ION-CONDUCTIVE SOLID STATE AND SOLID-STATE BATTERY

Abstract

The present invention provides an ion-conductive solid containing an oxide represented by the formula Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9(In the formula, X represents at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm; M1 represents at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr, and Ba; M2 represents at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe, and Sc; M3 represents at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn, and Ti; M4 represents at least one metal element selected from the group consisting of Nb and Ta; a, b, c, and d are specific real numbers; and the cases where X and M2 represent the same metal element are excluded.)

Description

[Technical area]

[0001] The present disclosure relates to an ion-conductive solid state and a solid state battery. [Technical background]

[0002] Conventionally, lightweight and high-capacity lithium-ion secondary batteries have been included in mobile devices such as smartphones and notebooks, as well as in transportation devices such as electric vehicles and hybrid electric vehicles.

[0003] However, because conventional lithium-ion secondary batteries used liquids containing flammable solvents as electrolytes, there were concerns about the leakage of the flammable solvents and ignition in the event of a battery short circuit. Therefore, in recent years, attention has been turned to secondary batteries that use ion-conductive solids as electrolytes, which are different from liquid electrolytes, to ensure safety. Such secondary batteries have been called all-solid-state batteries.

[0004] Solid electrolytes such as oxide-based solid electrolytes and sulfide-based solid electrolytes are widely known as electrolytes for all-solid-state batteries. Among them, oxide-based solid electrolytes do not react with atmospheric moisture and do not generate hydrogen sulfide. Therefore, oxide-based solid electrolytes are safer than sulfide-based solid electrolytes.

[0005] Such an all-solid-state battery includes: a cathode comprising a cathode active material; an anode comprising an anode active material; an electrolyte disposed between the cathode and the anode and comprising an ion-conductive solid; and, if necessary, a current collector (the cathode active material and the anode active material are collectively referred to as "electrode active material"). In a case where the all-solid-state battery is manufactured using an oxide-based solid electrolyte, heat treatment is performed to reduce the contact resistance between the particles of an oxide-based material included in the solid electrolyte. However, with a conventional oxide-based solid electrolyte, a high temperature of 900°C or more is required for the heat treatment, and therefore the solid electrolyte and the electrode active material may react to form a high-resistance phase.The high-resistance phase can lead to a decrease in the ionic conductivity of the ion-conductive solid and thus to a reduction in the performance of the solid-state battery.

[0006] Examples of oxide-based solid electrolytes that can be prepared by heat treatment at a temperature below 900°C include Li 2+x C 1-x B x O 3 (Non-Patent Document 1).

[0007] Furthermore, it is disclosed that the properties can be improved by using the above-described Li 2+x C 1-x B x O 3 contain a specific element in a specific ratio (Patent Document 1). [Citation list][Non-patent document] [Non-Patent Document 1] Solid State Ionic 288 (2016) 248-252 [Non-Patent Document 2] Acta Crystallographica Section A 32 (1976) 751 [Patent document]

[0008] [Patent Document 1] Japanese Patent No. 6948676 [Summary of the invention][Technical problem]

[0009] The present disclosure provides: an ion-conductive solid that can be produced by low-temperature heat treatment and has high ionic conductivity; and a solid-state battery comprising the ion-conductive solid. [Solution to the problem]

[0010] An ionically conductive solid of the present disclosure is an ionically conductive solid comprising an oxide represented by a general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 (in the formula, X is at least one metal element selected from the group consisting of Lu, Ho, Er and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn and Ti, M4 is at least one metal element selected from the group consisting of Nb and Ta, and a is 0.000 ≤ a ≤ 0.800, b is 0.000 ≤ b ≤ 0.900, c is 0.000 ≤ c ≤ 0.800, d is 0.000 ≤ d ≤ 0.800, and a, b, c and d are real numbers satisfying 0.000 ≤ a + b + c + d < 1.000, provided that a case where X and M2 are the same metal elements is excluded).

[0011] A solid-state battery according to the present disclosure is a solid-state battery comprising at least: a cathode; an anode; and an electrolyte, wherein at least one selected from the group consisting of the cathode, the anode, and the electrolyte comprises the ion-conductive solid of the present disclosure. [Advantageous effects of the invention]

[0012] According to one aspect of the present disclosure, there can be obtained: an ion-conductive solid that can be produced by low-temperature heat treatment and has high ionic conductivity; and an all-solid-state battery comprising the ion-conductive solid. [Description of the embodiments]

[0013] In the present disclosure, the description "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range that includes lower and upper limits, which are endpoints, unless otherwise specified. When describing numerical ranges incrementally, the upper and lower limits of each numerical range may optionally be combined.

[0014] In this disclosure, the term "solid" refers to the state of matter that has a specific shape and volume, in the three states of matter. A powdery state is included in "solid."

[0015] An ionically conductive solid of the present disclosure is an ionically conductive solid comprising an oxide represented by a general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 .

[0016] In the formula, X is at least one metal element selected from the group consisting of Lu, Ho, Er and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn and Ti, M4 is at least one metal element selected from the group consisting of Nb and Ta, and a is 0.000 ≤ a ≤ 0.800, b is 0.000 ≤ b ≤ 0.900, c is 0.000 ≤ c ≤ 0.800, d is 0.000 ≤ d ≤ 0.800, and a, b, c and d are real numbers satisfying 0.000 ≤ a + b + c + d < 1.000, provided that a case where X and M2 are the same metal elements is excluded.

[0017] “A case where X and M2 are the same metal elements is excluded” refers to a case wherein, when X is Lu, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, In, Fe and Sc, wherein, when X is Ho, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Lu, In, Fe and Sc, wherein, when X is Er, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Lu, In, Fe and Sc, or wherein, when X is Tm, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Lu, In, Fe and Sc.

[0018] The reason why the ion-conductive solid having the oxide represented by the above general formula is improved in its ion conductivity is presumed by the present inventors as follows.

[0019] The substitution of Y in Li 6 YB 3 O 9 , which is shown in Comparative Example 1 in Patent Document 1, by at least one element selected from the group consisting of Lu, Ho, Er, and Tm, which are metal elements with smaller ionic radii than Y, leads to a reduction in the lattice constant and the lattice volume. As a result, Li + move easily, and therefore the ionic conductivity is improved.

[0020] In Patent Document 1, Y, which is a trivalent metal element, is partially substituted by a quadrivalent to pentavalent metal element, that is, the substitution between elements different in valence provides adjustment of charge balance and improvement of ion-conductive properties.

[0021] The use of a metal element with a suitable ionic radius as metal element X instead of Y leads to a reduction in the lattice constant and lattice volume. As a result, Li + move more easily, further improving ionic conductivity. Furthermore, combined use with substitution between elements of different valences also corresponds to a preferred aspect.

[0022] X preferably has an ionic radius of 0.900 to 1.017 Å, more preferably 0.920 to 1.015 Å, even more preferably 0.940 to 1.015 Å, and most preferably 0.975 to 1.015 Å. The range described above leads to a reduction in the lattice constant and the lattice volume. As a result, Li + move easily, thereby improving ionic conductivity. An ionic radius of less than 0.900 Å cannot provide an objective monoclinic structure, so an ionically conductive solid cannot be achieved.

[0023] The values ​​for the ionic radii can be those described in Non-Patent Document 2. For example, the ionic radius of Y 3+ 1.019 Å, the ionic radius of Lu 3+ is 0.977 Å, the ionic radius of Ho 3+ is 1.015 Å, the ionic radius of Er 3+ is 1.004 Å and the ionic radius of Tm 3+ is 0.994 Å.

[0024] The ion-conductive solid of the present disclosure preferably includes a monoclinic crystal structure.

[0025] The ion-conductive solid of the present disclosure preferably has a volume-average particle diameter of 0.1 µm or more and 28.0 µm or less, more preferably 0.2 µm or more and 26.0 µm or less, even more preferably 0.3 µm or more and 20.0 µm or less, even more preferably 0.3 µm or more and 15.0 µm or less, and even more preferably 0.5 µm or more and 10.0 µm or less. The above-described range leads to a reduction in grain boundary resistance in an ion-conductive solid and a further improvement in ionic conductivity.

[0026] The volume-average particle diameter of the ion-conductive solid can be controlled by pulverization or classification.

[0027] In the general formula above, a is a real number satisfying 0.000 ≤ a ≤ 0.800. a is 0.000 ≤ a ≤ 0.800, preferably 0.000 ≤ a ≤ 0.600, more preferably 0.000 ≤ a ≤ 0.400, even more preferably 0.000 ≤ a ≤ 0.100, particularly preferably 0.000 ≤ a ≤ 0.050, and most preferably 0.000 ≤ a ≤ 0.030.

[0028] In the general formula above, b is a real number satisfying 0.000 ≤ b ≤ 0.900. b is 0.000 ≤ b ≤ 0.900, preferably 0.000 ≤ b ≤ 0.600, more preferably 0.000 ≤ b ≤ 0.500, even more preferably 0.000 ≤ b ≤ 0.400, even more preferably 0.000 ≤ b ≤ 0.100, particularly preferably 0.000 ≤ b ≤ 0.050, and most preferably 0.000 ≤ b ≤ 0.030.

