] (wherein, for M=Ti, when ε=0, x is greater than 0 and less than 0.2,

[0059] For M=Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0060] For M=Zr, Ce, ε is greater than 0.05,

[0061] When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1)

[0062] y is 0~1, ε is 0~0.7, and δ is 0~1 / 2.

[0063] [9] A proton conductive solid electrolyte,

[0064] By the general formula: Ba 1-ε A 1-x M x O 3-δ H y Indicates that A is the ionic radius of all ions except Ce, In, Zr and Zn. M is an element other than A and Zn whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1,

[0065] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0066] For M=Zr, Ce, ε is greater than 0.05,

[0067] When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1)

[0068] y is 0~1, ε is 0~0.7, and δ is 0~1 / 2.

[0069]

[10] A proton conductive solid electrolyte,

[0070] By the general formula: BaA 1-x-z M1 x M2 z O 3-δ H y express,

[0071] z is greater than 0 and less than 1, y is 0 to 1, δ is 0 to 1 / 2,

[0072] Any one of the following (28) to (35).

[0073] (28) From the general formula: BaSc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, Mo and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Mo and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0074] (29) From the general formula: BaSc 1-x-z Ge x M z O 3-δ H yIt means that x is greater than 0 and less than 1, and M is an element other than Sc, Ge and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ge and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc.

[0075] (30) From the general formula: BaSc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Nb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Nb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0076] (31) From the general formula: BaSc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Ta and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ta and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0077] (32) From the general formula: BaSc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, V and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, V and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0078] (33) From the general formula: BaSc 1-x-z W x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, W and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, W and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0079] (34) From the general formula: BaSc 1-x-z Ce x M z O 3-δ H y Indicates that x is greater than 0 and less than 1, and M is an element other than Sc, Ce, Zr, and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ce, and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc (wherein, in the case of z=0, x is greater than 0 and less than 0.2. For M=Cr, Fe, Mn, Co, or Ni, the range of x=0.01 to 0.02 is excluded; for M=Mo, Nb, Ta, V, W, or Sb, the range of z=0.01 to 0.2 or x=0.74 to 0.84 is excluded)

[0080] (35) From the general formula: BaSc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Sb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Sb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0081]

[11] A proton conductive solid electrolyte,

[0082] By the general formula: Ba 1-ε A 1-x-z M1 x M2 z O 3-δ H y express,

[0083] z is greater than 0 and less than 1, y is 0 to 1, ε is 0 to 0.7, δ is 0 to 1 / 2,

[0084] Any one of the following (36) to (43).

[0085] (36) According to the general formula: Ba 1-ε Sc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, Mo and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Mo and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0086] (37) According to the general formula: Ba 1-ε Sc 1-x-z Ge x M z O 3-δ H y It means that x is greater than 0 and less than 1, and M is an element other than Sc, Ge and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ge and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc.

[0087] (38) According to the general formula: Ba 1-ε Sc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Nb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Nb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0088] (39) According to the general formula: Ba 1-ε Sc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Ta and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ta and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0089] (40) According to the general formula: Ba 1-ε Sc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, V and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, V and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0090] (41) According to the general formula: Ba 1-ε Sc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, W and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, W and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0091] (42) According to the general formula: Ba 1-ε Sc 1-x-z Ce x M z O 3-δ H y It means that x is greater than 0 and less than 0.8, and M is an element other than Sc, Ce and Zn (in addition, Zr is also excluded when ε=0) with an ionic radius of 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ce and Zn with an average ionic radius of 70 to 130% of the ionic radius of Sc (except for the range of ε=0 to 0.2 or x=0.01 to 0.02 for M=Cr, Fe, Mn, Co or Ni, and the range of z=0.01 to 0.2 or x=0.74 to 0.84 for M=Mo, Nb, Ta, V, W or Sb).

[0092] (43) According to the general formula: Ba 1-ε Sc 1-x-z Sb x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Sb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Sb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0093]

[12] A proton conductive solid electrolyte,

[0094] By the general formula: Ba 5-α R 2+x Al 2+y M 1+z O 13+δ express,

[0095] α is greater than or equal to 0 and less than or equal to 2, x is greater than or equal to -1 and less than or equal to 1, y is greater than or equal to -1 and less than or equal to 1, z is greater than or equal to -0.5 and less than or equal to 0.5, δ is greater than or equal to -1 and less than or equal to 1,

[0096] In the general formula, R is a cation of an element selected from the group consisting of rare earth elements and Ga, and M is a cation of an element selected from the group consisting of Hf, Sn, and Zr.

[0097]

[13] The proton conductive solid electrolyte according to

[12] ,

[0098] By the general formula: Ba5R2Al2MO 13 It indicates that M is a cation of one element selected from the group consisting of Hf and Sn.

[0099]

[14] The proton conductive solid electrolyte according to

[12] or

[13] ,

[0100] In the general formula, M is Sn, and R is Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm or Yb.

[0101]

[15] The proton conductive solid electrolyte according to any one of [1] to

[14] ,

[0102] For use at temperatures between 100 and 700°C.

[0103]

[16] The proton conductive solid electrolyte according to any one of [1] to

[14] ,

[0104] For use at temperatures between 200 and 400°C.

[0105]

[17] The proton conductive solid electrolyte according to any one of [1] to

[14] ,

[0106] When measuring the proton conductivity in the particle, log[σ(Scm -1 )] indicates that the temperature at which the conductivity is greater than -2.0 is below 350°C.

[0107]

[18] The proton conductive solid electrolyte according to any one of [1] to

[14] ,

[0108] Used in solid oxide fuel cells (SOFC), proton ceramic fuel cells (PCFC), sensors, batteries, electrodes, electrolytes, hydrogen permeable membranes, catalysts, photocatalysts, electrical / electronic / communication equipment, energy / environment-related equipment, or optical equipment.

[0109]

[19] The proton conductive solid electrolyte according to any one of [1] to

[14] ,

[0110] Used in solid oxide fuel cells (SOFC), proton ceramic fuel cells (PCFC), sensors or hydrogen permeation membranes.

[0111]

[20] an electrolyte layer,

[0112] Contains the proton conductive solid electrolyte according to any one of [1] to

[14] .

[0113]

[21] a battery,

[0114] The electrolyte layer described in

[20] is provided.

[0115]

[22] The battery according to

[21] ,

[0116] It is a solid oxide fuel cell (SOFC) or a proton ceramic fuel cell (PCFC).

[0117] In addition, the present invention has the following aspects.

[0118] [1A] A proton conductive solid electrolyte having the general formula: Ba 1-α Sc 1-x Mo x O 3-δ H y It means that α is -0.2~0.2, x is 0.1~0.3, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0119] [2A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Ge x O 3-δ H y It means that x is 0.25 to 0.35, y is 0 to 1-x, and δ is 0 to 1 / 2-x / 2.

[0120] [3A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0121] [4A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0122] [5A] A proton conductive solid electrolyte having the general formula: BaSc 1-x V x O 3-δ H y It means that x is 0.2~0.25, y is 0~1-2x, and δ is 0~1 / 2-x.

[0123] [6A] A proton conductive solid electrolyte having the general formula: BaSc 1-x W x O 3-δ H y It means that x is 0.15~0.25, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0124] [7A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Ce x O 3-δ H y It means that x is 0.35~0.45, y is 0~1-x, and δ is 0~1 / 2-x / 2.

[0125] [8A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Sb x O 3-δ H y It means that x is 0.35~0.45, y is 0~1-2x, and δ is 0~1 / 2-x.

[0126] [9A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Mo x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, and δ is 0 to 1 / 2.

[0127] [10A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Ge x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is between 0 and 1, and δ is between 0 and 1 / 2.

[0128] [11A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0129] [12A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0130] [13A] A proton conductive solid electrolyte having the general formula: BaSc 1-x V x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0131] [14A] A proton conductive solid electrolyte having the general formula: BaSc 1-x W x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, and δ is 0 to 1 / 2.

[0132] [15A] A proton conductive solid electrolyte having the general formula: BaSc 1-x Sb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0133] [16A] A proton conductive solid electrolyte having the general formula: BaA 1-x M x O 3-δ H y Indicates that A is the ionic radius other than Ce, In, and Zr. M is an element other than A, Zr, and Ce whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1,

[0134] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0135] When M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1)

[0136] y is 0~1, δ is 0~1 / 2.

[0137] [17A] A proton conductive solid electrolyte having the general formula: BaSc 1-x M x O 3-δ H y represents, M represents a mixed composition of multiple elements other than Sc, Zr, and Ce, the average ion radius of M is 70 to 130% of the ion radius of Sc, and x is greater than 0 and less than 1,

[0138] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0139] When M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1)

[0140] y is 0~1, δ is 0~1 / 2.

[0141] [18A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x Mo x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0142] [19A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x Ge x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0143] [20A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x Nb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0144] [21A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x Ta x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0145] [22A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x V x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0146] [23A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x W x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0147] [24A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x Ce x O 3-δ H y It means that x is greater than 0 and less than 1, y is 0 to 1, ε is greater than 0.05 to 0.7 (when 0.05<ε<0.2, 0<x<0.5), and δ is 0 to 1 / 2.

[0148] [25A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x Sb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0149] [26A] A proton conductive solid electrolyte having the general formula: Ba1-ε Sc 1-x M x O 3-δ H y It means that M is an element other than Sc, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixed composition of multiple elements other than Sc, whose average ionic radius is 70 to 130% of the ionic radius of Sc, and x is greater than 0 and less than 1,

[0150] (wherein, for M=Ti, when ε=0, x is greater than 0 and less than 0.2,

[0151] For M=Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0152] For M=Zr, Ce, ε is greater than 0.05,

[0153] When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1)

[0154] y is 0~1, ε is 0~0.7, and δ is 0~1 / 2.

[0155] [27A] A proton conductive solid electrolyte having the general formula: Ba 1-ε A 1-x M x O 3-δ H y Indicates that A is the ionic radius other than Ce, In, and Zr. M is an element other than A whose ionic radius is 70 to 130% of the ionic radius of A, or a mixture of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1,

[0156] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0157] For M=Zr, Ce, ε is greater than 0.05,

[0158] When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1)

[0159] y is 0~1, ε is 0~0.7, and δ is 0~1 / 2.

[0160] [28A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and Mo whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Mo whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0161] [29A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z Ge x M z O 3-δ H y It means that x is greater than 0 and less than 1, z is greater than 0 and less than 1, M is an element other than Sc and Ge whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Ge whose average ionic radius is 70 to 130% of the ionic radius of Sc, y is 0 to 1, and δ is 0 to 1 / 2.

[0162] [30A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Nb whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Nb whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0163] [31A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z Ta x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Ta whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Ta whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0164] [32A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and V whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and V whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0165] [33A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and W whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and W whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0166] [34A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z Ce x M z O 3-δ H yIt means that x is greater than 0 and less than 1, z is greater than 0 and less than 1, M is an element other than Sc, Ce and Zr, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc and Ce, whose average ionic radius is 70 to 130% of the ionic radius of Sc (wherein, when z=0, x is greater than 0 and less than 0.2. For M=Cr, Fe, Mn, Co or Ni, the range of x=0.01 to 0.02 is excluded; for M=Mo, Nb, Ta, V, W or Sb, the range of z=0.01 to 0.2 or x=0.74 to 0.84 is excluded), y is 0 to 1, and δ is 0 to 1 / 2.

[0167] [35A] A proton conductive solid electrolyte having the general formula: BaSc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Sb whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Sb whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0168] [36A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and Mo whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Mo whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0169] [37A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z Ge x M z O 3-δ H yIt means that x is greater than 0 and less than 1, z is greater than 0 and less than 1, M is an element other than Sc and Ge whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Ge whose average ionic radius is 70 to 130% of the ionic radius of Sc, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0170] [38A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Nb whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Nb whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0171] [39A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Ta whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Ta whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0172] [40A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z V x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and V whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and V whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0173] [41A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and W whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and W whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0174] [42A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z Ce x M z O 3-δ H y It means that x is greater than 0 and less than 0.8, z is greater than 0 and less than 1, M is an element other than Sc and Ce (excluding Zr when ε=0) with an ionic radius of 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc and Ce with an average ionic radius of 70 to 130% of the ionic radius of Sc (except for the range of ε=0 to 0.2 or x=0.01 to 0.02 for M=Cr, Fe, Mn, Co or Ni, and the range of z=0.01 to 0.2 or x=0.74 to 0.84 for M=Mo, Nb, Ta, V, W or Sb), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0175] [43A] A proton conductive solid electrolyte having the general formula: Ba 1-ε Sc 1-x-z Sb x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Sb whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc and Sb whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0176] [44A] A proton conductive solid electrolyte having the general formula: Ba5R2Al2MO 13 It means that R in the general formula is a cation of an element selected from the group consisting of rare earth elements and Ga, and M is a cation of an element selected from the group consisting of Hf and Sn.

[0177] [45A] According to the proton conductive solid electrolyte described in [44A], M in the general formula is Sn, and R is Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm or Yb.

[0178] [46A] The proton conductive solid electrolyte according to any one of [1A] to [45A], which is used under a temperature condition of 100 to 700°C.

[0179] [47A] The proton conductive solid electrolyte according to any one of [1A] to [46A], which is used under a temperature condition of 200 to 400°C.

[0180] [48A] The proton conductive solid electrolyte according to any one of [1A] to [47A], wherein when the proton conductivity in the particle is measured, log[σ(Scm -1 )] indicates that the temperature at which the conductivity is greater than -2.0 is below 350°C.

[0181] [49A] The proton conductive solid electrolyte according to any one of [1A] to [48A] is used for a solid oxide fuel cell (SOFC), a proton ceramic fuel cell (PCFC), a sensor, a battery, an electrode, an electrolyte, a hydrogen permeable membrane, a catalyst, a photocatalyst, an electrical / electronic / communication device, an energy / environment-related device, or an optical device.

[0182] [50A] The proton conductive solid electrolyte according to any one of [1A] to [49A], which is used for a solid oxide fuel cell (SOFC), a proton ceramic fuel cell (PCFC), a sensor or a hydrogen permeable membrane.

[0183] [51A] An electrolyte layer comprising the proton conductive solid electrolyte according to any one of [1A] to [50A].

[0184] [52A] A battery comprising the electrolyte layer according to claim [51A].

[0185] [53A] The battery according to [52A] is a solid oxide fuel cell (SOFC) or a protonic ceramic fuel cell (PCFC).

[0186] Effects of the Invention

[0187] According to the present invention, a proton conductive solid electrolyte capable of exhibiting excellent proton conductivity in low and medium temperature ranges, an electrolyte layer using the proton conductive solid electrolyte, and a battery can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0188] Figure 1 It is a schematic diagram showing the crystal structure of the compound (A) according to the present embodiment.

[0189] Figure 2 It is a schematic diagram showing the crystal structure of the compound (B) according to the present embodiment.

[0190] Figure 3 It means Test Example 1: BaSc 0.8 Mo 0.2 O 3-δ Graph of the results of XRD measurement.

[0191] Figure 4 It means test example 2: BaSc 0.75 Mo 0.25 O 3-δ Graph of the results of XRD measurement.

[0192] Figure 5 It means Test Example 3: BaSc 0.85 Mo 0.15 O 3-δ Graph of the results of XRD measurement.

[0193] Figure 6 It means Test Example 4: BaSc 0.7 Ge 0.3 O 3-δ Graph of the results of XRD measurement.

[0194] Figure 7 Test Example 5: BaSc 0.75 Ge 0.25 O 3-δ Graph of the results of XRD measurement.

[0195] Figure 8 It means Test Example 6: BaSc 0.65Ge 0.35 O 3-δ Graph of the results of XRD measurement.

[0196] Fig. 9 It means Test Example 7: BaSc 0.8 Nb 0.2 O 3-δ Graph of the results of XRD measurement.

[0197] Fig.10 Test Example 8: BaSc 0.75 Nb 0.25 O 3-δ Graph of the results of XRD measurement.

[0198] Fig.11 It means Test Example 9: BaSc 0.7 Nb 0.3 O 3-δ Graph of the results of XRD measurement.

[0199] Fig.12 It means Test Example 10: BaSc 0.65 Nb 0.35 O 3-δ Graph of the results of XRD measurement.

[0200] Fig.13 It means Test Example 11: BaSc 0.6 Nb 0.4 O 3-δ Graph of the results of XRD measurement.

[0201] Fig.14 It means Test Example 12: BaSc 0.7 Ta 0.3 O 3-δ Graph of the results of XRD measurement.

[0202] Fig.15 It means Test Example 13: BaSc 0.8 V 0.2 O 3-δ Graph of the results of XRD measurement.

[0203] Fig.16 It means Test Example 14: BaSc 0.75 V 0.25 O 3-δ Graph of the results of XRD measurement.

[0204] Fig.17 It means Test Example 15: BaSc 0.8 W 0.2 O 3-δGraph of the results of XRD measurement.

[0205] Fig.18 It means Test Example 16: BaSc 0.6 Ce 0.4 O 3-δ Graph of the results of XRD measurement.

[0206] Fig.19 It means Test Example 17: BaSc 0.6 Sb 0.4 O 3-δ Graph of the results of XRD measurement.

[0207] Fig. 20 It means Test Example 1: BaSc 0.8 Mo 0.2 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0208] Fig.21 It means test example 2: BaSc 0.75 Mo 0.25 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0209] Fig. 22 It means Test Example 3: BaSc 0.85 Mo 0.15 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0210] Fig.23 It means Test Example 4: BaSc 0.7 Ge 0.3 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0211] Fig.24 Test Example 5: BaSc 0.75 Ge 0.25 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0212] Fig.25 It means Test Example 6: BaSc 0.65 Ge0.35 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0213] Fig.26 It means Test Example 7: BaSc 0.8 Nb 0.2 O 3-δ A graph showing the bulk conductivity and grain boundary conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0214] Fig. 27 Test Example 8: BaSc 0.75 Nb 0.25 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0215] Fig.28 It means Test Example 9: BaSc 0.7 Nb 0.3 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0216] Fig.29 It means Test Example 10: BaSc 0.65 Nb 0.35 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0217] Fig.30 It means Test Example 11: BaSc 0.6 Nb 0.4 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0218] Fig.31 It means Test Example 12: BaSc 0.7 Ta 0.3 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0219] Fig.32 It means Test Example 13: BaSc 0.8 V0.2 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0220] Fig.33 It means Test Example 14: BaSc 0.75 V 0.25 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0221] Fig.34 It means Test Example 15: BaSc 0.8 W 0.2 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0222] Fig.35 It means Test Example 16: BaSc 0.6 Ce 0.4 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0223] Fig.36 It means Test Example 17: BaSc 0.6 Sb 0.4 O 3-δ A graph showing the DC total conductivity measured by cooling and maintaining the temperature in humid air (water vapor partial pressure: 18°C, 0.02 atm).

[0224] Fig.37 This is a graph showing the intra-grain conductivity and grain boundary conductivity of Test Example 1.

[0225] Fig.38 This is a graph showing a comparison of the electrical conductivity at each temperature between Test Example 1 and the conventional material.

[0226] Fig.39 This is a graph showing the time dependency of the electrical conductivity of each gas atmosphere in Experimental Example 1.

[0227] Fig.40 This is a graph showing the oxygen partial pressure dependence of the DC total conductivity in a dry atmosphere and a wet atmosphere in Test Example 1.

[0228] Fig.41 This is a graph showing the Arrhenius curve of the DC total conductivity for each gas atmosphere in Experimental Example 1.

[0229] Fig.42 This is a graph showing the oxygen partial pressure dependency of the body conductivity in Test Example 1.

[0230] Fig.43 This is a graph showing the thermogravimetric analysis results of Test Example 1.

[0231] Fig.44 Graph showing the temperature dependence of the proton concentration estimated from the thermogravimetric analysis results of Test Example 1.

[0232] Fig.45 This is a graph showing the Arrhenius curve of the diffusion coefficient of Test Example 1.

[0233] Fig.46 It is a graph showing the stability of Test Example 1 in an oxidizing atmosphere, a reducing atmosphere and in CO 2 .

[0234] Fig.47 This is a graph showing the results of XRD measurement for each of the synthesis examples of Test Examples 18 to 27.

[0235] Fig.48 It represents Test Example 18: Ba5Nd2Al2SnO 13 A graph of the total DC conductivity.

[0236] Fig.49 It represents Test Example 19: Ba5Sm2Al2SnO 13 A graph of the total DC conductivity.

[0237] Fig.50 It represents Test Example 20: Ba5Gd2Al2SnO 13 A graph of the total DC conductivity.

[0238] Fig.51 It represents Test Example 21: Ba5Dy2Al2SnO 13 A graph of the total DC conductivity.

[0239] Fig.52 It represents Test Example 22: Ba5Ho2Al2SnO 13 A graph of the total DC conductivity.

[0240] Fig.53 It represents Test Example 23: Ba5Er2Al2SnO 13 A graph of the total DC conductivity.

[0241] Fig.54 It represents Test Example 24: Ba5Tm2Al2SnO 13 A graph of the total DC conductivity.

[0242] Fig.55 Test Example 25: Ba5Yb2Al2SnO 13 A graph of the total DC conductivity.

[0243] Fig.56 It represents Test Example 26: Ba5Y2Al2SnO 13 A graph of the total DC conductivity.

[0244] Fig.57 It represents Test Example 27: Ba5Eu2Al2SnO 13 A graph of the total DC conductivity.

[0245] Fig.58 This is a graph showing the summary of the DC total conductivity of Test Examples 18 to 27.

[0246] Fig.59 It means Test Example 28: BaSc 0.775 Mo 0.225 O 3-δ Graph of the results of XRD measurement.

[0247] Fig.60 It means Test Example 28: BaSc 0.775 Mo 0.225 O 3-δ Graph of bulk conductivity in humid air.

[0248] Fig.61 It means Test Example 29: BaSc 0.725 Mo 0.275 O 3-δ Graph of the results of XRD measurement.

[0249] Fig.62 It means Test Example 29: BaSc 0.725 Mo 0.275 O 3-δ Graph of bulk conductivity in humid air.

[0250] Fig.63 It means Test Example 30: BaSc 0.7 W 0.3 O 3-δ Graph of the results of XRD measurement.

[0251] Fig.64 It means Test Example 31: BaSc 0.75 W 0.25 O 3-δ Graph of the results of XRD measurement.

[0252] Fig.65 It means Test Example 31: BaSc 0.75 W 0.25 O 3-δ Plot of total DC conductivity in humid air.

[0253] Fig.66 It means Test Example 32: BaSc 0.8 W 0.2 O 3-δ Graph of the results of XRD measurement.

[0254] Fig.67 It means Test Example 32: BaSc 0.8 W 0.2 O 3-δ Plot of total DC conductivity in humid air.

[0255] Fig.68 It represents Test Example 23: Ba5Er2Al2SnO 13 A graph comparing the conductivity at each temperature of existing materials.

[0256] Fig.69 About Test Example 23: Ba5Er2Al2SnO 13 , a graph showing the oxygen partial pressure dependence of the DC total conductivity in a dry atmosphere and a wet atmosphere at various temperatures.

[0257] Fig.70 About Ba5Er2Al2SnO 13 , a graph showing the time dependence of the electrical conductivity of each gas atmosphere.

[0258] Fig.71 It represents Test Example 23: Ba5Er2Al2SnO 13 Thermogravimetric analysis results of .

[0259] Fig.72 It represents Test Example 33: Ba5Er2Al2Sn 0.5 Zr 0.5 O 13 Graph of the results of XRD measurement.

[0260] Fig.73 It represents Test Example 33: Ba5Er2Al2Sn 0.5 Zr 0.5 O 13 Plot of total DC conductivity in humid air.

[0261] Fig.74 It indicates test example 34: Ba5Er 1.9 Al 2.1 SnO13 Graph of the results of XRD measurement.

[0262] Fig.75 It represents Test Example 35: Ba5Er2Al 2.1 Sn 0.9 O 12.95 Graph of the results of XRD measurement. DETAILED DESCRIPTION

[0263] Hereinafter, the proton conductive solid electrolyte, electrolyte layer, and battery according to the present invention will be described with reference to embodiments thereof, but the present invention is not limited to the following embodiments.

[0264] (Proton conductive solid electrolyte)

[0265] In this embodiment, first, the solid electrolyte is a solid material that conducts ions, and also includes materials that conduct both ions and electrons (or holes). It should be noted that each compound included in the following solid electrolyte also includes a small amount of impurity phase, but a substantially single-phase compound can be used.

[0266] A proton conductive solid electrolyte is a solid electrolyte mainly containing protons as carriers. Here, as a proton conductive solid electrolyte, there are proton-oxide ion mixed conductivity, proton-oxide ion-hole mixed conductivity, proton-oxide ion-electron mixed conductivity solid electrolytes, etc., which contain not only protons but also oxide ions, electrons, holes of electrons, etc. as carriers.