[0029] In the general formula above, c is a real number satisfying 0.000 ≤ c ≤ 0.800. c is 0.000 ≤ c ≤ 0.800, preferably 0.000 ≤ c ≤ 0.600, more preferably 0.000 ≤ c ≤ 0.400, even more preferably 0.000 ≤ c ≤ 0.150, even more preferably 0.000 ≤ c ≤ 0.100, particularly preferably 0.000 ≤ c ≤ 0.050, and most preferably 0.000 ≤ c ≤ 0.030. c can preferably be 0.050 ≤ c ≤ 0.200, more preferably 0.080 ≤ c ≤ 0.150.

[0030] In the general formula above, d is a real number satisfying 0.000 ≤ d ≤ 0.800. d is 0.000 ≤ d ≤ 0.800, preferably 0.000 ≤ d ≤ 0.600, more preferably 0.000 ≤ d ≤ 0.400, even more preferably 0.000 ≤ d ≤ 0.100, particularly preferably 0.000 ≤ d ≤ 0.050, and most preferably 0.010 ≤ d ≤ 0.030.

[0031] In the general formula above, a + b + c + d is a real number satisfying 0.000 ≤ a + b + c + d < 1.000. a + b + c + d is 0.000 ≤ a + b + c + d < 1.000, preferably 0.000 ≤ a + b + c + d < 0.900, more preferably 0.000 ≤ a + b + c + d < 0.800, even more preferably 0.000 ≤ a + b + c + d < 0.700, even more preferably 0.000 ≤ a + b + c + d ≤ 0.600, particularly preferably 0.010 ≤ a + b + c + d < 0.500, particularly preferably 0.050 ≤ a + b + c + d < 0.300, and most preferably 0.080 ≤ a + b + c + d < 0.250.

[0032] In X 1-a-b-c-d The 1-abcd is preferably 0.300 ≤ 1-abcd, more preferably 0.500 ≤ 1-abcd, even more preferably 0.700 ≤ 1-abcd, and even more preferably 0.750 ≤ 1-abcd. The upper limit is not particularly limited and is preferably less than 1.000, 0.950 or less, or 0.900 or less. Examples preferably include ranges of 0.300 ≤ 1-abcd < 1.000, 0.500 ≤ 1-abcd ≤ 0.950, and 0.700 ≤ 1-abcd ≤ 0.900.

[0033] The ion-conductive solid of the present disclosure may have, for example, the following embodiments, but is not limited to the embodiments.

[0034] (1) It is allowed that a is 0.010 ≤ a ≤ 0.100, b is 0.000 ≤ b ≤ 0.200, c is 0.000 ≤ c ≤ 0.200, d is 0.010 ≤ d ≤ 0.100, and a, b, c and d satisfy 0.010 ≤ a + b + c + d < 0.300.

[0035] (2) It is allowed that a is 0.010 ≤ a ≤ 0.030, b is 0.030 ≤ b ≤ 0.100, c is 0.010 ≤ c ≤ 0.030, d is 0.010 ≤ d ≤ 0.030, and a, b, c and d satisfy 0.050 ≤ a + b + c + d < 0.160.

[0036] (3) It is allowed that a is 0.000 ≤ a ≤ 0.010, b is 0.000 ≤ b ≤ 0.100, c is 0.050 ≤ c ≤ 0.150, d is 0.000 ≤ d ≤ 0.030, and a, b, c and d satisfy 0.050 ≤ a + b + c + d < 0.250.

[0037] M1, M2, M3, and M4 in the above general formula are optional. In other words, at least one of a, b, c, and d can be zero.

[0038] In the above general formula, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba.

[0039] M1 is at least one selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba, preferably at least one selected from the group consisting of Mg, Zn, Ca, Sr and Ba, and more preferably at least one selected from the group consisting of Mg, Ca and Sr.

[0040] In the above general formula, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc.

[0041] M2 is at least one selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc, preferably at least one selected from the group consisting of La, Eu, Gd, Tb, Dy, Lu, In and Fe, and more preferably at least one selected from the group consisting of Gd, Dy, Lu, In and Fe. M2 may be at least one selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, In, Fe and Sc.

[0042] In the above general formula, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn and Ti.

[0043] M3 is at least one selected from the group consisting of Zr, Ce, Hf, Sn and Ti, preferably at least one selected from the group consisting of Zr, Ce, Hf and Sn, and more preferably at least one selected from the group consisting of Zr, Ce and Hf.

[0044] In the above general formula, M4 is at least one metal element selected from the group consisting of Nb and Ta.

[0045] M4 is at least one selected from the group consisting of Nb and Ta, and preferably Nb.

[0046] Furthermore, the substitution of some of the elements X, which are trivalent metal elements, by using specific elements M1, M2, M3, and M4 in the specific rate ranges leads to an adjustment of the charge balance by substitution between elements with different valences. This creates a state in which Li + is deficient in the crystal lattice. Li + , which is located near a place where Li + missing, moves to fill this spot, thereby improving ionic conductivity.

[0047] A method for producing the ion-conductive solid of the present disclosure is described below.

[0048] The method for producing the ion-conductive solid of the present disclosure may be the following aspect, but is not limited thereto.

[0049] A method for producing an ion-conductive solid containing an oxide represented by a general formula Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 is shown, where the method may include: a primary firing step of heat treating raw materials mixed to obtain the oxide represented by the general formula at a temperature below the melting point of the oxide.

[0050] In the formula, X is at least one metal element selected from the group consisting of Lu, Ho, Er and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn and Ti, M4 is at least one metal element selected from the group consisting of Nb and Ta, and a is 0.000 ≤ a ≤ 0.800, b is 0.000 ≤ b ≤ 0.900, c is 0.000 ≤ c ≤ 0.800, d is 0.000 ≤ d ≤ 0.800, and a, b, c and d are real numbers satisfying 0.000 ≤ a + b + c + d < 1.000, provided that a case where X and M2 are the same metal elements is excluded.

[0051] The method for producing the ion-conductive solid of the present disclosure may include the primary firing step of weighing and mixing the raw materials to obtain the oxide represented by the above general formula, heat-treating the raw materials at a temperature lower than the melting point of the oxide, and thereby producing the ion-conductive solid including the oxide. The ion-conductive solid may be obtained through the primary firing step.

[0052] The method may further include, if necessary, a secondary firing step in which the ion-conductive solid containing the obtained oxide is heat-treated at a temperature below the melting point of the oxide and a sintered body of the ion-conductive solid containing the oxide is produced.

[0053] The method for producing the ion-conductive solid of the present disclosure, which includes the above-described primary firing step and the above-described secondary firing step, will be described in detail below. However, the present disclosure is not limited to the following method. Primary firing step

[0054] In the primary firing step, raw materials such as Li 2 CO 3 , H 3 BO 3 , Ho 2 O 3 , ZrO 2 , CEO 2 or HfO 2 of chemical reagent grade in stoichiometric amounts and mixed to obtain a general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 (wherein X is at least one metal element selected from the group consisting of Lu, Ho, Er and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn and Ti, M4 is at least one metal element selected from the group consisting of Nb and Ta, and a is 0.000 ≤ a ≤ 0.800, b is 0.000 ≤ b ≤ 0.900, c is 0.000 ≤ c ≤ 0.800, d is 0.000 ≤ d ≤ 0.800, and a, b, c and d are real numbers satisfying 0.000 ≤ a + b + c + d < 1.000, provided that a case where X and M2 are the same metal elements is excluded).

[0055] The equipment used for mixing is not particularly limited. For example, a pulverization-type mixer such as a planetary ball mill can be used as the equipment. The material and capacity of a container used in mixing, as well as the material and diameter of the ball, are not particularly limited and can be selected according to the type and quantity of raw materials used. For example, a 45 mL container made of zirconia and a 5 mm diameter ball made of zirconia can be used. In addition, the mixing treatment conditions are not particularly limited, but can be set to a speed of 50 to 2000 rpm and a time of 10 to 60 minutes, for example.

[0056] The powder mixture of each of the raw materials described above is obtained through the mixing treatment. The resulting powder mixture is then molded under pressure to produce pellets. As the pressure molding method, a known pressure molding method such as a cold uniaxial molding method or a cold isostatic pressure molding method can be used. The pressure molding condition in the primary firing step is not particularly limited, but can be set to a pressure of, for example, 100 MPa to 200 MPa.

[0057] The resulting pellets are fired using a device such as an atmospheric furnace. The temperature at which the primary firing and solid-phase synthesis are carried out is not particularly limited, as long as the temperature is below the melting point of the ion-conductive solid, which is represented by the general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4d B 3 O 9 . A temperature at which the primary firing is performed can be set, for example, to less than 700°C, 680°C or less, 670°C or less, 660°C or less, or 650°C or less, and, for example, to 500°C or more. The numerical ranges can be optionally combined. The temperature in such a range as described above sufficiently enables solid-phase synthesis. The duration of the primary firing step is not particularly limited, but can be set, for example, to about 700 to 750 minutes.