[0267] (First Embodiment)

[0268] (Compound (A): Ba 1-ε A 1-x M x O 3-δ H y )

[0269] Generally speaking, one embodiment of the compound of the present embodiment is a compound represented by the following general formula (A), or a proton conductive solid electrolyte included in the following compound (A).

[0270] Ba 1-ε A 1-x M x O 3-δ H y …(A)

[0271] [In formula (A), A is an element selected from Sc or an element having an ionic radius of 70 to 130% of the ionic radius of Sc. M is a metal element.]

[0272] Here, compound (A) is a so-called perovskite proton conductor. A perovskite proton conductor refers to a compound having a perovskite structure, a deformed perovskite structure, or a structure related to perovskite, and capable of conducting electricity through proton conduction as described below. A compound having a perovskite structure refers to a compound having a structure containing a perovskite unit or a compound having a structure similar thereto.

[0273] In the formula (A), A is Sc or an element having an ionic radius of 70 to 130% of the ionic radius of Sc. A may also be a mixed composition of multiple elements other than Sc. Specifically, A is an element having an ionic radius of about Elements with an ionic radius of about The mixed composition of the average ionic radius.

[0274] This is because in the compound of the formula (A) contained in the proton conductive solid electrolyte of the present embodiment, it is preferred that A is Sc, but any element that can be used in place of Sc and has the same crystal structure can be used appropriately.

[0275] Here, as elements within the above-mentioned range of ionic radius, elements with ionic radius of Al, Li; 0.53, 0.58, 0.645, 0.67 or Mn; 0.54, 0.58, 0.64 or V; 0.525, 0.545, 0.575 or Os; Cd; 0.73 or U; 0.71, 0.72, 0.75 and can be used Np of the ionic radius; 0.53 or I; Pm; 0.56 or Te et al.

[0276] In addition, in the compound contained in the proton conductive solid electrolyte in the present embodiment, M of the compound of formula (A) is a metal element. M of the compound of formula (A) is preferably Mo, Ge, Nb, Ta, V, W, Ce or Sb, more preferably Mo, Ge, and particularly preferably Mo.

[0277] In addition, the composition represented by M may be a single element or a mixed composition of two elements M1 and M2.

[0278] In addition, the compound contained in the proton conductive solid electrolyte in the present embodiment may also be a compound of formula (A) wherein M is a mixed composition of multiple elements. Here, M being a mixed composition of multiple elements means that M is a hypothetical element in which multiple elements are mixed in a certain ratio, for example, a composition in which m elements of M1, M2, ..., Mm are mixed in a certain ratio is represented by M.

[0279] That is, in the following formula, M1 and M2 may be metal compositions of the same element, different elements, or a plurality of elements, and may mainly contain metal elements.

[0280] In the above formula (A), specific values ​​of x, y, σ, and ε will be described with reference to the specific composition described later.

[0281] Here, the Ba (atom) deficiency amount ε in the formula (A) is also referred to as the A site deficiency amount or the Ba deficiency amount, and the substitution amount x of the A element to the M element is also referred to as the A element substitution amount, the M element substitution amount or the B site substitution amount.

[0282] The compound of this embodiment is a proton conductor. The proton conductivity of a proton conductor is relatively high at low temperatures, so a proton conductive solid electrolyte suitable for a low-temperature operating fuel cell can be obtained.

[0283] Figure 1 BaSc in the compound of formula (A) 0.8 Mo 0.2 O 3-δ It should be noted that even when an element having an ionic radius of 70 to 130% of the ionic radius of Sc is used in place of Sc in formula (A), the crystal structure is substantially the same.

[0284] The composition of the compound of the present embodiment can be determined by X-ray diffraction (XRD), fluorescent X-ray analysis (XRF), energy dispersive X-ray analysis (EDS), ICP emission analysis, or the like.

[0285] As specific examples of this embodiment, compound (A) may include compounds represented by the following [1] to

[11] .

[0286] [1](1) A proton conductive solid electrolyte having the general formula: Ba 1-α Sc 1-x Mo x O 3-δ H y It means that α is -0.2~0.2, x is 0.1~0.3, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0287] [2] A proton conductive solid electrolyte,

[0288] By the general formula: BaA 1-x M x O 3-δ H y Indicates that A is the ionic radius of all ions except Ce, In, Zr and Zn. M is an element other than A, Zr, Ce and Zn whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A and Zn whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1,

[0289] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0290] When M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1),

[0291] y is 0~1, δ is 0~1 / 2.

[0292] [3] The proton conductive solid electrolyte according to [2],

[0293] A is Sc, M is Mo, Ge, Nb, Ta, V, W or Sb,

[0294] When M is Mo or W, x is greater than 0 and less than 1 / 3; when M is Ge, x is greater than 0 and less than 1 / 2; when M is Nb, Ta, V or Sb, x is greater than 0 and less than 1 / 2.

[0295] [4] The proton conductive solid electrolyte according to [2] or [3],

[0296] Any one of the following (2) to (8).

[0297] (2) From the general formula: BaSc 1-x Ge x O 3-δ H y It means that x is 0.25 to 0.35, y is 0 to 1-x, and δ is 0 to 1 / 2-x / 2.

[0298] (3) From the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0299] (4) From the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0300] (5) From the general formula: BaSc 1-x V x O 3-δ H y It means that x is 0.2~0.25, y is 0~1-2x, and δ is 0~1 / 2-x.

[0301] (6) From the general formula: BaSc 1-x W x O 3-δ H y It means that x is 0.15~0.25, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0302] (7) From the general formula: BaSc 0.6 Ce 0.4 O 3-δ express.

[0303] (8) From the general formula: BaSc 1-x Sb x O 3-δ H y It means that x is 0.35~0.45, y is 0~1-2x, and δ is 0~1 / 2-x.

[0304] [5] A proton conductive solid electrolyte,

[0305] By the general formula: BaSc 1-x M x O 3-δ H y represents, M represents a mixed composition of multiple elements other than Sc, Zr, Ce and Zn, the average ion radius of M is 70 to 130% of the ion radius of Sc, x is greater than 0 and less than 1,

[0306] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0307] When M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1)

[0308] y is 0~1, δ is 0~1 / 2.

[0309] [6] A proton conductive solid electrolyte,

[0310] By the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y express,

[0311] M is Mo, Ge, Nb, Ta, V, W or Sb,

[0312] y is 0 to 1, ε is 0 to 0.7, δ is 0 to 1 / 2,

[0313] In the case where M is Ge, x is greater than 0 and less than 1 / 2,

[0314] When M is Nb, Ta, V or Sb, x is greater than 0 and less than 1 / 2,

[0315] When M is Mo or W, x is greater than 0 and less than 1 / 3.

[0316] [7] A proton conductive solid electrolyte,

[0317] By the general formula: Ba 1-ε Sc 1-x Ce x O 3-δ H y It means that x is greater than 0 and less than 1, y is 0 to 1, ε is greater than 0.05 to 0.7 (where 0.05 < ε < 0.2, 0 < x < 0.5), and δ is 0 to 1 / 2

[0318] [8] A proton conductive solid electrolyte,

[0319] By the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y It indicates that M is an element other than Sc and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixed composition of multiple elements other than Sc and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc, and x is greater than 0 and less than 1,

[0320] (wherein, for M=Ti, when ε=0, x is greater than 0 and less than 0.2,

[0321] For M=Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0322] For M=Zr, Ce, ε is greater than 0.05,

[0323] When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1)

[0324] y is 0~1, ε is 0~0.7, and δ is 0~1 / 2.

[0325] [9] A proton conductive solid electrolyte,

[0326] By the general formula: Ba 1-ε A 1-x M x O 3-δ H y Indicates that A is the ionic radius of all ions except Ce, In, Zr and Zn. M is an element other than A and Zn whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1,

[0327] (wherein, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95,

[0328] For M=Zr, Ce, ε is greater than 0.05,

[0329] When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1)

[0330] y is 0~1, ε is 0~0.7, and δ is 0~1 / 2.

[0331]

[10] A proton conductive solid electrolyte,

[0332] By the general formula: BaA 1-x-z M1 x M2 z O 3-δ H y express,

[0333] z is greater than 0 and less than 1, y is 0 to 1, δ is 0 to 1 / 2,

[0334] Any one of the following (28) to (35).

[0335] (28) From the general formula: BaSc 1-x-z Mo x Mz O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, Mo and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Mo and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0336] (29) From the general formula: BaSc 1-x-z Ge x M z O 3-δ H y It means that x is greater than 0 and less than 1, and M is an element other than Sc, Ge and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ge and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc.

[0337] (30) From the general formula: BaSc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Nb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Nb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0338] (31) From the general formula: BaSc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Ta and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ta and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0339] (32) From the general formula: BaSc 1-x-z V x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, V and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, V and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0340] (33) From the general formula: BaSc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, W and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, W and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0341] (34) From the general formula: BaSc 1-x-z Ce x M z O 3-δ H y It indicates that x is greater than 0 and less than 1, and M is an element other than Sc, Ce, Zr and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ce and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (wherein, when z=0, x is greater than 0 and less than 0.2. With respect to M=Cr, Fe, Mn, Co or Ni, the range of x=0.01 to 0.02 is excluded; with respect to M=Mo, Nb, Ta, V, W or Sb, the range of z=0.01 to 0.2 or x=0.74 to 0.84 is excluded).

[0342] (35) From the general formula: BaSc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Sb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Sb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0343]

[11] A proton conductive solid electrolyte,

[0344] By the general formula: Ba 1-ε A 1-x-z M1 x M2 z O 3-δ H y express,

[0345] z is greater than 0 and less than 1, y is 0 to 1, ε is 0 to 0.7, δ is 0 to 1 / 2,

[0346] Any one of the following (36) to (43).

[0347] (36) According to the general formula: Ba 1-ε Sc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, Mo and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Mo and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0348] (37) According to the general formula: Ba 1-ε Sc 1-x-z Ge x M z O 3-δ H y It means that x is greater than 0 and less than 1, and M is an element other than Sc, Ge and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ge and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc.

[0349] (38) According to the general formula: Ba 1-ε Sc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Nb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Nb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0350] (39) According to the general formula: Ba 1-ε Sc1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Ta and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ta and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0351] (40) According to the general formula: Ba 1-ε Sc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, V and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, V and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0352] (41) According to the general formula: Ba 1-ε Sc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, W and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, W and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0353] (42) According to the general formula: Ba 1-ε Sc 1-x-z Ce x M z O 3-δ H yIt means that x is greater than 0 and less than 0.8, and M is an element other than Sc, Ce and Zn (in addition, Zr is also excluded when ε=0) with an ionic radius of 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ce and Zn with an average ionic radius of 70 to 130% of the ionic radius of Sc (except for the range of ε=0 to 0.2 or x=0.01 to 0.02 for M=Cr, Fe, Mn, Co or Ni, and the range of z=0.01 to 0.2 or x=0.74 to 0.84 for M=Mo, Nb, Ta, V, W or Sb).

[0354] (43) According to the general formula: Ba 1-ε Sc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Sb and Zn, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Sb and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84).

[0355] In addition, as another aspect of the present embodiment, compound (A) may include compounds represented by the following compositions 1 to 7.

[0356] (Composition 1)

[0357] Composition 1 is composed of the general formula: Ba 1-α A 1-x M x O 3-δ H y Represents the compound.

[0358] Specifically,

[0359] (1A) For example, it can be, by the general formula: Ba 1-α Sc 1-x Mo x O 3-δ H y It means that α is -0.2~0.2, x is 0.1~0.3, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0360] (2A) Alternatively, it may be, by the general formula: BaSc 1-x Ge x O 3-δ H yIt means that x is 0.25 to 0.35, y is 0 to 1-x, and δ is 0 to 1 / 2-x / 2.

[0361] (3A) Alternatively, it may be, by the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0362] (4A) Alternatively, it may be, from the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is 0.2~0.4, y is 0~1-2x, and δ is 0~1 / 2-x.

[0363] (5A) Alternatively, it may be, from the general formula: BaSc 1-x V x O 3-δ H y It means that x is 0.2~0.25, y is 0~1-2x, and δ is 0~1 / 2-x.

[0364] (6A) Alternatively, it may be, from the general formula: BaSc 1-x W x O 3-δ H y It means that x is 0.15~0.25, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

[0365] (7A) Alternatively, it may be, from the general formula: BaSc 0.6 Ce 0.4 O 3-δ express.