[0058] The primary firing step described above enables the production of the ion-conductive solid containing the oxide represented by the general formula above: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9. The powder of the ion-conductive solid containing the oxide can also be obtained by pulverizing the ion-conductive solid containing the oxide with a mortar / pepper or a planetary mill. Secondary firing step

[0059] In the secondary firing step, the sintered body of the ion-conductive solid containing the oxide is obtained by optionally pressure-molding and firing at least one selected from the group consisting of the ion-conductive solid containing the oxide obtained in the primary firing step and the powder of the ion-conductive solid containing the oxide.

[0060] It is acceptable to simultaneously perform compression molding and secondary firing using discharge plasma sintering (hereinafter also referred to simply as "SPS"), hot pressing, or the like, or it is acceptable to produce pellets by uniaxial cold forming and then perform secondary firing in an ambient atmosphere, an oxidizing atmosphere, a reducing atmosphere, or the like. The conditions described above make it possible to obtain an ion-conductive solid with high ionic conductivity without causing melting by heat treatment. The conditions for compression molding in the secondary firing step are not particularly limited, but can be set to a pressure of, for example, 10 MPa to 100 MPa.

[0061] The temperature at which the secondary firing is carried out is lower than the melting point of the ion-conductive solid, which is represented by the general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9The temperature at which the secondary firing is performed is preferably less than 700°C, more preferably 680°C or less, even more preferably 670°C or less, and particularly preferably 660°C or less. The lower limit of the temperature is not particularly limited. It is preferable to lower the lower limit as much as possible. For example, the lower limit is 500°C or more. The numerical ranges can be optionally combined and set in a range of, for example, 500°C or more and less than 700°C. The above-described range enables the ion-conductive solid of the present disclosure including the oxide to be prevented from melting or decomposing in the secondary firing step, and the sintered body of the ion-conductive solid of the present disclosure including the oxide that has been sufficiently sintered to be obtained.

[0062] The time for the secondary firing step can be changed depending on the temperature or pressure at which the secondary firing step is performed, etc., but is preferably 24 hours or less, and may be set to 14 hours or less. The time for the secondary firing step can be set to, for example, 5 minutes or more, 1 hour or more, and 6 hours or more.

[0063] A method for cooling the sintered body of the ion-conductive solid of the present disclosure including the oxide obtained in the secondary firing step is not particularly limited, but may be subjected to natural radiation cooling (radiation cooling in a furnace), rapid cooling, or cooling slower than natural radiation cooling, or may be maintained at a certain temperature during cooling.

[0064] A solid-state battery of the present disclosure will be described below.

[0065] A solid-state battery typically comprises: a cathode, an anode, an electrolyte disposed between the cathode and the anode and containing an ion-conductive solid, and optionally a current collector.

[0066] The solid-state battery of the present disclosure is a solid-state battery comprising at least: a cathode; an anode; and an electrolyte, wherein at least one selected from the group consisting of the cathode, the anode, and the electrolyte comprises the ion-conductive solid of the present disclosure.

[0067] The all-solid-state battery of the present disclosure may be a bulk-type battery or a thin-film battery. The specific shape of the all-solid-state battery of the present disclosure is not particularly limited, but examples of the shape include coin, button, sheet, and layered shapes.

[0068] The all-solid-state battery of the present disclosure includes the electrolyte. In the all-solid-state battery of the present disclosure, at least the electrolyte preferably includes the ion-conductive solid of the present disclosure.

[0069] The solid electrolyte in the all-solid-state battery of the present disclosure may include the ion-conductive solid of the present disclosure, may include another ion-conductive solid, or may include an ionic liquid or a gel polymer. The other ion-conductive solid is not particularly limited, but may include an ion-conductive solid commonly used in an all-solid-state battery, e.g., LiI, Li 3 PO 4 , Li 7 La 3 Zr 2 O 12 or the like. The content of the ion-conductive solid of the present disclosure in the electrolyte in the all-solid-state battery of the present disclosure is not particularly limited, but is preferably 25 mass% or more, more preferably 50 mass% or more, even more preferably 75 mass% or more, and particularly preferably 100 mass%.

[0070] The all-solid-state battery of the present disclosure includes the cathode. The cathode may include a cathode active material or may include a cathode active material and the ion-conductive solid of the present disclosure. As the cathode active material, a known cathode active material such as a sulfide containing a transition metal element or an oxide containing lithium and a transition metal element can be used without particular limitation. Examples include LiNiVO 4 , LiCoPO 4 , LiCoVO 4 , LiMn 1.6 No 0.4 O 4 , LiMn 2 O 4 , LiCoO 2 , Fe 2 (SO 4 ) 3 , LiFePO 4 , LiNi 1 / 3 Mn 1 / 3 Co 1 / 3 O 2 , LiNi 1 / 2 Mn 1 / 2 O 2 , LiNiO 2 , Li 1-x (Fe,Mn,Co) 1-x O 2 , LiNi 0,8 Co 0,15 Al 0,05 O 2 .

[0071] Furthermore, the cathode may include a binder, an electrically conductive agent, and / or the like. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, and polyvinyl alcohol. Examples of the electrically conductive agent include natural graphite, artificial graphite, acetylene black, and ethylene black.

[0072] The all-solid-state battery of the present disclosure includes the anode. The anode may include the anode active material or may include the anode active material and the ion-conductive solid of the present disclosure. As the anode active material, a known anode active material such as an inorganic compound such as lithium, a lithium alloy, or a tin compound, a carbonaceous material capable of absorbing and releasing lithium ions, or a conductive polymer may be used without particular limitation. Examples include Li 4 Ti 5 O12 .

[0073] Furthermore, the anode may comprise a binder, an electrically conductive agent, and / or the like. Similar binders and electrically conductive agents as used in the cathode may be used as the binder and electrically conductive agent.

[0074] As used herein, the term "electrode having electrode active material" means that an electrode has an electrode active material as a constituent, element, or property. For example, a case where an electrode active material is contained in an electrode and a case where an electrode active material is applied to a surface of an electrode also correspond to the term "having" described above.

[0075] The cathode and the anode can be manufactured by a known method such as mixing, molding, heat treatment, or the like of raw materials. Thus, it is assumed that the ion-conductive solid penetrates into gaps and the like between such electrode active materials to facilitate the safety of a conduction path for lithium ions. It is assumed that the formation of a high-resistance phase resulting from the reaction between the ion-conductive solid and the electrode active material can be suppressed because the ion-conductive solid of the present disclosure can be manufactured by heat treatment at a low temperature compared to conventional technologies.

[0076] The cathode and anode described above may comprise the current collector. A known current collector such as aluminum, titanium, stainless steel, nickel, iron, calcined carbon, a conductive polymer, or electrically conductive glass can be used as the current collector. Furthermore, aluminum, copper, or the like, whose surface is treated with carbon, nickel, titanium, silver, or the like to improve adhesion, electrical conductivity, oxidation resistance, and the like, can be used as the current collector.

[0077] The all-solid-state battery of the present disclosure can be manufactured by a known method, for example, in which the cathode, the solid electrolyte, and the anode are layered, formed, and heat-treated. It is believed that the formation of a high-resistance phase caused by the reaction between the ion-conductive solid and the electrode active material can be suppressed because the ion-conductive solid of the present disclosure can be manufactured by heat treatment at a low temperature compared to conventional technologies. Therefore, it is believed that the all-solid-state battery with superior performance characteristics can be obtained.

[0078] The following describes a method for measuring the composition and each physical property according to the present disclosure. -Methods for identifying and analyzing the metals contained

[0079] The composition of the ion-conductive solid is analyzed by wavelength-dispersive X-ray fluorescence analysis (hereinafter also referred to as "XRF") using a sample solidified by a compression molding method. However, if analysis is difficult due to particle size effects or the like, it is preferable to vitrify the ion-conductive solid using a glass bead technique and analyze its composition by XRF. If the peaks of yttrium and the peaks of the contained metals in the XRF overlap, the composition analysis is preferably performed by inductively coupled plasma spectrochemical analysis (ICP-AES).

[0080] For XRF, the ZSX Primus II, manufactured by Rigaku Corporation, is used as the analyzer. The analysis conditions are set to use Rh as the anode of an X-ray tube, a vacuum atmosphere, an analysis diameter of 10 mm, an analysis range of 17 degrees to 81 degrees, a step of 0.01 degrees, and a scan speed of 5 seconds per step. Furthermore, detection is performed by a proportional counter when measuring a light element and by a scintillation counter when measuring a heavy element.

[0081] The identification of an element is done based on the peak position of an XRF spectrum, and the molar ratios of the concentrations are calculated based on a count rate (unit: cps), i.e. the number of X-ray photons per unit time, to determine a, b, c and d. Examples

[0082] Examples in which the ion-conductive solid of the present disclosure was specifically prepared and evaluated are described below as examples. The present disclosure is not limited to the following examples. [Example 1]-Primary firing step

[0083] Using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Nb 2 O 5(manufactured by MITSUI MINING & SMELTING CO., LTD., purity 99.9%) as raw materials, each raw material was weighed in stoichiometric amounts so that d was a value specified in Table 1, and mixed in a P-7 planetary mill manufactured by Fritsch GmbH at a disk speed of 300 rpm for 30 minutes. The planetary mill used a 5 mm diameter zirconia ball and a 45 mL container.