[0366] (8A) Alternatively, it may be, from the general formula: BaSc 1-x Sb x O 3-δ H y It means that x is 0.35~0.45, y is 0~1-2x, and δ is 0~1 / 2-x.

[0367] (Composition 2)

[0368] Composition 2 is composed of the general formula: BaA 1-x M x O 3-δ H y Represents the compound.

[0369] Specifically,

[0370] (9A) For example, it can also be, from the general formula: BaSc 1-x Mo x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, and δ is 0 to 1 / 2.

[0371] (10A) Alternatively, it may be, from the general formula: BaSc 1-x Ge x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is between 0 and 1, and δ is between 0 and 1 / 2.

[0372] (11A) Alternatively, it may be, from the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0373] (12A) Alternatively, it may be, from the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0374] (13A) Alternatively, it may be, from the general formula: BaSc 1-x V x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0375] (14A) Alternatively, it may be, from the general formula: BaSc 1-x W x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, and δ is 0 to 1 / 2.

[0376] (15A) Alternatively, it may be, from the general formula: BaSc 1-x Sb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, and δ is 0 to 1 / 2.

[0377] (Composition 3)

[0378] Composition 3 is composed of the general formula: BaA 1-x M x O 3-δH y In general, composition 3 is obtained by expanding M of composition 2 to various elements.

[0379] Specifically,

[0380] (16A) For example, it can also be, from the general formula: BaA 1-x M x O 3-δ H y Indicates that A is the ionic radius other than Ce, In, and Zr. M is an element other than A, Zr, and Ce whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1, (wherein, for M=Ge, Sn, and Hf, x is greater than 0 and less than 0.95, when M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1), y is 0 to 1, and δ is 0 to 1 / 2. Here, the element with an ionic radius of 70 to 130% of the ionic radius of Sc can be selected from the aforementioned elements.

[0381] (17A) Alternatively, it may be, from the general formula: BaSc 1-x M x O 3-δ H y Indicates that M represents a mixed composition of multiple elements other than Sc, Zr, and Ce, the average ionic radius of M is 70% to 130% of the ionic radius of Sc, x is greater than 0 and less than 1 (wherein, for M=Ge, Sn, Hf, x is greater than 0 and less than 0.95, when M is a mixed element containing Ti and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1), y is 0 to 1, and δ is 0 to 1 / 2.

[0382] (Composition 4)

[0383] Composition 4 is composed of the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y Generally, composition 4 is a composition obtained by adding a Ba defect (A site defect) to composition 2.

[0384] Specifically, for example,

[0385] (18A) can be, by the general formula: Ba1-ε Sc 1-x Mo x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0386] (19A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x Ge x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0387] (20A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x Nb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0388] (21A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x Ta x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0389] (22A) Alternatively, it can be, according to the general formula: Ba 1-ε Sc 1-x V x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0390] (23A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x W x O 3-δ H y It means that x is greater than 0 and less than 1 / 3, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0391] (24A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x Ce x O 3-δ H yIt means that x is greater than 0 and less than 1, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2. When ε=0, x is greater than 0 and less than 0.8.

[0392] (25A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x Sb x O 3-δ H y It means that x is greater than 0 and less than 1 / 2, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0393] (Composition 5)

[0394] Composition 5 is the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y In general, composition 5 is obtained by expanding M in composition 4 to various elements.

[0395] Specifically,

[0396] (26A) For example, it can also be, from the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y It means that M is an element other than Sc, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixed composition of multiple elements other than Sc, whose average ionic radius is 70 to 130% of the ionic radius of Sc, x is greater than 0 and less than 1, (wherein, for M = Ti, in the case of ε = 0, x is greater than 0 and less than 0.2, for M = Ge, Sn, Hf, x is greater than 0 and less than 0.95, for M = Zr, Ce, ε is greater than 0.05, when M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, Ni, the ratio of the Cr, Fe, Mn, Co or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2. Here, the element with an ionic radius of 70 to 130% of the ionic radius of Sc can be selected from the aforementioned elements.

[0397] (27A) Alternatively, it can be, from the general formula: Ba 1-ε A 1-x M x O 3-δ H y Indicates that A is the ionic radius other than Ce, In, and Zr. elements, M is an element other than A whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1, (wherein, for M=Ge, Sn, Hf, x is greater than 0 and less than 0.95, for M=Zr, Ce, ε is greater than 0.05, when M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, Ni, the ratio of Cr, Fe, Mn, Co or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0398] (Composition 6)

[0399] Composition 6 is composed of the general formula: BaA 1-x-z M1 x M2 z O 3-δ H y Represents the compound.

[0400] Specifically,

[0401] (28A) For example, it can also be, from the general formula: BaSc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and Mo, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Mo, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0402] (29A) Alternatively, it may be, from the general formula: BaSc 1-x-z Ge x M z O 3-δ H y It means that x is greater than 0 and less than 1, z is greater than 0 and less than 1, M is an element other than Sc and Ge, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Ge, and the average ionic radius is 70 to 130% of the ionic radius of Sc, y is 0 to 1, and δ is 0 to 1 / 2.

[0403] (30A) Alternatively, it may be, from the general formula: BaSc 1-x-z Nbx M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Nb, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Nb, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0404] (31A) Alternatively, it may be, from the general formula: BaSc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Ta, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Ta, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0405] (32A) Alternatively, it may be, from the general formula: BaSc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and V, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and V, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0406] (33A) Alternatively, it may be, from the general formula: BaSc 1-x-z W x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and W, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and W, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0407] (34A) Alternatively, it may be, from the general formula: BaSc 1-x-z Ce x M z O 3-δ H y It means that x is greater than 0 and less than 1, z is greater than 0 and less than 1, M is an element other than Sc, Ce and Zr, whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc and Ce, whose average ionic radius is 70 to 130% of the ionic radius of Sc (wherein, when z=0, x is greater than 0 and less than 0.2. For M=Cr, Fe, Mn, Co or Ni, the range of x=0.01 to 0.02 is excluded; for M=Mo, Nb, Ta, V, W or Sb, the range of z=0.01 to 0.2 or x=0.74 to 0.84 is excluded), y is 0 to 1, and δ is 0 to 1 / 2.

[0408] (35A) Alternatively, it may be, from the general formula: BaSc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Sb, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Sb, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, and δ is 0 to 1 / 2.

[0409] (Composition 7)

[0410] Composition 7 is composed of the general formula: Ba 1-ε A 1-x-z M1 x M2 z O 3-δ H y Generally, composition 7 is a composition obtained by adding a Ba defect (A site defect) to composition 6.

[0411] Specifically,

[0412] (36A) For example, it can also be, from the general formula: Ba 1-ε Sc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and Mo, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Mo, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0413] (37A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z Ge x M z O 3-δ H y It means that x is greater than 0 and less than 1, z is greater than 0 and less than 1, M is an element other than Sc and Ge, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Ge, and the average ionic radius is 70 to 130% of the ionic radius of Sc, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0414] (38A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Nb, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Nb, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0415] (39A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z Ta x M z O 3-δ H yIt means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Ta, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Ta, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0416] (40A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and V, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and V, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0417] (41A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, z is greater than 0 and less than 1, M is an element other than Sc and W, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and W, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0418] (42A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z Ce x M z O 3-δ H yIt means that x is greater than 0 and less than 0.8, z is greater than 0 and less than 1, M is an element other than Sc and Ce (excluding Zr when ε=0) with an ionic radius of 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc and Ce with an average ionic radius of 70 to 130% of the ionic radius of Sc (except for the range of ε=0 to 0.2 or x=0.01 to 0.02 for M=Cr, Fe, Mn, Co or Ni, and the range of z=0.01 to 0.2 or x=0.74 to 0.84 for M=Mo, Nb, Ta, V, W or Sb), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0419] (43A) Alternatively, it can be, from the general formula: Ba 1-ε Sc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, z is greater than 0 and less than 1, M is an element other than Sc and Sb, whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixture of multiple elements other than Sc and Sb, and the average ionic radius is 70 to 130% of the ionic radius of Sc (except for M=Ce, x=0.01 to 0.2 or z=0.74 to 0.84), y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

[0420] (Effects of this embodiment)

[0421] The proton conductive solid electrolyte including the compound of the present embodiment has high proton conductivity in a low to medium temperature range.

[0422] As a prior art, it is known to replace Zr oxide of barium zirconate with dopants such as Sc, Y, and lanthanide elements, and attempt to increase the proton concentration by increasing the replacement rate of dopants such as Sc. In addition, in Patent Document 3, proton conductivity is increased by increasing the proportion of Sc and the proportion of protons.

[0423] On the other hand, in the present embodiment, it was found that the proton conductivity can be further improved by using Sc—Mo and an element having an ion radius close to these elements instead of the same crystal structure of Zr—Sc in Patent Document 3.

[0424] The compound of this embodiment has a proton conductivity far higher than that of the conventional proton conductor 20Y:BZ. 1-x M x O 3-δ ,BaCe 1-x Mx O 3-δ (M=mainly Y, Sc, etc.) The compound of this embodiment uses Sr or an element with an ion radius close thereto instead of Zr or Ce, and uses Mo, Ge, etc. as M. In particular, when M=Mo is used, a proton conductivity approximately one order of magnitude higher than that of the prior art can be obtained.

[0425] In particular, the compound of this embodiment has a proton conductivity far higher than that of the conventional proton conductor 20Y:BZ. Specifically, at 175°C, BaSc 0.8 Mo 0.2 O 3-δ The intragranular conductivity of 20Y:BZ is about 10 times that of 20Y:BZ at the same temperature ( Fig.38 ).

[0426] In addition, in 10 -25 In a wide oxygen partial pressure range from about 0 atm to about 0 atm, the total conductivity is almost independent of the oxygen partial pressure, is substantially constant, and has high stability. The compound of this embodiment suggests that proton conduction is dominant.

[0427] (Second Embodiment)

[0428] (Compound (B): Ba 5-α R 2+x Al 2+y M 1+z O 13+δ )

[0429] One embodiment of the compound of the present embodiment is a proton conductive solid electrolyte including a compound represented by the following general formula (B) and the following compound (B).

[0430] Ba 5-α R 2+x Al 2+y M 1+z O 13+δ …(B)

[0431] [In formula (B), α is 0 to 2, x is −1 to 1, y is −1 to 1, z is −0.5 to 0.5, δ is −1 to 1,

[0432] In the general formula, R is a cation of an element selected from the group consisting of rare earth elements and Ga, and M is a cation of an element selected from the group consisting of Hf, Sn and Zr]

[0433] Here, the compound of formula (B) is a so-called hexagonal perovskite-related compound. The hexagonal perovskite-related compound in this embodiment refers to a compound having a layered structure including a hexagonal perovskite unit or a compound having a structure similar thereto.

[0434] In addition, the compound contained in the proton conductive solid electrolyte in the present embodiment is a compound of formula (B) wherein R is a cation of an element selected from the group consisting of rare earth elements and Ga. Preferably, R of the compound of formula (B) is Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm or Yb.

[0435] In addition, for the compound contained in the proton conductive solid electrolyte in this embodiment, M of the compound of formula (B) is Hf, Sn or Zr. Among them, M is preferably Sn. In addition, the composition represented by M of the compound of formula (B) can be a single element or a mixed composition of multiple elements such as Sn, Hf, and Zr.

[0436] The compound contained in the proton conductive solid electrolyte of the present embodiment is more preferably one in which M in the general formula is Sn, and R is Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm, or Yb.

[0437] As more specific examples of the compound of formula (B), Ba5Er2Al2Sn 1-x Zr x O 13 ,Ba5Er 2- x Al 2+x SnO 13 , or Ba5Er 2+x Al2Sn 1-x O 13-x / 2 wait.

[0438] (Compound (B1): Ba5R2Al2MO 13 )

[0439] In addition, as a specific example of the compound included in the compound (B), one embodiment of the compound of the present embodiment may be a compound represented by the following general formula (B1), that is, a proton conductive solid electrolyte including the following compound (B1).

[0440] Ba5R2Al2MO 13 …(B1)

[0441] [In formula (B1), R is a cation of an element selected from the group consisting of rare earth elements, In and Ga, and M is a cation of an element selected from the group consisting of Hf and Sn]

[0442] More preferably, R is a cation of one element selected from the group consisting of rare earth elements and Ga.

[0443] Figure 2 Ba5Nd2Al2SnO in the compound of formula (B1) 13 It should be noted that even when R=Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm or Yb is used in formula (B1), the crystal structure is substantially the same.

[0444] Conventionally, Ba5Nd2Al2ZrO is known as a proton conductor. 13 The compound (B1) of the present embodiment can exhibit more excellent proton conductivity in a low to medium temperature range, particularly by using Sn or Hf instead of the above-mentioned conventional compound Zr.

[0445] (Proton Conducting Properties of the Compounds of the Present Embodiment)

[0446] In this embodiment, it is considered that the compounds having the above conditions of the compounds (A) and (B) have properties as various ion conductors. In particular, it is assumed that when the above compounds are used as proton conductors, effective conductivity can be obtained. Proton conductors refer to compounds that pass protons (hydrogen ions, H + ) to conduct electricity. In addition, the proton conductive solid electrolyte using the compound of this embodiment is preferably used at a temperature of 200 to 1200°C, more preferably at a temperature of 200 to 1000°C, further preferably at 200°C or more and less than 700°C, and particularly preferably at 200 to 600°C. By using it under such temperature conditions, it can stably operate in a wider temperature range than conventional fuel cells, so there are fewer restrictions on the device or configuration required for the operation, and a wide range of applications can be obtained.

[0447] Note that the proton conductive solid electrolyte using the compound of the present embodiment can also operate at a temperature higher than 600° C., which is the operating temperature of a solid oxide fuel cell (SOFC), for example.

[0448] When the proton conductive solid electrolyte of the present embodiment is measured for the proton conductivity in the particle, log[σ(Scm -1 The temperature at which the conductivity represented by )] is greater than -2.0 is preferably 350° C. or less. In addition, the temperature is more preferably 320° C. or less. By making the conductivity below 350° C. sufficiently high, it can be particularly suitable for batteries and other devices that have high conductivity at low temperatures and operate at low temperatures.

[0449] The proton conductive solid electrolyte may be used in the form of a film, layer (sheet or plate) based on a crystal of a powder. Alternatively, it may be used in the form of a powder.

[0450] The proton conductive solid electrolyte may contain one compound equivalent to the above-mentioned compound (A) or (B), or may contain two or more. The proton conductive solid electrolyte may also contain compounds other than the above-mentioned compound (A) or (B). For example, other proton conductive compounds may also be contained. However, in the case where the electrolyte is processed into a film-like, layered material or the like, in order to obtain a uniform material, it is preferred that the content ratio of the compound equivalent to compound (A) or (B) is high, or it may be composed only of the compound.

[0451] The proton conductive solid electrolyte of the present embodiment may be composed of a single crystal when in powder form, or may be an aggregate of a plurality of crystal grains. In addition, the aggregate may be a polycrystalline body.

[0452] The average particle size of the crystal grains is preferably greater than 3 μm. By making the average particle size of the crystal grains within the above range, the resistance caused by grain boundary conduction in the proton conductive solid electrolyte can be suppressed, and the proton conductivity can be further improved. In addition, the average particle size of the crystal grains of the proton conductive solid electrolyte is further preferably 6 to 7 μm. By making the average particle size of the crystal grains within the above range, the increase in resistance caused by grain boundary conduction in the proton conductive solid electrolyte can be suppressed, and the proton conductivity can be further improved.

[0453] (Proton conductive solid electrolyte layer)

[0454] The proton conductive solid electrolyte of the present embodiment can be formed into a layer, or formed in a manner contained in a layered structure, and used as a proton conductive solid electrolyte layer. The proton conductive solid electrolyte layer may include other ion conductors, etc. in addition to the proton conductive solid electrolyte of the present embodiment. Batteries using the proton conductive solid electrolyte of the present embodiment exhibit high conductivity. In addition, in order to effectively operate as a low-temperature working battery described later, it is preferred that the proton conductive solid electrolyte layer contains, for example, 50% by mass or more, preferably 70% by mass or more, of a proton conductive solid electrolyte containing the compound of the present embodiment.

[0455] (Proton conductive solid electrolyte or battery including a proton conductive solid electrolyte layer)

[0456] The proton conductive solid electrolyte of the present embodiment or the electrolyte layer including the proton conductive solid electrolyte can be used for a battery including the electrolyte layer. The proton conductive solid electrolyte of the present embodiment can be particularly suitably used for a fuel cell as described above.

[0457] The proton conductive solid electrolyte in this embodiment, or a battery using an electrolyte layer containing the proton conductive solid electrolyte, can be particularly suitable for low-temperature operating batteries. In this embodiment, as described above, the low-temperature operating battery is a battery that operates at 200 to 1200°C, preferably 200 to 1000°C, more preferably 200 or more and less than 700°C, and particularly preferably 200 to 600°C.

[0458] The battery in this embodiment includes, for example, an anode, a cathode, and the above-mentioned proton conductive solid electrolyte layer interposed therebetween. The cathode and the proton conductive solid electrolyte may form an integrated cathode-proton conductive solid electrolyte layer assembly.

[0459] (Other uses of proton conductive solid electrolytes)

[0460] In the past, proton conductive solid electrolytes containing perovskite structures, deformed perovskite structures, compounds having perovskite-related structures, or hexagonal perovskite-related compounds have shown high ion conductivity and are therefore widely used in batteries, sensors, ion concentrators, membranes for ion separation or permeation, and catalysts, etc. The proton conductive solid electrolyte of the present embodiment can be used in the same manner as these. For example, the proton conductive solid electrolyte of the present embodiment can be used in other batteries, sensors, electrodes, electrolytes, hydrogen concentrators, hydrogen separation membranes, hydrogen permeation membranes, hydrogen pumps, catalysts, photocatalysts, electrical / electronic / communication equipment, energy / environment-related equipment, or optical equipment, etc., in addition to fuel cells.

[0461] The proton conductive solid electrolyte layer of the present embodiment described above can be particularly suitably used in fuel cells, sensors, etc. Examples of fuel cells include solid oxide fuel cells (SOFCs) and proton ceramic fuel cells (PCFCs).

[0462] The proton conductive solid electrolyte of this embodiment can be used as a sensor for electrolytes such as gas sensors. By installing a sensing electrode corresponding to the gas to be detected on the electrolyte, a gas sensor or a gas detector can be formed. For example, a hydrogen sensor can be obtained, a carbon dioxide sensor can be obtained when a sensing electrode containing carbonate is used, a NOx sensor can be obtained when a sensing electrode containing nitrate is used, and a SOx sensor can be obtained when a sensing electrode containing sulfate is used. In addition, by assembling an electrolytic cell, a capture device or a decomposition device for NOx and / or SOx contained in the exhaust gas can be formed.

[0463] The proton conductive solid electrolyte of the present embodiment can also be used as an adsorbent or adsorption separation agent for ions or the like, or various catalysts.

[0464] The proton conductive solid electrolyte of this embodiment may also function as an activator for various rare earth elements in the ion conductor to form a luminescence center (color center). In this case, it can be used as a wavelength changing material or the like.

[0465] The proton conductive solid electrolyte of the present embodiment may become a superconductor by being doped with electron carriers or hole carriers.

[0466] The proton conductive solid electrolyte of this embodiment can also use the proton conductive solid electrolyte as an ion conductor, attach an inorganic compound or the like that is colored or discolored due to the embedding / de-embedding of conductive ions on its surface, and then form a light-transmitting electrode such as ITO thereon, thereby making an all-solid electrochromic element. By using this all-solid electrochromic element, an electrochromic display with memory characteristics that suppresses power consumption can be provided.

[0467] (Method for producing proton conductive solid electrolyte)

[0468] The method for producing a proton conductive solid electrolyte according to the present embodiment produces the compound by a solid phase reaction method.

[0469] The solid phase reaction method can be carried out by a conventionally known process, for example, mixing the starting materials so that the molar ratio of the elements becomes the target chemical composition, pressing and molding into pellets, and calcining to produce a perovskite-type compound or a hexagonal perovskite-related compound.

[0470] First, a starting material containing an element of a target chemical composition is prepared. The starting material may be dried in advance. Drying can be performed at 200 to 1000° C. for 5 to 20 hours using an electric furnace or the like.

[0471] Next, the starting materials are mixed in such a way that the molar ratio of the elements becomes the target chemical composition. The composition of the molar ratio can be based on the molar ratio of the cations. Mixing and grinding can be appropriately performed, for example, using an agate mortar and mixing and grinding by dry mixing and grinding or wet mixing and grinding using ethanol, and repeating for 0.5 to 2 hours.

[0472] The obtained mixture is pressurized into particles. The molding can be performed by pressurizing the mixture after pre-calcining. The pre-calcination can be performed at 300 to 1100° C. for 5 to 24 hours using an electric furnace or the like. After pre-calcination, the mixture can be crushed again and the above-mentioned mixed grinding can be performed. The mixture is formed into particles at 62 to 150 MPa.

[0473] The molded particles are calcined (sintered) at 1400 to 1700° C. for 3 to 24 hours in the atmosphere, more preferably at 1450 to 1600° C. for 8 to 13 hours.

[0474] The compound of the present embodiment can be efficiently produced by these production methods, synthesis methods, and calcination conditions.

[0475] Example

[0476] Hereinafter, although an Example is shown and this embodiment is demonstrated, this invention is not limited to the following Example.

[0477] [Test Examples 1 to 17: Compound (A), BaA 1-x M x O 3-δ Synthesis and analysis of

[0478] (BaSc 0.8 Mo 0.2 O 3-δ Synthesis of

[0479] The sample was synthesized by a solid phase reaction method. BaCO3, Sc2O3, and MoO3 were used as starting materials. The starting materials were dried at 300°C for 12 hours in advance and weighed with an electronic balance. Dry mixing and grinding and wet mixing and grinding using ethanol were repeated for 30 to 60 minutes using an agate mortar. The obtained mixture was pre-calcined at 900°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding for 30 to 60 minutes in an agate mortar. A uniaxial press was used to pressurize at 150MPa, thereby forming the mixture into particles with a diameter of 20mm. The obtained particles were placed in an electric furnace and sintered at 1500°C for 12 hours in the atmosphere. As a result, particles as sintered bodies were obtained.

[0480] (Synthesis of other compositions of compound (A))

[0481] About BaSc 0.8 Mo 0.2 O 3-δ Other equivalent to BaA 1-x M x O 3-δ Other compounds were synthesized by the same steps as above and the following steps.

[0482] The sample was synthesized by solid phase reaction method. As starting materials, BaCO3, Sc2O3, MoO3, GeO2, Nb2O5, Ta2O5, WO3, V2O5, CeO2, Sb2O3 were used. The starting materials were dried at 300°C for 12 hours and weighed with an electronic balance. Dry mixing and grinding for 30 to 60 minutes and wet mixing and grinding using ethanol were repeated using an agate mortar.

[0483] (About Ba-Sc-Mo-O series)

[0484] The obtained mixture was pre-calcined at 900°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into pellets with a diameter of 20 mm. The obtained pellets were placed in an electric furnace and sintered at 1500°C for 12 hours in the atmosphere.

[0485] (About Ba-Sc-Ge-O system)

[0486] The obtained mixture was pre-calcined at 900°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into granules with a diameter of 20 mm. The obtained granules were placed in an electric furnace and sintered at 1600°C for 12 hours in the atmosphere.

[0487] (About Ba-Sc-Nb-O system)

[0488] The obtained mixture was pre-calcined at 900°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into granules with a diameter of 20 mm. The obtained granules were placed in an electric furnace and sintered at 1600°C for 12 hours in the atmosphere.

[0489] (About Ba-Sc-Ta-O system)

[0490] The obtained mixture was pre-calcined at 900°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into granules with a diameter of 20 mm. The obtained granules were placed in an electric furnace and sintered at 1600°C for 12 hours in the atmosphere.

[0491] (About Ba-Sc-WO system)

[0492] The obtained mixture was pre-calcined at 1000°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into granules with a diameter of 20 mm. The obtained granules were placed in an electric furnace and sintered at 1600°C for 12 hours in the atmosphere.

[0493] (About Ba-Sc-VO system)

[0494] The obtained mixture was pre-calcined at 1000°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into pellets with a diameter of 20 mm. The obtained pellets were placed in an electric furnace and sintered at 1450°C for 12 hours in the atmosphere.

[0495] (About Ba-Sc-Ce-O system)

[0496] The obtained mixture was pre-calcined at 1000°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into granules with a diameter of 20 mm. The obtained granules were placed in an electric furnace and sintered at 1600°C for 12 hours in the atmosphere.

[0497] (About Ba-Sc-Sb-O system)

[0498] The obtained mixture was pre-calcined at 1000°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was repeatedly subjected to wet mixing and grinding using ethanol and dry mixing and grinding in an agate mortar for 30 to 60 minutes. The mixture was pressurized at 150 MPa using a uniaxial press and formed into granules with a diameter of 20 mm. The obtained granules were placed in an electric furnace and sintered at 1500°C for 12 hours in the atmosphere.