[0084] After mixing, the mixed powder was cold uniaxially formed at 147 MPa using an electrically driven 100 kN press P3052-10 manufactured by NPa SYSTEM Co., Ltd., and fired in an ambient atmosphere. The heating temperature was set at 650°C and the residence time was set at 720 minutes.

[0085] The obtained ion-conductive solid containing the oxide was milled for 180 minutes at a disk speed of 230 rpm in the Planetary Mill P-7 manufactured by Fritsch GmbH to produce the powder of the ion-conductive solid containing the oxide. -Secondary firing step

[0086] The powder of the ion-conductive solid containing the oxide obtained as described above was molded and secondary fired to prepare a sintered body of the ion-conductive solid containing the oxide of Example 1. For molding, the powder was uniaxially cold formed at 147 MPa using a 100 kN electric-driven device P3052-10 manufactured by NPa SYSTEM Co. The secondary firing was performed in an ambient atmosphere, the heating temperature was set at 650°C, and the residence time was set at 720 minutes. [Example 2]

[0087] The sintered body of the ion-conductive solid containing the oxide of Example 2 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 1. [Example 3]

[0088] The sintered body of the ion-conductive solid containing the oxide of Example 3 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), ZrO 2 (manufactured by NIPPON DENKO CO., LTD., purity 99.9%), CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO, LTD., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 1. [Example 4]

[0089] The sintered body of the ion-conductive solid containing the oxide of Example 4 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that the values ​​listed in Table 1 were achieved. [Example 5]

[0090] The sintered body of the ion-conductive solid containing the oxide of Example 5 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and HfO 2(manufactured by New Metals and Chemicals Corporation, Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 1. [Example 6]

[0091] The sintered body of the ion-conductive solid including the oxide of Example 6 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that c was a value shown in Table 1. [Example 7]

[0092] The sintered body of the ion-conductive solid containing the oxide of Example 7 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 1. [Example 8]

[0093] The sintered body of the ion-conductive solid containing the oxide of Example 8 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99% by mass), SnO 2(manufactured by Mitsuwa Chemicals Co., Ltd., purity 99.9%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 9]

[0094] The sintered body of the ion-conductive solid containing the oxide of Example 9 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 10]

[0095] The sintered body of the ion-conductive solid containing the oxide of Example 10 was prepared in the same step as in Example 1, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Fe 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 95.0 mass%) and TiO 2 (manufactured by TOHO TITANIUM CO., LTD., purity 99%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 11]

[0096] The sintered body of the ion-conductive solid containing the oxide of Example 11 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 12]

[0097] The sintered body of the ion-conductive solid containing the oxide of Example 12 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), B 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Lu 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 1. [Example 13]

[0098] The sintered body of the ion-conductive solid containing the oxide of Example 13 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CeO 2(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and c were the values ​​shown in Table 1. [Example 14]

[0099] The sintered body of the ion-conductive solid containing the oxide of Example 14 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), La 2 O 3(manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CaO (manufactured by KANTO CHEMICAL CO., INC., purity 97.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 15]

[0100] The sintered body of the ion-conductive solid containing the oxide of Example 15 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), La 2 O 3(manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 16]

[0101] The sintered body of the ion-conductive solid containing the oxide of Example 16 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 17]

[0102] The sintered body of the ion-conductive solid containing the oxide of Example 17 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tm 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 18]

[0103] The sintered body of the ion-conductive solid containing the oxide of Example 18 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 1. [Example 19]

[0104] The sintered body of the ion-conductive solid containing the oxide of Example 19 was prepared in the same step as in Example 1, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99% by mass), Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO., LTD, purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 1. [Example 20]

[0105] The sintered body of the ion-conductive solid containing the oxide of Example 20 was prepared in the same step as in Example 1, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Pr 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 1. [Example 21]

[0106] The sintered body of the ion-conductive solid containing the oxide of Example 21 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 1. [Example 22]

[0107] The sintered body of the ion-conductive solid containing the oxide of Example 22 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd, purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 1. [Example 23]

[0108] The sintered body of the ion-conductive solid containing the oxide of Example 23 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Nd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 24]

[0109] The sintered body of the ion-conductive solid containing the oxide of Example 24 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 25]

[0110] The sintered body of the ion-conductive solid containing the oxide of Example 25 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 1. [Example 26]

[0111] The sintered body of the ion-conductive solid containing the oxide of Example 26 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 27]

[0112] The sintered body of the ion-conductive solid containing the oxide of Example 27 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 28]

[0113] The sintered body of the ion-conductive solid containing the oxide of Example 28 was prepared in the same step as in Example 1, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Gd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Dy 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and CaO (manufactured by KANTO CHEMICAL CO, INC., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 29]

[0114] The sintered body of the ion-conductive solid containing the oxide of Example 29 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 30]

[0115] The sintered body of the ion-conductive solid containing the oxide of Example 30 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 31]

[0116] The sintered body of the ion-conductive solid including the oxide of Example 31 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b was a value shown in Table 1. [Example 32]

[0117] The sintered body of the ion-conductive solid containing the oxide of Example 32 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 33]

[0118] The sintered body of the ion-conductive solid containing the oxide of Example 33 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 34]

[0119] The sintered body of the ion-conductive solid containing the oxide of Example 34 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 1. [Example 35]

[0120] The sintered body of the ion-conductive solid containing the oxide of Example 35 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and SrO (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 98 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1. [Example 36]

[0121] The sintered body of the ion-conductive solid containing the oxide of Example 36 was prepared in the same step as in Example 1, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 1. [Example 37]

[0122] The sintered body of the ion-conductive solid containing the oxide of Example 37 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 1. [Example 38]

[0123] The sintered body of the ion-conductive solid containing the oxide of Example 38 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 1. [Example 39]

[0124] The sintered body of the ion-conductive solid containing the oxide of Example 39 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 1. [Example 40]

[0125] The sintered body of the ion-conductive solid containing the oxide of Example 40 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 1. [Example 41]

[0126] The sintered body of the ion-conductive solid containing the oxide of Example 41 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 1. [Example 42]

[0127] The sintered body of the ion-conductive solid containing the oxide of Example 42 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 1. [Example 43]

[0128] The sintered body of the ion-conductive solid containing the oxide of Example 43 was prepared in the same step as in Example 1, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Sc 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 1. [Example 44]

[0129] The sintered body of the ion-conductive solid including the oxide of Example 44 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and a disk speed in pulverization was set to 300 rpm. [Example 45]

[0130] The sintered body of the ion-conductive solid including the oxide of Example 45 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and that a disk rotation speed in pulverization was set to 300 rpm. [Example 46]

[0131] The sintered body of the ion-conductive solid including the oxide of Example 46 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and that a disk rotation speed in pulverization was set to 300 rpm. [Example 47]

[0132] The sintered body of the ion-conductive solid including the oxide of Example 47 was prepared in the same step as in Example 1, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 1, and that a disk rotation speed in pulverization was set to 150 rpm and a pulverization time was set to 60 minutes. [Comparison example 1]

[0133] The sintered body of the ion-conductive solid containing the oxide of Comparative Example 1 was prepared in the same step as in Example 1, except that Lu 2 O 3 as raw material in Example 1 by Y 2 O 3 was replaced and each raw material was weighed in stoichiometric amounts so that d was a value given in Table 1. [Comparison example 2]

[0134] The sintered body of the ion-conductive solid containing the oxide of Comparative Example 2 was prepared in the same step as in Example 2, except that Lu 2 O 3 as raw material in Example 2 by Y 2 O 3 and each raw material was weighed in stoichiometric amounts so that c was a value given in Table 1. [Comparison example 3]

[0135] The sintered body of the ion-conductive solid containing the oxide, Comparative Example 3, was prepared in the same step as in Example 3, except that Lu 2 O 3 as raw material in Example 3 by Y 2 O 3 and each raw material was weighed in stoichiometric amounts so that c and d were the values ​​given in Table 1. [Example 101]-Primary firing step

[0136] Using Li 2CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO., LTD., purity 99.9%) as raw materials, each raw material was weighed in stoichiometric amounts so that d was a value given in Table 2, and mixed in a P-7 planetary mill manufactured by Fritsch GmbH at a disk speed of 300 rpm for 30 minutes. The planetary mill used a 5 mm diameter zirconia ball and a 45 mL container.

[0137] After mixing, the mixed powder was cold uniaxially formed at 147 MPa using a 100 kN electrically driven P3052-10 molding machine manufactured by NPa SYSTEM Co. and fired in an ambient atmosphere. The heating temperature was set at 650°C and the residence time was set at 720 minutes.

[0138] The obtained ion-conductive solid containing the oxide was milled for 180 minutes at a disk speed of 230 rpm in the Planetary Mill P-7 manufactured by Fritsch GmbH to produce the powder of the ion-conductive solid containing the oxide. -Secondary firing step

[0139] The powder of the ion-conductive solid containing the oxide obtained as described above was molded and secondary fired to prepare a sintered body of the ion-conductive solid containing the oxide of Example 101. For molding, the powder was cold uniaxially formed at 147 MPa using a 100 kN electric-driven device P3052-10 manufactured by NPa SYSTEM Co. The secondary firing was carried out in an ambient atmosphere, the heating temperature was set to 650°C, and the residence time was set to 720 minutes. [Example 102]

[0140] The sintered body of the ion-conductive solid containing the oxide of Example 102 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 2. [Example 103]

[0141] The sintered body of the ion-conductive solid containing the oxide of Example 103 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), ZrO 2(manufactured by NIPPON DENKO CO., LTD., purity 99.9%), CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO, LTD., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 2. [Example 104]

[0142] The sintered body of the ion-conductive solid containing the oxide of Example 104 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that the values ​​listed in Table 2 were achieved. [Example 105]

[0143] The sintered body of the ion-conductive solid containing the oxide of Example 105 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 2. [Example 106]

[0144] The sintered body of the ion-conductive solid including the oxide of Example 106 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that c was a value shown in Table 2. [Example 107]

[0145] The sintered body of the ion-conductive solid containing the oxide of Example 107 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 2. [Example 108]

[0146] The sintered body of the ion-conductive solid containing the oxide of Example 108 was prepared in the same step as in Example 101, except for using Li2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99 mass%) and SnO 2 (manufactured by Mitsuwa Chemicals Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 109]

[0147] The sintered body of the ion-conductive solid containing the oxide of Example 109 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 110]

[0148] The sintered body of the ion-conductive solid containing the oxide of Example 110 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Fe 2 O 3(manufactured by Wako Pure Chemical Industries, Ltd., purity 95.0 mass%) and TiO 2 (manufactured by TOHO TITANIUM CO., LTD., purity 99%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 111]

[0149] The sintered body of the ion-conductive solid containing the oxide of Example 111 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 112]

[0150] The sintered body of the ion-conductive solid containing the oxide of Example 112 was prepared in the same step as in Example 101, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and c were the values ​​shown in Table 2. [Example 113]

[0151] The sintered body of the ion-conductive solid containing the oxide of Example 113 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), La 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CaO (manufactured by KANTO CHEMICAL CO., INC., purity 97.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 114]

[0152] The sintered body of the ion-conductive solid containing the oxide of Example 114 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 115]

[0153] The sintered body of the ion-conductive solid containing the oxide of Example 115 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 116]

[0154] The sintered body of the ion-conductive solid containing the oxide of Example 116 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tm 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 117]

[0155] The sintered body of the ion-conductive solid containing the oxide of Example 117 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), SnO 2 (manufactured by Mitsuwa Chemicals Co., Ltd., purity 99.9%) and Nb 2 O 5(manufactured by MITSUI MINING & SMELTING CO., LTD., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 2. [Example 118]

[0156] The sintered body of the ion-conductive solid containing the oxide of Example 118 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99% by mass), Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO., LTD., purity 99.9%) and Ta 2 O 5(manufactured by KANTO CHEMICAL CO, INC., purity 99 mass%) as raw materials, with each raw material used in the examples described above being weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 2. [Example 119]

[0157] The sintered body of the ion-conductive solid containing the oxide of Example 119 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Pr 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 2. [Example 120]

[0158] The sintered body of the ion-conductive solid containing the oxide of Example 120 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 2. [Example 121]

[0159] The sintered body of the ion-conductive solid containing the oxide of Example 121 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd., purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 2. [Example 122]

[0160] The sintered body of the ion-conductive solid containing the oxide of Example 122 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Nd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 123]

[0161] The sintered body of the ion-conductive solid containing the oxide of Example 123 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 124]

[0162] The sintered body of the ion-conductive solid containing the oxide of Example 124 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 2. [Example 125]

[0163] The sintered body of the ion-conductive solid containing the oxide of Example 125 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 126]

[0164] The sintered body of the ion-conductive solid containing the oxide of Example 126 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 127]

[0165] The sintered body of the ion-conductive solid containing the oxide of Example 127 was prepared in the same step as in Example 101, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Gd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Dy 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and CaO (manufactured by KANTO CHEMICAL CO, INC., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 128]

[0166] The sintered body of the ion-conductive solid containing the oxide of Example 128 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 129]

[0167] The sintered body of the ion-conductive solid containing the oxide of Example 129 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 130]

[0168] The sintered body of the ion-conductive solid including the oxide of Example 130 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that b was a value shown in Table 2. [Example 131]

[0169] The sintered body of the ion-conductive solid containing the oxide of Example 131 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 132]

[0170] The sintered body of the ion-conductive solid containing the oxide of Example 132 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 2. [Example 133]

[0171] The sintered body of the ion-conductive solid containing the oxide of Example 133 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and SrO (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 98 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2. [Example 134]

[0172] The sintered body of the ion-conductive solid containing the oxide of Example 134 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 2. [Example 135]

[0173] The sintered body of the ion-conductive solid containing the oxide of Example 135 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 2. [Example 136]

[0174] The sintered body of the ion-conductive solid containing the oxide of Example 136 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 2. [Example 137]

[0175] The sintered body of the ion-conductive solid containing the oxide of Example 137 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 2. [Example 138]

[0176] The sintered body of the ion-conductive solid containing the oxide of Example 138 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 2. [Example 139]

[0177] The sintered body of the ion-conductive solid containing the oxide of Example 139 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 2. [Example 140]

[0178] The sintered body of the ion-conductive solid containing the oxide of Example 140 was prepared in the same step as in Example 101, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 2. [Example 141]

[0179] The sintered body of the ion-conductive solid containing the oxide of Example 141 was prepared in the same step as in Example 101, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Sc 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 2. [Example 142]

[0180] The sintered body of the ion-conductive solid including the oxide of Example 142 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2, and that a disk speed in pulverization was set to 300 rpm. [Example 143]

[0181] The sintered body of the ion-conductive solid including the oxide of Example 143 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2, and that a disk rotation speed in pulverization was set to 300 rpm. [Example 144]

[0182] The sintered body of the ion-conductive solid including the oxide of Example 144 was prepared in the same step as in Example 101, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 2, and a disk speed in pulverization was set to 300 rpm. [Example 201]-Primary firing step

[0183] Using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO., LTD., purity 99.9%) as raw materials, each raw material was weighed in stoichiometric amounts so that d was a value given in Table 3, and mixed in a P-7 planetary mill manufactured by Fritsch GmbH at a disk speed of 300 rpm for 30 minutes. The planetary mill used a 5 mm diameter zirconia ball and a 45 mL container.

[0184] After mixing, the mixed powder was cold uniaxially formed at 147 MPa using a 100 kN electrically driven P3052-10 molding machine manufactured by NPa SYSTEM Co. and fired in ambient atmosphere. The heating temperature was set at 650°C and the residence time was set at 720 minutes.

[0185] The obtained ion-conductive solid containing the oxide was milled for 180 minutes at a disk speed of 230 rpm in the Planetary Mill P-7 manufactured by Fritsch GmbH to produce the powder of the ion-conductive solid containing the oxide. -Secondary firing step

[0186] The powder of the ion-conductive solid containing the oxide obtained as described above was molded and secondary fired to prepare a sintered body of the ion-conductive solid containing the oxide of Example 1. For molding, the powder was cold uniaxially formed at 147 MPa using a 100 kN electric machine P3052-10 manufactured by NPa SYSTEM Co. Secondary firing was performed in an ambient atmosphere, the heating temperature was set at 650°C, and the residence time was set at 720 minutes. [Example 202]

[0187] The sintered body of the ion-conductive solid containing the oxide of Example 202 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 3. [Example 203]

[0188] The sintered body of the ion-conductive solid containing the oxide of Example 203 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), ZrO 2 (manufactured by NIPPON DENKO CO., LTD., purity 99.9%), CeO 2(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO, LTD., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 3. [Example 204]

[0189] The sintered body of the ion-conductive solid containing the oxide of Example 204 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that the values ​​listed in Table 3 were achieved. [Example 205]

[0190] The sintered body of the ion-conductive solid containing the oxide of Example 205 was prepared in the same step as in Example 201, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 3. [Example 206]

[0191] The sintered body of the ion-conductive solid including the oxide of Example 206 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c was a value shown in Table 3. [Example 207]

[0192] The sintered body of the ion-conductive solid containing the oxide of Example 207 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 3. [Example 208]

[0193] The sintered body of the ion-conductive solid containing the oxide of Example 208 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99 mass%) and SnO 2(manufactured by Mitsuwa Chemicals Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 209]

[0194] The sintered body of the ion-conductive solid containing the oxide of Example 209 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 210]

[0195] The sintered body of the ion-conductive solid containing the oxide of Example 210 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), Fe 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 95.0 mass%) and TiO 2 (manufactured by TOHO TITANIUM CO., LTD., purity 99%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 211]

[0196] The sintered body of the ion-conductive solid containing the oxide of Example 211 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 212]

[0197] The sintered body of the ion-conductive solid containing the oxide of Example 212 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and c were the values ​​shown in Table 3. [Example 213]

[0198] The sintered body of the ion-conductive solid containing the oxide of Example 213 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), La 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CaO (manufactured by KANTO CHEMICAL CO., INC., purity 97.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 214]

[0199] The sintered body of the ion-conductive solid containing the oxide of Example 214 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 215]

[0200] The sintered body of the ion-conductive solid containing the oxide of Example 215 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tb 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 216]

[0201] The sintered body of the ion-conductive solid containing the oxide of Example 216 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 217]