[0499] (XRD measurement)

[0500] In order to evaluate the generated phase of the obtained sintered body by X-ray diffraction (XRD), the sintered body was crushed and then ground with an agate mortar for 30 to 60 minutes. For each test example, XRD measurement was performed using a diffraction device Rigaku MiniFlex. The lattice constant was determined by Tewold analysis of the obtained XRD data.

[0501] Figure 3 Test Example 1: BaSc0.8 Mo 0.2 O 3-δ

[0502] Figure 4 Test Example 2: BaSc 0.75 Mo 0.25 O 3-δ

[0503] Figure 5 Test Example 3: BaSc 0.85 Mo 0.15 O 3-δ

[0504] Figure 6 Test Example 4: BaSc 0.7 Ge 0.3 O 3-δ

[0505] Figure 7 Test Example 5: BaSc 0.75 Ge 0.25 O 3-δ

[0506] Figure 8 Test Example 6: BaSc 0.65 Ge 0.35 O 3-δ

[0507] Fig. 9 Test Example 7: BaSc 0.8 Nb 0.2 O 3-δ

[0508] Fig.10 Test Example 8: BaSc 0.75 Nb 0.25 O 3-δ

[0509] Fig.11 Test Example 9: BaSc 0.7 Nb 0.3 O 3-δ

[0510] Fig.12 Test Example 10: BaSc 0.65 Nb 0.35 O 3-δ

[0511] Fig.13 Test Example 11: BaSc 0.6 Nb 0.4 O 3-δ

[0512] Fig.14 Test Example 12: BaSc 0.7 Ta 0.3 O 3-δ

[0513] Fig.15 Test Example 13: BaSc 0.8 V 0.2 O 3-δ

[0514] Fig.16 Test Example 14: BaSc 0.75 V 0.25 O 3-δ

[0515] Fig.17 Test Example 15: BaSc 0.8 W 0.2 O 3-δ

[0516] Fig.18 Test Example 16: BaSc 0.6 Ce 0.4 O 3-δ

[0517] Fig.19 Test Example 17: BaSc 0.6 Sb 0.4 O 3-δ The results of XRD measurement.

[0518] In addition, lattice constants are shown in Tables 1 and 2. The lattice constants in Tables 1 and 2 are values ​​obtained by structural optimization of density functional theory calculations described later.

[0519] Tables 1 and 2 show the Ba values ​​estimated by structural optimization based on DFT calculation. 1-α A 1-x M x O 3-δ The lattice constant a a=b=c, α=β=γ=90°.

[0520] [Table 1]

[0521]

[0522] [Table 2]

[0523]

[0524] (Total conductivity measurement)

[0525] The conductivity of each test example was measured by the direct current four-terminal method. The water vapor partial pressure P(H2O) was 0.02 atm at 18°C ​​and the water vapor partial pressure P(H2O) was <1.5×10 -4 The proton conductivity was evaluated by measuring the conductivity in a dry atmosphere of 1000 atm. In addition, the proton conductivity was evaluated not only in a wet atmosphere of light water (H2O) but also in a wet atmosphere of heavy water (D2O). The synthesized sample was formed into a diameter of The particles were sintered again at 1500°C for 12 hours in the atmosphere to prepare a sample for conductivity measurement. Four platinum wires were wound around the sintered body, and platinum slurry was applied to the platinum wires to make the sample and the platinum wires adhere closely. In order to remove the organic components contained in the platinum slurry, it was heated at 900°C for 1 hour in an electric furnace.

[0526] Fig. 20 Test Example 1: BaSc 0.8 Mo 0.2 O 3-δ

[0527] Fig.21 Test Example 2: BaSc 0.75 Mo 0.25 O 3-δ

[0528] Fig. 22 Test Example 3: BaSc 0.85 Mo 0.15 O 3-δ

[0529] Fig.23 Test Example 4: BaSc 0.7 Ge 0.3 O 3-δ

[0530] Fig.24 Test Example 5: BaSc 0.75 Ge 0.25 O 3-δ

[0531] Fig.25 Test Example 6: BaSc 0.65 Ge 0.35 O 3-δ

[0532] Fig.26 Test Example 7: BaSc 0.8 Nb 0.2 O 3-δ

[0533] Fig. 27 Test Example 8: BaSc0.75 Nb 0.25 O 3-δ

[0534] Fig.28 Test Example 9: BaSc 0.7 Nb 0.3 O 3-δ

[0535] Fig.29 Test Example 10: BaSc 0.65 Nb 0.35 O 3-δ

[0536] Fig.30 Test Example 11: BaSc 0.6 Nb 0.4 O 3-δ

[0537] Fig.31 Test Example 12: BaSc 0.7 Ta 0.3 O 3-δ

[0538] Fig.32 Test Example 13: BaSc 0.8 V 0.2 O 3-δ

[0539] Fig.33 Test Example 14: BaSc 0.75 V 0.25 O 3-δ

[0540] Fig.34 Test Example 15: BaSc 0.8 W 0.2 O 3-δ

[0541] Fig.35 Test Example 16: BaSc 0.6 Ce 0.4 O 3-δ

[0542] Fig.36 Test Example 17: BaSc 0.6 Sb 0.4 O 3-δ Arrhenius curve of the DC total conductivity measured by cooling in humid air and maintaining it at a certain temperature.

[0543] It should be noted that Fig.26 In the figure, bulk conductivity is represented by (○) and grain boundary conductivity is represented by (□).

[0544] Fig.37 Test Example 1: BaSc 0.8 Mo 0.2 O 3-δ Arrhenius plots of intragranular conductivity and grain boundary conductivity.

[0545] It should be noted that in Fig.37 In the figure, the dotted line represents the Norby gap and the dashed line represents the proton conductivity of 0.01 S / cm.

[0546] Fig.38 Test Example 1: BaSc 0.8 Mo 0.2 O 3-δ Comparison of the Arrhenius curve of the conductivity of the conventional material. Fig.37 As existing materials, 60Sc:BZ, 20Y:BZ, Ba5Er2Al2ZrO 13 .

[0547] As the existing material, the highest performance proton conductor is 60Sc:BZ or BaZr. 0.4 Sc 0.6 O 3-δ , Test Example 1 shows a higher proton conductivity than that. In addition, especially for the currently used material close to practical application, 20Y:BZ, namely BaZr 0.8 Y 0.2 O 3-δ , the proton conductivity of Test Example 1 is about 10 times higher. That is, Test Example 1 can be said to be a promising new substance.

[0548] In addition, the proton conductivity required for practical use is usually 0.01 Scm -1 (log[σ(Scm -1 )] = -2.0). In the prior art proton conductor, the proton conductivity cannot reach 0.01 Scm unless it is at a high temperature. -1 , 20Y:BZ reached at 534℃, 60Sc:BZ reached at 396℃. On the other hand, Fig.37 , 38 It is found that the compound of Test Example 1 reaches the proton conductivity required for practical use at 320° C. That is, the compound shows a proton conductivity required for practical use at a temperature 214° C. lower than that of the material 20Y:BZ currently in practical use.

[0549] In addition, the technical issues required for practical application are Fig.37 , 38The dashed V-shaped line in the graph indicates that the curve should reach a point above the Norby Gap. Among existing materials, 60Sc:BZ only reaches this point in a narrow temperature range of about 280°C. In contrast, the compound of Test Example 1 reaches the Norby Gap in a wide temperature range of about 250 to 400°C, and is expected to have high practicality.

[0550] (Oxygen partial pressure dependence of total conductivity)

[0551] The oxygen partial pressure dependence of the total conductivity was measured by the direct current four-terminal method. The sample was prepared in the same manner as the total conductivity measurement described above, and the oxygen partial pressure was controlled using oxygen, nitrogen, or nitrogen-hydrogen mixed gas. The oxygen partial pressure was monitored using an oxygen sensor located downstream of the device.

[0552] Fig.39 The time dependence of the conductivity when switching from light water (H2O) to heavy water (D2O) and then to humid air of light water (H2O) is shown, i.e., a curve diagram of the relaxation process, for Experimental Example 1. As can be seen from the figure, when switching to the D2O atmosphere, the total conductivity decreases, and the ratio of the conductivity in the H2O air to that in the D2O air is 1.33, which is close to the ideal value of 1.41 in the classical theory of proton conduction, so it can be seen that proton conduction is dominant.

[0553] Fig.40 A graph showing the oxygen partial pressure dependence of dry atmosphere and humid atmosphere at 300° C. for Test Example 1. The total conductivity in the humid atmosphere is 10 times higher than that in the dry atmosphere, and the total conductivity is almost independent of the oxygen partial pressure, indicating that protons are the dominant conductive species.

[0554] Fig.41 A graph showing another Arrhenius curve of the electrical conductivity of each gas atmosphere with respect to Experimental Example 1 is shown.

[0555] The total conductivity in dry air is a roughly linear straight line, but in a humid atmosphere, it shows a nonlinear total conductivity. The total conductivity in light water H2O air is higher than that in dry air, especially 40 times higher at 300°C. This result strongly suggests proton conduction. In addition, the conductivity in light water H2O air is 1.1 to 1.6 times higher than that in heavy water D2O air, which also strongly suggests that proton conduction is dominant.

[0556] (Body conductivity evaluation)

[0557] The bulk conductivity was determined by the AC impedance method. The atmosphere was controlled using air, nitrogen, or nitrogen-hydrogen mixed gas. The oxygen partial pressure was monitored using an oxygen sensor installed downstream of the device.

[0558] Fig.42 The graph shows the oxygen partial pressure dependence of the bulk conductivity of Test Example 1. The graph shows the oxygen partial pressure dependence of the bulk conductivity at 310°C and 147°C in a humid atmosphere. It is found that the bulk conductivity does not depend on the oxygen partial pressure, and the chemical stability and electrical stability are high on the oxidation side and the reduction side.

[0559] (Thermogravimetric analysis)

[0560] The proton concentration was measured using a thermogravimetric analyzer (manufactured by NETZSCH, product name: STA449F3 Jupiter). After heating at 1000°C for 160 minutes in a dry nitrogen atmosphere, the temperature was lowered while balancing in a humid nitrogen atmosphere. It is assumed that the cause of the mass increase observed in this operation is hydration, which determines the proton concentration at each temperature.

[0561] Fig.43 A graph showing the results of thermal mass (TG) analysis of Test Example 1.

[0562] Fig.44 A graph showing the temperature dependence of the proton concentration estimated from the thermal mass analysis results of Test Example 1.

[0563] (Calculation of Diffusion Coefficient)

[0564] The temperature dependence of the proton diffusion coefficient was calculated by using the bulk proton conductivity measured by the AC impedance method and the proton concentration measured by the thermogravimetric analysis. Specifically, the calculation was performed based on the Nernst-Einstein equation.

[0565] Fig.45 Arrhenius curve diagram showing the diffusion coefficient of Test Example 1. In the figure, Test Example 1 is compared with the conventional material BaZr 0.8 Y 0.2 O 3-δ ,BaSc 0.6 Zr 0.4 O 3-δ .

[0566] As can be seen from the figure, Test Example 1 shows a proton diffusion coefficient that is about 10 times higher than that of the existing material. It is believed that the high proton conductivity of Test Example 1 is due to the high diffusion coefficient.

[0567] (Chemical stability)

[0568] This material shows a high proton conductivity of 10mS / cm above 320°C and can be used as a proton conductive solid electrolyte for fuel cells. Therefore, the stability in a carbon dioxide gas flow at 320°C, a nitrogen-5% hydrogen mixed gas, and an oxygen gas was evaluated. After measuring the X-ray diffraction data of the sample before the stability test, the powder sample was annealed in a tubular furnace at 320°C in carbon dioxide gas, a nitrogen-hydrogen mixed gas, and oxygen for 24 hours. X-ray diffraction data was collected for the powder sample after annealing, and the chemical stability was evaluated.

[0569] Fig.46 The stability curves in oxidizing, reducing atmospheres and CO2 of Test Example 1 are shown. The powdered samples were annealed under each condition (O2, N2+H2, CO2, before the test) in the figure to evaluate their chemical stability. The simulation results of BaCO3 are also shown.

[0570] The XRD pattern of Test Example 1 did not change before and after the stability test, and it showed excellent chemical stability in O2 (oxidizing atmosphere), 95% N2 + 5% H2 (reducing atmosphere) and CO2.

[0571] [Compound (B), Ba5R2Al2SnO 13 Synthesis and analysis of

[0572] The sample was synthesized by solid phase reaction method. As starting materials, BaCO3, SnO2, Al2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3, Yb2O3, Y2O3, Nd2O3 were used. The starting materials were dried at 300°C for 12 hours. In addition, Nd2O3 was dried at 1000°C for 12 hours. The samples were weighed with an electronic balance, and dry mixing and grinding for 30 to 60 minutes and wet mixing and grinding using ethanol were repeated using an agate mortar.

[0573] (Ba5Nd2Al2SnO 13 、Ba5Sm2Al2SnO 13 、Ba5Eu2Al2SnO 13 、Ba5Gd2Al2SnO 13 、Ba5Dy2Al2SnO 13 、Ba5Y2Al2SnO 13 Synthesis of

[0574] The obtained mixture was pre-calcined at 1000°C for 12 hours in the atmosphere using an electric furnace. The pre-calcined mixture was dry-mixed and ground in an agate mortar for 30 to 60 minutes. The mixture was formed into granules with a diameter of 20 mm using a uniaxial press and pressurized at 200 MPa using a cold isostatic pressing device (CIP). The obtained granules were placed in an electric furnace and sintered at 1400°C for 12 hours in the atmosphere.

[0575] (Ba5Ho2Al2SnO 13 、Ba5Er2Al2SnO 13 、Ba5Tm2Al2SnO 13 、Ba5Yb2Al2SnO 13 Synthesis of

[0576] The mixture obtained using an electric furnace was pre-calcined at 1000°C for 12 hours in the atmosphere. The pre-calcined mixture was dry-ground in an agate mortar for 30 to 60 minutes. The mixture was formed into granules with a diameter of 20 mm using a uniaxial press and pressurized at 200 MPa using a cold isostatic pressing device (CIP). The obtained granules were placed in an electric furnace and sintered at 1500°C for 12 hours in the atmosphere.

[0577] (X-ray diffraction measurement)

[0578] In order to evaluate the generated phase of the obtained sintered body by X-ray diffraction (XRD), the sintered body was crushed and then repeatedly ground in wet and dry conditions using ethanol in an agate mortar for 30 to 60 minutes. XRD measurement was performed using an X-ray diffraction device Rigaku MiniFlex. The lattice constant of the perovskite oxide was obtained by Tewold analysis of the obtained XRD data.

[0579] Table 3 shows the estimated Ba5R2Al2MO 13 lattice constant.

[0580] Table 4 shows the lattice constants of the perovskite oxide synthesized in the above test example, which were refined by the Tewold analysis of XRD data. Table 4 shows the lattice constant a of the perovskite proton conductor obtained by the Tewold analysis of XRD data at room temperature. a=b=c, α=β=γ=90°. The numbers in parentheses are the estimated standard deviation esd when refined, which is the last digit of the lattice constant. For example, the esd of 4.1463(2) is 0.0002.

[0581] [Table 3]

[0582]

[0583] [Table 4]

[0584]

[0585] Fig.47 The results of XRD measurement of each synthesis example of R=Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm, and Yb are shown.

[0586] (Total conductivity measurement)

[0587] (Ba5Nd2Al2SnO 13 、Ba5Sm2Al2SnO 13 、Ba5Eu2Al2SnO 13 、Ba5Gd2Al2SnO 13 、Ba5Dy2Al2SnO 13 、Ba5Y2Al2SnO 13 Determination of

[0588] The conductivity of each test example was measured by the direct current four-probe method. The synthesized sample was formed into a diameter of The particles were sintered at 1400°C for 12 hours to produce a sample for conductivity measurement. Four platinum wires were wound around the sintered body for total conductivity measurement using the DC four-terminal method. Platinum slurry was applied to the platinum wires to make the sample and the platinum wires adhere closely. In order to remove the organic components contained in the platinum slurry, it was heated at 1000°C for 1 hour using an electric furnace.

[0589] (Ba5Ho2Al2SnO 13 、Ba5Er2Al2SnO 13 、Ba5Tm2Al2SnO 13 、Ba5Yb2Al2SnO 13 Determination of

[0590] The conductivity of each test example was measured by the direct current four-probe method. The synthesized sample was formed into a diameter of The particles were sintered at 1500°C for 12 hours to prepare a sample for conductivity measurement. Four platinum wires were wound around the sintered body for total conductivity measurement using the DC four-terminal method. Platinum slurry was applied to the platinum wires to make the sample and the platinum wires adhere closely. In order to remove the organic components contained in the platinum slurry, it was heated at 1000°C for 1 hour using an electric furnace.

[0591] Fig.48 Test Example 18: Ba5Nd2Al2SnO 13

[0592] Fig.49Test Example 19: Ba5Sm2Al2SnO 13

[0593] Fig.50 Test Example 20: Ba5Gd2Al2SnO 13

[0594] Fig.51 Test Example 21: Ba5Dy2Al2SnO 13

[0595] Fig.52 Test Example 22: Ba5Ho2Al2SnO 13

[0596] Fig.53 Test Example 23: Ba5Er2Al2SnO 13

[0597] Fig.54 Test Example 24: Ba5Tm2Al2SnO 13

[0598] Fig.55 Test Example 25: Ba5Yb2Al2SnO 13

[0599] Fig.56 Test Example 26: Ba5Y2Al2SnO 13

[0600] Fig.57 Test Example 27: Ba5Eu2Al2SnO 13 Each atmosphere condition is shown in its own figure.

[0601] Fig.58 A graph showing a summary of the electrical conductivities of Test Examples 18 to 27 is shown.

[0602] In any test example, as a benchmark, at 1000 / T(K -1 )=1.2 and 1log[σ(Scm -1 )] is about -3, and it is expected to be used in proton conductive solid electrolytes with high practicality.

[0603] [Structural optimization calculation]

[0604] The structure optimization calculation was carried out based on density functional theory, and the lattice constant obtained by the structure optimization was obtained.

[0605] Density functional theory calculations using the generalized gradient approximation and the PBE functional were performed using the program VASP. Tables 1 and 2 show the results of the lattice constants.

[0606] The structures in which any of the compositions are optimized all maintain the crystal structure of the compound of the present embodiment, indicating the possibility that these compositions can be synthesized. It is believed that these compounds also exhibit proton conduction.

[0607] [Test Example 28: BaSc 0.775 Mo 0.225 O 3-δ Synthesis and analysis of

[0608] As the general formula Ba 1-α Sc 1-x Mo x O 3-δ H y The compounds shown in the examples were subjected to the same BaSc 0.775 Mo 0.225 O 3-δ synthesis.

[0609] Fig.59 Test Example 28: BaSc 0.775 Mo 0.225 O 3-δ The results of XRD measurement.

[0610] The electrical conductivity of the compound of Test Example 28 obtained was measured in the same manner as in Test Examples 1 to 17.

[0611] Fig.60 Test Example 28: BaSc 0.775 Mo 0.225 O 3-δ The volume conductivity is measured by cooling in humid air (water vapor partial pressure: 18°C, 0.02 atm) and maintaining the temperature.

[0612] [Test Example 29: BaSc 0.725 Mo 0.275 O 3-δ Synthesis and analysis of

[0613] As the general formula: Ba 1-α Sc 1-x Mo x O 3-δ H y The compounds shown in the examples were subjected to the same BaSc 0.725 Mo 0.275 O 3-δ synthesis.

[0614] Fig.61 Test Example 29: BaSc 0.725 Mo 0.275 O 3-δ The results of XRD measurement.

[0615] The electrical conductivity of the compound of Test Example 29 obtained was measured in the same manner as in Test Examples 1 to 17.

[0616] Fig.62 Test Example 29: BaSc 0.725 Mo 0.275 O 3-δ The volume conductivity is measured by cooling in humid air (water vapor partial pressure: 18°C, 0.02 atm) and maintaining the temperature.

[0617] [Test Example 30: BaSc 0.7 W 0.3 O 3-δ Synthesis and analysis of

[0618] As the general formula: BaSc 1-x W x O 3-δ H y The compounds shown in the examples were subjected to the same BaSc 0.7 W 0.3 O 3-δ synthesis.

[0619] Fig.63 Test Example 30: BaSc 0.7 W 0.3 O 3-δ The results of XRD measurement.

[0620] [Test Example 31: BaSc 0.75 W 0.25 O 3-δ Synthesis and analysis of

[0621] As the general formula: BaSc 1-x W x O 3-δ H y The compounds shown in the examples were subjected to the same BaSc 0.75 W 0.25 O 3-δ synthesis.

[0622] Fig.64 Test Example 31: BaSc 0.75 W 0.25 O 3-δ The results of XRD measurement.

[0623] The electrical conductivity of the compound of Test Example 31 thus obtained was measured in the same manner as in Test Examples 1 to 17.

[0624] Fig.65 Test Example 31: BaSc 0.75 W 0.25 O 3-δ The DC total conductivity is measured by cooling in humid air (water vapor partial pressure: 18°C, 0.02 atm) and maintaining the temperature.

[0625] [Test Example 32: BaSc 0.8 W 0.2 O 3-δ Synthesis and analysis of

[0626] As the general formula: BaSc 1-x W x O 3-δ H y The compounds shown in the examples were subjected to the same BaSc 0.8 W 0.2 O 3-δ Synthesis (same as in Test Example 15, but synthesis and measurement were performed again).

[0627] Fig.66 Test Example 32: BaSc 0.8 W 0.2 O 3-δ The results of XRD measurement.

[0628] The electrical conductivity of the compound of Test Example 32 thus obtained was measured in the same manner as in Test Examples 1 to 17.

[0629] Fig.67 Test Example 32: BaSc 0.8 W 0.2 O 3-δ The DC total conductivity is measured by cooling in humid air (water vapor partial pressure: 18°C, 0.02 atm) and maintaining the temperature.

[0630] [Analysis of the Compound of Test Example 23]

[0631] Test Example 23: About Ba5Er2Al2SnO 13 The compounds were further analyzed.

[0632] Fig.68 It represents Test Example 23: Ba5Er2Al2SnO 13A graph comparing the conductivity of the conventional material at each temperature. The figure is a comparison of bulk (intra-particle) conductivity, and the dotted line represents the Norby gap.

[0633] As shown in the figure, the compound of Test Example 23 is better than the conventional materials Y10: BC and Y20: BZ (BaZr) at any temperature between 200 and 350 degrees. 0.8 Y 0.2 O 3-δ ) has high bulk conductivity.

[0634] Fig.69 About Test Example 23: Ba5Er2Al2SnO 13 , a graph showing the oxygen partial pressure dependence of the DC total conductivity in a dry atmosphere and a wet atmosphere at various temperatures.

[0635] As shown in the figure, the electrolyte range that is independent of the oxygen partial pressure P(O2) suggests ion conduction. Since the conductivity in a humid atmosphere is higher than that in a dry atmosphere, proton conduction is suggested.

[0636] Fig.70 About Test Example 23: Ba5Er2Al2SnO 13 , a graph showing the time dependence of the electrical conductivity of each gas atmosphere.

[0637] As shown in the figure, the conductivity in the H2O atmosphere is about 1.5 times higher than that in the D2O atmosphere, thus suggesting proton conduction.

[0638] Fig.71 It represents Test Example 23: Ba5Er2Al2SnO 13 Thermogravimetric analysis results of .

[0639] The vertical axis of the graph represents the water absorption x of the sample. In the graph, x increases with cooling.

[0640] Based on these results, it can be said that Test Example 23 is an expected new substance.

[0641] [Test Examples 33 to 35: Ba 5-α R 2+x Al 2+y M 1+z O 13+δ Synthesis and analysis of compounds]

[0642] Synthesis belongs to Ba 5-α R 2+x Al 2+y M 1+z O 13+δ The compounds were analyzed.

[0643] Test Example 33: Ba5Er2Al2Sn 0.5 Zr 0.5 O 13

[0644] Test Example 34: Ba5Er 1.9 Al 2.1 SnO 13

[0645] Test Example 35: Ba5Er2Al 2.1 Sn 0.9 O 12.95

[0646] The synthesis was performed in the same manner as in the above-mentioned Test Example 23. The XRD measurement was performed in the same manner as in the above-mentioned Test Example 23.

[0647] Fig.72 Test Example 33: Ba5Er2Al2Sn 0.5 Zr 0.5 O 13 The results of XRD measurement.

[0648] Fig.73 Test Example 33: Ba5Er2Al2Sn 0.5 Zr 0.5 O 13 The DC total conductivity is measured by cooling in humid air (water vapor partial pressure: 18°C, 0.02 atm) and maintaining the temperature.