[0202] The sintered body of the ion-conductive solid containing the oxide of Example 217 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 3. [Example 218]

[0203] The sintered body of the ion-conductive solid containing the oxide of Example 218 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd, purity 95 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99% by mass), Nb 2 O5 (manufactured by MITSUI MINING & SMELTING CO., LTD, purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 3. [Example 219]

[0204] The sintered body of the ion-conductive solid containing the oxide of Example 219 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and Pr 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 3. [Example 220]

[0205] The sintered body of the ion-conductive solid containing the oxide of Example 220 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 3. [Example 221]

[0206] The sintered body of the ion-conductive solid containing the oxide of Example 221 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd.) Purity 95% by mass, Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd, purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 3. [Example 222]

[0207] The sintered body of the ion-conductive solid containing the oxide of Example 222 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%), Nd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 223]

[0208] The sintered body of the ion-conductive solid containing the oxide of Example 223 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 224]

[0209] The sintered body of the ion-conductive solid containing the oxide of Example 224 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 3. [Example 225]

[0210] The sintered body of the ion-conductive solid containing the oxide of Example 225 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 226]

[0211] The sintered body of the ion-conductive solid containing the oxide of Example 226 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 227]

[0212] The sintered body of the ion-conductive solid containing the oxide of Example 227 was prepared in the same step as in Example 201, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd, purity 95 mass%), Gd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Dy 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and CaO (manufactured by KANTO CHEMICAL CO, INC., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 228]

[0213] The sintered body of the ion-conductive solid containing the oxide of Example 228 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 229]

[0214] The sintered body of the ion-conductive solid containing the oxide of Example 229 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 3. [Example 230]

[0215] The sintered body of the ion-conductive solid including the oxide of Example 230 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b was a value shown in Table 3. [Example 231]

[0216] The sintered body of the ion-conductive solid containing the oxide of Example 231 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95% by mass), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 232]

[0217] The sintered body of the ion-conductive solid containing the oxide of Example 232 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd, purity 95 mass%), Ho 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd, purity 99.9 mass%) and SrO (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 98 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3. [Example 233]

[0218] The sintered body of the ion-conductive solid containing the oxide of Example 233 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 3. [Example 234]

[0219] The sintered body of the ion-conductive solid containing the oxide of Example 234 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 3. [Example 235]

[0220] The sintered body of the ion-conductive solid containing the oxide of Example 235 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 3. [Example 236]

[0221] The sintered body of the ion-conductive solid containing the oxide of Example 236 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 3. [Example 237]

[0222] The sintered body of the ion-conductive solid containing the oxide of Example 237 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 3. [Example 238]

[0223] The sintered body of the ion-conductive solid containing the oxide of Example 238 was prepared in the same step as in Example 201, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 3. [Example 239]

[0224] The sintered body of the ion-conductive solid containing the oxide of Example 239 was prepared in the same step as in Example 201, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and Sc 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 3. [Example 240]

[0225] The sintered body of the ion-conductive solid including the oxide of Example 240 was prepared in the same step as in Example 201, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3, and that a disk speed in pulverization was set to 300 rpm. [Example 241]

[0226] The sintered body of the ion-conductive solid including the oxide of Example 241 was prepared in the same step as in Example 201, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3, and that a disk speed in pulverization was set to 300 rpm. [Example 242]

[0227] The sintered body of the ion-conductive solid including the oxide of Example 242 was prepared in the same step as in Example 201, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 3, and a disk rotation speed in pulverization was set to 300 rpm. [Example 301]-Primary firing step

[0228] Using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO., LTD., purity 99.9%) as raw materials, each raw material was weighed in stoichiometric amounts so that d was a value given in Table 4 and mixed in a P-7 planetary mill manufactured by Fritsch GmbH at a disk speed of 300 rpm for 30 minutes. The planetary mill used a 5 mm diameter zirconia ball and a 45 mL container.

[0229] After mixing, the mixed powder was cold uniaxially formed at 147 MPa using a 100 kN electrically driven P3052-10 molding machine manufactured by NPa SYSTEM Co. and fired in an ambient atmosphere. The heating temperature was set at 650°C and the residence time was set at 720 minutes.

[0230] The obtained ion-conductive solid containing the oxide was milled for 180 minutes at a disk speed of 230 rpm in the Planetary Mill P-7 manufactured by Fritsch GmbH to produce the powder of the ion-conductive solid containing the oxide. -Secondary firing step

[0231] The powder of the ion-conductive solid containing the oxide obtained as described above was molded and secondary fired to produce a sintered body of the ion-conductive solid containing the oxide of Example 301. For molding, the powder was cold uniaxially molded at 147 MPa using a 100 kN electric-driven device P3052-10 manufactured by NPa SYSTEM Co. The secondary firing was carried out in an ambient atmosphere, the heating temperature was set at 650°C, and the residence time was set at 720 minutes. [Example 302]

[0232] The sintered body of the ion-conductive solid containing the oxide of Example 302 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value shown in Table 4. [Example 303]

[0233] The sintered body of the ion-conductive solid containing the oxide of Example 303 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), ZrO 2 (manufactured by NIPPON DENKO CO., LTD., purity 99.9%), CeO2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) and Nb 2 O 5 (manufactured by MITSUI MINING & SMELTING CO, LTD., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 4. [Example 304]

[0234] The sintered body of the ion-conductive solid containing the oxide of Example 304 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that the values ​​listed in Table 4 were achieved. [Example 305]

[0235] The sintered body of the ion-conductive solid containing the oxide of Example 305 was prepared in the same step as in Example 301, except for using Li 2 CO3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that c was a value as shown in Table 4. [Example 306]

[0236] The sintered body of the ion-conductive solid including the oxide of Example 306 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c was a value shown in Table 4. [Example 307]

[0237] The sintered body of the ion-conductive solid containing the oxide of Example 307 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 4. [Example 308]

[0238] The sintered body of the ion-conductive solid containing the oxide of Example 308 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99 mass%) and SnO2 (manufactured by Mitsuwa Chemicals Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 309]

[0239] The sintered body of the ion-conductive solid containing the oxide of Example 309 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 310]

[0240] The sintered body of the ion-conductive solid containing the oxide of Example 310 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Fe 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 95.0 mass%) and TiO 2 (manufactured by TOHO TITANIUM CO., LTD., purity 99%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 311]

[0241] The sintered body of the ion-conductive solid containing the oxide of Example 311 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 312]

[0242] The sintered body of the ion-conductive solid containing the oxide of Example 312 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CeO 2 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and c were the values ​​shown in Table 4. [Example 313]

[0243] The sintered body of the ion-conductive solid containing the oxide of Example 313 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), La 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), MgO (manufactured by Ube Material Industries, Ltd., purity 99.0 mass%) and CaO (manufactured by KANTO CHEMICAL CO., INC., purity 97.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 314]

[0244] The sintered body of the ion-conductive solid containing the oxide of Example 314 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Lu 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 315]

[0245] The sintered body of the ion-conductive solid containing the oxide of Example 315 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) and MnO (manufactured by KANTO CHEMICAL CO., INC., purity 80.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 316]

[0246] The sintered body of the ion-conductive solid containing the oxide of Example 316 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that c and d were the values ​​shown in Table 4. [Example 317]

[0247] The sintered body of the ion-conductive solid containing the oxide of Example 317 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), In 2 O 3 (manufactured by Shinko Chemical Co., Ltd., purity 99% by mass), Nb 2O 5 (manufactured by MITSUI MINING & SMELTING CO., LTD, purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 4. [Example 318]

[0248] The sintered body of the ion-conductive solid containing the oxide of Example 318 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Pr 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 4. [Example 319]

[0249] The sintered body of the ion-conductive solid containing the oxide of Example 319 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 4. [Example 320]

[0250] The sintered body of the ion-conductive solid containing the oxide of Example 320 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%), HfO 2 (manufactured by New Metals and Chemicals Corporation, Ltd., purity 99.9%) and Ta 2 O 5 (manufactured by KANTO CHEMICAL CO., INC., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 4. [Example 321]

[0251] The sintered body of the ion-conductive solid containing the oxide of Example 321 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3(manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Nd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Sm 2 O 3 (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9 mass%) and ZnO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 322]

[0252] The sintered body of the ion-conductive solid containing the oxide of Example 322 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 323]

[0253] The sintered body of the ion-conductive solid containing the oxide of Example 323 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 4. [Example 324]

[0254] The sintered body of the ion-conductive solid containing the oxide of Example 324 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Eu 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 325]

[0255] The sintered body of the ion-conductive solid containing the oxide of Example 325 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 326]

[0256] The sintered body of the ion-conductive solid containing the oxide of Example 326 was prepared in the same step as in Example 301, except for using Li 2 CO 3(manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Gd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Dy 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 95 mass%) and CaO (manufactured by KANTO CHEMICAL CO, INC., purity 99.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 327]

[0257] The sintered body of the ion-conductive solid containing the oxide of Example 327 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 328]

[0258] The sintered body of the ion-conductive solid containing the oxide of Example 328 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 329]

[0259] The sintered body of the ion-conductive solid including the oxide of Example 329 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b was a value shown in Table 4. [Example 330]