[0649] Fig.74 Test Example 34: Ba5Er 1.9 Al 2.1 SnO 13 The results of XRD measurement.

[0650] Fig.75 Test Example 35: Ba5Er2Al 2.1 Sn 0.9 O 12.95 The results of XRD measurement.

[0651] These compounds can also be expected to be applicable to electrolytes and batteries that are useful in the same way as in Test Example 23.

[0652] Industrial Applicability

[0653] According to the proton conductive solid electrolyte, electrolyte layer and battery of the present invention, a proton conductive solid electrolyte capable of exhibiting high proton conductivity and stability in low and medium temperature ranges, an electrolyte layer and a battery using the proton conductive solid electrolyte can be obtained.

[0654] The proton conductive solid electrolyte, electrolyte layer and battery of the present invention can also be applied to solid oxide fuel cells (SOFCs), proton ceramic fuel cells (PCFCs), sensors, batteries, electrodes, electrolytes, hydrogen permeable membranes, catalysts, photocatalysts, electrical / electronic / communication equipment, energy / environment-related equipment or optical equipment, etc.

Claims

1. A proton-conductive solid electrolyte, (1) According to the general formula: Ba 1-α Sc 1-x Mo x O 3-δ H y It means that α is -0.2~0.2, x is 0.1~0.3, y is 0~1-3x, and δ is 0~1 / 2-3x / 2.

2. A proton-conductive solid electrolyte, By the general formula: BaA 1-x M x O 3-δ H y Indicates that A is the ionic radius of all ions except Ce, In, Zr and Zn. M is an element other than A, Zr, Ce and Zn whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A and Zn whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1, Wherein, for M=Ge, Sn, Hf, x is greater than 0 and less than 0.95, When M is a mixed element containing any one of Cr, Fe, Mn, Co, Ni and Ti, the ratio of Cr, Fe, Mn, Co or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1, y is 0~1, and δ is 0~1 / 2.

3. The proton conductive solid electrolyte according to claim 2, wherein: A is Sc, M is Mo, Ge, Nb, Ta, V, W or Sb, When M is Mo or W, x is greater than 0 and less than 1 / 3; when M is Ge, x is greater than 0 and less than 1 / 2; when M is Nb, Ta, V or Sb, x is greater than 0 and less than 1 / 2.

4. The proton conductive solid electrolyte according to claim 2 or 3, The proton conductive solid electrolyte is any one of the following (2) to (8): (2) From the general formula: BaSc 1-x Ge x O 3-δ H y It means that x is 0.25 to 0.35, y is 0 to 1-x, and δ is 0 to 1 / 2-x / 2; (3) From the general formula: BaSc 1-x Nb x O 3-δ H y It means that x is 0.2 to 0.4, y is 0 to 1-2x, and δ is 0 to 1 / 2-x; (4) From the general formula: BaSc 1-x Ta x O 3-δ H y It means that x is 0.2 to 0.4, y is 0 to 1-2x, and δ is 0 to 1 / 2-x; (5) From the general formula: BaSc 1-x V x O 3-δ H y Indicates that x is 0.2 to 0.25, y is 0 to 1-2x, and δ is 0 to 1 / 2-x; (6) From the general formula: BaSc 1-x W x O 3-δ H y It means that x is 0.15 to 0.25, y is 0 to 1-3x, and δ is 0 to 1 / 2-3x / 2; (7) From the general formula: BaSc 0.6 Ce 0.4 O 3-δ express; (8) From the general formula: BaSc 1-x Sb x O 3-δ H y Indicates that x is 0.35 to 0.45, y is 0 to 1-2x, δ is 0~1 / 2-x.

5. A proton-conductive solid electrolyte, By the general formula: BaSc 1-x M x O 3-δ H y represents, M represents a mixed composition of multiple elements other than Sc, Zr, Ce and Zn, the average ion radius of M is 70 to 130% of the ion radius of Sc, x is greater than 0 and less than 1, Wherein, for M=Ge, Sn, Hf, x is greater than 0 and less than 0.95, When M is a mixed element containing any one of Cr, Fe, Mn, Co, Ni and Ti, the ratio of Cr, Fe, Mn, Co or Ni in M ​​is greater than 0.2 and less than 1, or x is greater than 0.2 and less than 1, y is 0~1, and δ is 0~1 / 2.

6. A proton-conductive solid electrolyte, By the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y express, M is Mo, Ge, Nb, Ta, V, W or Sb, y is 0 to 1, ε is 0 to 0.7, δ is 0 to 1 / 2, In the case where M is Ge, x is greater than 0 and less than 1 / 2, When M is Nb, Ta, V or Sb, x is greater than 0 and less than 1 / 2, When M is Mo or W, x is greater than 0 and less than 1 / 3.

7. A proton conductive solid electrolyte, By the general formula: Ba 1-ε Sc 1-x Ce x O 3-δ H y It means that x is greater than 0 and less than 1, y is 0 to 1, and ε is greater than 0.05 to 0.

7. In the formula, when 0.05<ε<0.2, 0<x<0.5, and δ is 0 to 1 / 2.

8. A proton conductive solid electrolyte, By the general formula: Ba 1-ε Sc 1-x M x O 3-δ H y It indicates that M is an element other than Sc and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or M is a mixed composition of multiple elements other than Sc and Zn, whose average ionic radius is 70 to 130% of the ionic radius of Sc, and x is greater than 0 and less than 1, In the formula, for M=Ti, when ε=0, x is greater than 0 and less than 0.2, For M=Ge, Sn, Hf, x is greater than 0 and less than 0.95, For M=Zr, Ce, ε is greater than 0.05, When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

9. A proton conductive solid electrolyte, By the general formula: Ba 1-ε A 1-x M x O 3-δ H y Indicates that A is the ionic radius of all ions except Ce, In, Zr and Zn. M is an element other than A and Zn whose ionic radius is 70 to 130% of the ionic radius of A, or a mixed composition of multiple elements other than A whose average ionic radius is 70 to 130% of the ionic radius of A, x is greater than 0 and less than 1, Wherein, for M=Ge, Sn, Hf, x is greater than 0 and less than 0.95, For M=Zr, Ce, ε is greater than 0.05, When M is a mixed element containing any one of Ti, Zr, Ce and any one of Cr, Fe, Mn, Co, and Ni, the ratio of Cr, Fe, Mn, Co, or Ni in M ​​is greater than 0.2 and less than 1, ε is greater than 0.2, or x is greater than 0.2 and less than 1, y is 0 to 1, ε is 0 to 0.7, and δ is 0 to 1 / 2.

10. A proton conductive solid electrolyte, By the general formula: BaA 1-x-z M1 x M2 z O 3-δ H y express, z is greater than 0 and less than 1, y is 0 to 1, δ is 0 to 1 / 2, Any one of the following (28) to (35): (28) From the general formula: BaSc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, Mo and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Mo and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (29) From the general formula: BaSc 1-x-z Ge x M z O 3-δ H y It indicates that x is greater than 0 and less than 1, and M is an element other than Sc, Ge and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Ge and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc; (30) From the general formula: BaSc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Nb and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Nb and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (31) From the general formula: BaSc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Ta and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Ta and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (32) From the general formula: BaSc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, V and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, V and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (33) From the general formula: BaSc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, W and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, W and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (34) From the general formula: BaSc 1-x-z Ce x M z O 3-δ H y It means that x is greater than 0 and less than 1, and M is an element other than Sc, Ce, Zr and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ce and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, when z=0, x is greater than 0 and less than 0.

2. For M=Cr, Fe, Mn, Co or Ni, the range of x=0.01 to 0.02 is excluded, and for M=Mo, Nb, Ta, V, W or Sb, the range of z=0.01 to 0.2 or x=0.74 to 0.84 is excluded; (35) From the general formula: BaSc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Sb and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Sb and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein for M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded).

11. A proton conductive solid electrolyte, By the general formula: Ba 1-ε A 1-x-z M1 x M2 z O 3-δ H y express, z is greater than 0 and less than 1, y is 0 to 1, ε is 0 to 0.7, δ is 0 to 1 / 2, Any one of the following (36) to (43): (36) According to the general formula: Ba 1-ε Sc 1-x-z Mo x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, Mo and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Mo and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (37) According to the general formula: Ba 1-ε Sc 1-x-z Ge x M z O 3-δ H y It indicates that x is greater than 0 and less than 1, and M is an element other than Sc, Ge and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Ge and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc; (38) According to the general formula: Ba 1-ε Sc 1-x-z Nb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Nb and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Nb and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (39) According to the general formula: Ba 1-ε Sc 1-x-z Ta x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, Ta and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Ta and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (40) According to the general formula: Ba 1-ε Sc 1-x-z V x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, and M is an element other than Sc, V and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, V and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (41) According to the general formula: Ba 1-ε Sc 1-x-z W x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 3, and M is an element other than Sc, W and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, W and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, with respect to M=Ce, the range of x=0.01 to 0.2 or z=0.74 to 0.84 is excluded; (42) According to the general formula: Ba 1-ε Sc 1-x-z Ce x M z O 3-δ H y It represents that x is greater than 0 and less than 0.8, M is an element other than Sc, Ce and Zn and excluding Zr when ε=0, whose ionic radius is 70-130% of the ionic radius of Sc, or a mixed composition of multiple elements other than Sc, Ce and Zn, whose average ionic radius is 70-130% of the ionic radius of Sc, wherein for M=Cr, Fe, Mn, Co or Ni, ε=0-0.2 or x=0.01-0.02 is excluded, and for M=Mo, Nb, Ta, V, W or Sb, z=0.01-0.2 or x=0.74-0.84 is excluded; (43) According to the general formula: Ba 1-ε Sc 1-x-z Sb x M z O 3-δ H y It means that x is greater than 0 and less than 1 / 2, M is an element other than Sc, Sb and Zn whose ionic radius is 70 to 130% of the ionic radius of Sc or a mixed composition of multiple elements other than Sc, Sb and Zn whose average ionic radius is 70 to 130% of the ionic radius of Sc, wherein, about M=Ce, The ranges of x=0.01 to 0.2 or z=0.74 to 0.84 are excluded.

12. A proton conductive solid electrolyte, By the general formula: Ba 5-α R 2+x Al 2+y M 1+z O 13+δ express, α is greater than or equal to 0 and less than or equal to 2, x is greater than or equal to -1 and less than or equal to 1, y is greater than or equal to -1 and less than or equal to 1, z is greater than or equal to -0.5 and less than or equal to 0.5, δ is greater than or equal to -1 and less than or equal to 1, In the general formula, R is a cation of an element selected from the group consisting of rare earth elements and Ga, and M is a cation of an element selected from the group consisting of Hf, Sn, and Zr.

13. The proton conductive solid electrolyte according to claim 12, The proton conductive solid electrolyte has the general formula: Ba5R2Al2MO 13 It indicates that M is a cation of one element selected from the group consisting of Hf and Sn.

14. The proton conductive solid electrolyte according to claim 12 or 13, wherein In the general formula, M is Sn, and R is Nd, Sm, Eu, Gd, Dy, Ho, Y, Er, Tm or Yb. 15 . The proton conductive solid electrolyte according to claim 1 , which is used under a temperature condition of 100 to 700° C. 16 . The proton conductive solid electrolyte according to claim 1 , which is used under a temperature condition of 200 to 400° C.

17. The proton conductive solid electrolyte according to any one of claims 1, 2, 5 to 12, wherein when the proton conductivity in the particle is measured, log[σ(Scm -1 )] indicates that the temperature at which the conductivity is greater than -2.0 is below 350°C.

18. The proton conductive solid electrolyte according to any one of claims 1, 2, 5 to 12, wherein the proton conductive solid electrolyte is used in a solid oxide fuel cell SOFC, a proton ceramic fuel cell PCFC, a sensor, a battery, an electrode, an electrolyte, a hydrogen permeable membrane, a catalyst, a photocatalyst, an electrical device, an electronic device, a communication device, an energy-related device, an environment-related device or an optical device.

19. The proton conductive solid electrolyte according to any one of claims 1, 2, and 5 to 12, which is used for a solid oxide fuel cell SOFC, a proton ceramic fuel cell PCFC, a sensor, or a hydrogen permeable membrane.

20. An electrolyte layer, A proton conductive solid electrolyte comprising any one of claims 1, 2, and 5 to 12.

21. A battery, A method of manufacturing the electrolyte layer according to claim 20.

22. The battery according to claim 21, The battery is a solid oxide fuel cell SOFC or a proton ceramic fuel cell PCFC.

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