[0260] The sintered body of the ion-conductive solid containing the oxide of Example 330 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), NiO (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.0 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 331]

[0261] The sintered body of the ion-conductive solid containing the oxide of Example 331 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5 mass%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Tb 2 O 3(manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.9 mass%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and BaO (manufactured by Wako Pure Chemical Industries, Ltd., purity 90.0 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 332]

[0262] The sintered body of the ion-conductive solid containing the oxide of Example 332 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b, c, and d were the values ​​shown in Table 4. [Example 333]

[0263] The sintered body of the ion-conductive solid containing the oxide of Example 333 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd, purity 99.9 mass%), Ho 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%), He 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd, purity 95 mass%) and SrO (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 98 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4. [Example 334]

[0264] The sintered body of the ion-conductive solid containing the oxide of Example 334 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and c were the values ​​shown in Table 4. [Example 335]

[0265] The sintered body of the ion-conductive solid containing the oxide of Example 335 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 4. [Example 336]

[0266] The sintered body of the ion-conductive solid containing the oxide of Example 336 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that a, b, and c were the values ​​shown in Table 4. [Example 337]

[0267] The sintered body of the ion-conductive solid containing the oxide of Example 337 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 4. [Example 338]

[0268] The sintered body of the ion-conductive solid containing the oxide of Example 338 was prepared in the same step as in Example 301, except that each raw material used in the examples described above was weighed in stoichiometric amounts so that b and d were the values ​​shown in Table 4. [Example 339]

[0269] The sintered body of the ion-conductive solid containing the oxide of Example 339 was prepared in the same step as in Example 301, except for using Li 2 CO 3 (manufactured by NACALAI TESQUE, INC., purity 99.0 mass%), H 3 BO 3 (manufactured by KANTO CHEMICAL CO., INC., purity 99.5%), Tm 2 O 3 (manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) and Sc 2 O 3(manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.9 mass%) as raw materials, with each raw material weighed in stoichiometric amounts so that b was a value shown in Table 4. [Example 340]

[0270] The sintered body of the ion-conductive solid including the oxide of Example 340 was prepared in the same step as in Example 301, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4, and a disk speed in pulverization was set to 300 rpm. [Example 341]

[0271] The sintered body of the ion-conductive solid including the oxide of Example 341 was prepared in the same step as in Example 301, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4, and a disk speed in pulverization was set to 300 rpm. [Example 342]

[0272] The sintered body of the ion-conductive solid including the oxide of Example 324 was prepared in the same step as in Example 301, except that each raw material used in the above-described examples was weighed in stoichiometric amounts so that a and b were the values ​​shown in Table 4, and a disk speed in pulverization was set to 300 rpm. [Comparison example 4]

[0273] Tm 2 O 3 as raw material in Example 4 was in Sc 2 O 3 (Ionic radius of Sc 3+ : 0.87 Å), and the preparation was carried out in the same step as in Example 4, but the same crystal structure as in Example 4 could not be obtained. The impedance of the resulting sintered body was measured by a method described below, but the resistance of the sintered body could not be measured, and the ionic conductivity was not obtained as a numerical value. [Comparison Example 5]

[0274] Tm 2 O 3 as raw material in Example 4 was Fe 2 O 3 (Ionic radius of Fe 3+: 0.78 Å) and the preparation was carried out in the same step as in Example 4, but the same crystal structure as in Example 4 could not be obtained. The impedance of the resulting sintered body was measured by a method described below, but the resistance of the sintered body could not be measured and the ionic conductivity was not obtained as a numerical value. [Comparison Example 6]

[0275] Tm 2 O 3 as raw material in Example 4 was in La 2 O 3 (Ionic radius of La 3+: 1.16 Å), and the preparation was carried out in the same step as in Example 4, but the same crystal structure as in Example 4 could not be obtained. The impedance of the resulting sintered body was measured by a method described below, but the resistance of the sintered body could not be measured, and the ionic conductivity was not obtained as a numerical value. The sintered bodies of the ion-conductive solids containing the oxides of Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342 were subjected to composition analysis according to the methods described above. Furthermore, the volume-average particle diameters of the powders of the ion-conductive solids obtained in Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342 and Comparative Examples 1 to 3 and the ionic conductivities of the sintered bodies of the ion-conductive solids were measured according to the following methods.

[0276] The methods for measuring ionic conductivities and volume-average particle diameters are described below. The evaluation results obtained are listed in Table 1, Table 2, Table 3, and Table 4. -Measurement of ionic conductivity

[0277] Two parallel, large-area surfaces of the sintered body of the ion-conductive solid containing the oxide obtained by secondary firing, which had a flat plate shape, were polished with sandpaper. The size of the sintered body of the ion-conductive solid containing the oxide and having the flat plate shape can be set to, for example, 0.9 cm × 0.9 cm × 0.05 cm, but is not limited to this. Polishing was first performed with #500 for 15 to 30 minutes, then with #1000 for 10 to 20 minutes, and finally with #2000 for 5 to 10 minutes. It was completed when no noticeable depression / protrusion or defect was visually observed on the polished surfaces.

[0278] After polishing, gold was deposited on the polished surfaces of the sintered body of the ion-conductive solid containing the oxide using an SC-701MkII ADVANCE sputtering device from Sanyu Electron Co., Ltd. A sample was prepared using the deposition conditions of Ar gas, a vacuum of 2 Pa to 5 Pa, and a deposition time of 5 minutes. After deposition, the AC impedance of the sample was measured.

[0279] For impedance measurement, an SI1260 impedance / gain phase analyzer and a 1296 dielectric interface system (both manufactured by Solartron) were used, and the measurement conditions were set to a temperature of 27°C, an amplitude of 20 mV, and a frequency of 0.1 Hz to 1 MHz.

[0280] The resistance of the ion-conductive solid oxide sintered body was calculated using a Nyquist plot obtained from the impedance measurement and the AC analysis software ZVIEW manufactured by Scribner. Using ZVIEW, an equivalent circuit corresponding to the sample was set up, and the fitting and analysis of the equivalent circuit and Nyquist plot were performed to calculate the resistance of the ion-conductive solid oxide sintered body. The ionic conductivity was calculated using the following equation using the calculated resistance, the thickness of the ion-conductive solid oxide sintered body, and the electrode area. Ionic conductivity (S / cm) = thickness (cm) of the sintered body of the ionically conductive solid containing oxide / (resistivity (Ω) of the sintered body of the ionically conductive solid containing oxide × electrode area (cm2))

[0281] For example, the ionic conductivity (S / cm) of the sintered body of the ion-conductive solid is preferably 8.00 × 10 -9 or more, more preferably 1.00 × 10 -8 or more, more preferably 1.00 × 10 -7 or more, more preferably 1.00 × 10 -6 or more, and particularly preferably 1.00 × 10 -5 or more. More preferred is the conductivity whose upper limit is not particularly limited and, for example, 1.00 × 10 -2 or less, 1.00 × 10 -3 or less, and 1.00 × 10 -4 or less. -Evaluation of the volume-average particle diameter

[0282] The particle size distribution of the ion-conductive solid powder containing the oxide obtained by treatment in a ball mill (Planetary Mill P-7, manufactured by Fritsch GmbH) after the first firing was measured using a laser diffraction / scattering particle size distribution measuring device LA-960V2 manufactured by HORIBA, Ltd. The refractive index was set to 1.8, and ethanol was used as the measuring solvent. The sample concentration was adjusted so that the transmittance was 90 to 70%. The volume-average particle diameter was calculated from the obtained frequency distribution. -Results

[0283] The stoichiometric amounts (values ​​of a, b, c, and d in the general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9) of the raw materials, the volume-average particle diameters and the ionic conductivities in the case of producing each of the sintered bodies of the ion-conductive solids including the oxides of Examples 1 to 47, 101 to 144, 201 to 242 and 301 to 342 and Comparative Examples 1 to 3 are shown in Table 1, Table 2, Table 3 and Table 4.

[0284] As a result of the composition analysis described above, it was confirmed that all of the sintered bodies of the ion-conductive solids containing the oxides of Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342 and Comparative Examples 1 to 3 had the compositions in the stoichiometric amounts of the raw materials shown in Table 1, Table 2, Table 3, and Table 4. Furthermore, the sintered bodies of the ion-conductive solids containing the oxides of Examples 1 to 47, 101 to 144, 201 to 242, and 301 to 342 were ion-conductive solids, indicating the high ionic conductivities even when firing was performed at a temperature of less than 700°C.

[0233] [Table 1] The 6+a-c-2d Lu 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 mean diameter [µm] Ionic conductivity [S / cm] M1 M2 M3 M4 a b c d Comparison example 1 - - - Nb 0 0 0 0,400 10,1 5,65×10 -10 Comparison example 2 - - This - 0 0 0,300 0 21,3 2,66×10 -8 Comparison example 3 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 15,1 8,73×10 -8 Example 1 - - - Nb 0 0 0 0,400 10,9 1,58×10 -7 Example 2 - - This - 0 0 0,300 0 13,1 4,16×10 -7 Example 3 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 14,8 5,07×10 -7 Example 4 - - - - 0 0 0 0 12,0 2,66×10 -7 Example 5 - - Hf - 0 0 0,100 0 7,7 2,32×10 -6 Example 6 - - Zr:Ce=4:1 - 0 0 0,125 0 8,1 3,06×10 -5 Example 7 - - Zr Nb 0 0 0,100 0,025 0,4 2,58×10 -5 Example 8 - In Sn - 0 0,500 0,400 0 9,3 1,97×10 -7 Example 9 - In Hf - 0 0,300 0,100 0 8,6 6,11×10 -6 Example 10 - Fe Ti - 0 0,100 0,800 0 10,1 1,37×10 -8 Example 11 - Fe Zr:Hf=4:1 - 0 0,400 0,100 0 9,9 3,08×10 -6 Example 12 - Ho - - 0 0,900 0 0 9,5 8,33×10 -6 Example 13 Mg This 0,025 0 0,025 0 9,1 7,84×10 -7 Example 14 Mg:Ca=1:1 La - - 0,100 0,800 0 0 9,1 5,64×10 -8 Example 15 Mn La - - 0,800 0,100 0 0 8,8 3,07×10 -8 Example 16 Mn Tb - - 0,050 0,100 0 0 21,0 1,22×10 -7 Example 17 Mn Tm - - 0,050 0,100 0 0 15,6 1,81×10 -7 Example 18 - - Sn Nb 0 0 0,100 0,400 13,7 9,67×10 -8 Example 19 - In - Nb:Ta=1:1 0 0,300 0 0,100 9,0 4,17×10 -6 Example 20 - Pr - - 0 0,500 0 0 8,1 4,32×10 -8 Example 21 - Pr:La=1:1 - Nb 0 0,100 0 0,800 10,6 7,82×10 -9 Example 22 - Sm Hf Ta 0 0,500 0,050 0,050 7,8 2,04×10 -7 Example 23 Zn Nd:Sm=1:1 - - 0,100 0,200 0 0 8,4 3,92×10 -7 Example 24 - Nd Zr - 0 0,100 0,100 0 8,8 2,08×10 -6 Example 25 - Eu - - 0 0,100 0 0 12,4 3,12×10 -7 Example 26 No Eu - 0,100 0,100 0 0 22,9 3,88×10 -7 Example 27 - Eu Zr:Hf=4:1 - 0 0,100 0,100 0 13,6 8,61×10 -6 Example 28 Ca Gd:Dy=1:1 - - 0,100 0,200 0 0 11,1 3,20×10 -7 Example 29 - Gd Zr - 0 0,100 0,100 0 7,7 1,07×10 -5 Example 30 - Dy Ti:Sn=1:1 - 0 0,100 0,100 0 12,4 4,03×10 -6 Example 31 - Dy - - 0 0,100 0 0 16,1 7,92×10 -8 Example 32 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 22,8 5,21×10 -7 Example 33 Ba Tb:Ho=1:1 - - 0,100 0,200 0 0 11,2 1,86×10 -7 Example 34 - Tb Hf Ta 0 0,100 0,050 0,050 9,0 6,74×10 -7 Example 35 Sr Er:Tm=1:1 - - 0,100 0,200 0 0 11,6 2,33×10 -7 Example 36 - Er Ti - 0 0,100 0,100 0 13,0 3,60×10 -7 Example 37 No Er Sn - 0,100 0,100 0,100 0 9,4 1,61×10 -7 Example 38 - Tm - Nb 0 0,100 0 0,100 8,0 1,70×10 -7 Example 39 - Tm Zr Ta 0 0,100 0,100 0,100 11,7 5,94×10 -6 Example 40 Mg Gd This - 0,100 0,100 0,100 0 10,6 4,10×10 -7 Example 41 - Gd - Nb 0 0,010 0 0,100 8,4 3,77×10 -7 Example 42 - Gd - Ta 0 0,100 0 0,800 11,4 5,62×10 -9 Example 43 - Sc - - 0 0,100 0 0 8,3 1,55×10 -8 Example 44 Mn Tb - - 0,050 0,100 0 0 9,9 1,89×10 -7 Example 45 No Eu - - 0,100 0,100 0 0 15,0 4,10×10 -7 Example 46 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 13,9 5,54×10 -7 Example 47 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 41,3 2,07×10 -7

[0285] In the table, Comparative Examples 1 to 3 each correspond to the oxide represented by the general formula: Li 6+a-c-2d Y 1-a-b-c-d M1 a M2b M3 c M4 d B 3 O 9 .

[0234] [Table 2] <h2 style=";text-align:left;direction:ltr">Li<h2 style=";text-align:left;direction:ltr"> 6+a-c-2d <h2 style=";text-align:left;direction:ltr"> Ho<h2 style=";text-align:left;direction:ltr"> 1-a-b-c-d <h2 style=";text-align:left;direction:ltr"> M1<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> M2<h2 style=";text-align:left;direction:ltr"> b <h2 style=";text-align:left;direction:ltr"> M3<h2 style=";text-align:left;direction:ltr"> c <h2 style=";text-align:left;direction:ltr"> M4<h2 style=";text-align:left;direction:ltr"> d <h2 style=";text-align:left;direction:ltr"> B<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> O<h2 style=";text-align:left;direction:ltr"> 9 mean diameter [µm] Ionic conductivity [S / cm] M1 M2 M3 M4 a b c d Comparison example 1 - - - Nb 0 0 0 0,400 10,1 5,65×10 -10 Comparison example 2 - - This - 0 0 0,300 0 21,3 2,66×10 -8 Comparison example 3 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 15,1 8,73×10 -8 Example 101 - - - Nb 0 0 0 0,400 8,5 1,33×10 -7 Example 102 - - This - 0 0 0,300 0 17,7 4,57×10 -7 Example 103 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 11,9 5,14×10 -7 Example 104 - - - - 0 0 0 0 13,2 2,39×10 -7 Example 105 - - Hf - 0 0 0,100 0 8,6 2,28×10 -6 Example 106 - - Zr:Ce=4:1 - 0 0 0,125 0 6,8 1,78×10 -5 Example 107 - - Zr Nb 0 0 0,100 0,025 0,7 1,56×10 -5 Example 108 - In Sn - 0 0,500 0,400 0 9,1 2,11×10 -7 Example 109 - In Hf - 0 0,300 0,100 0 8,0 5,22×10 -6 Example 110 - Fe Ti - 0 0,100 0,800 0 13,4 1,77×10 -8 Example 111 - Fe Zr:Hf=4:1 - 0 0,400 0,100 0 11,2 2,61×10 -6 Example 112 Mg - This - 0,025 0 0,025 0 8,5 7,63×10 -7 Example 113 Mg:Ca=1:1 La - - 0,100 0,800 0 0 10,2 9,79×10 -8 Example 114 Mn Lu - - 0,800 0,100 0 0 9,6 6,42×10 -8 Example 115 Mn Tb - - 0,050 0,100 0 0 21,7 3,02×10 -7 Example 116 Ba Tm - - 0,050 0,100 0 0 12,0 1,87×10 -7 Example 117 - - Sn Nb 0 0 0,100 0,400 12,3 7,88×10 -8 Example 118 - In - Nb:Ta=1:1 0 0,300 0 0,100 10,5 4,13×10 -6 Example 119 - Pr - - 0 0,500 0 0 9,4 5,39×10 -8 Example 120 - Pr:La=1:1 - Nb 0 0,100 0 0,800 8,1 7,71×10 -9 Example 121 - Sm Hf Ta 0 0,500 0,050 0,050 8,1 2,40×10 -7 Example 122 Zn Nd:Sm=1:1 - - 0,100 0,200 0 0 8,9 5,06×10 -7 Example 123 - Nd Zr - 0 0,100 0,100 0 9,3 2,11×10 -6 Example 124 - Eu - - 0 0,100 0 0 10,1 3,30×10 -7 Example 125 No Eu - - 0,100 0,100 0 0 21.4 4,28×10 -7 Example 126 - Eu Zr:Hf=4:1 - 0 0,100 0,100 0 15,3 8.55×10 -6 Example 127 Ca Gd:Dy=1:1 - - 0,100 0,200 0 0 14,8 4,07×10 -7 Example 128 - Gd Zr - 0 0,100 0,100 0 9,0 1,88×10 -5 Example 129 - Dy Ti:Sn=1:1 - 0 0,100 0,100 0 16,1 4,64×10 -6 Example 130 - Dy - - 0 0,100 0 0 14,2 7,06×10 -8 Example 131 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 24,5 5,44×10 -7 Example 132 - Tb Hf Ta 0 0,100 0,050 0,050 9,9 6,40×10 -7 Example 133 Sr Er:Tm=1:1 - - 0,100 0,200 0 0 10,6 2,09×10 -7 Example 134 - Er Ti - 0 0,100 0,100 0 12,2 4,59×10 -7 Example 135 No Er Sn - 0,100 0,100 0,100 0 8,3 1,78×10 -7 Example 136 - Tm - Nb 0 0,100 0 0,100 9,7 2,15×10 -7 Example 137 - Tm Zr Ta 0 0,100 0,100 0,100 16,0 5,96×10 -6 Example 138 Mg Gd This - 0,100 0,100 0,100 0 10,1 4,38×10 -7 Example 139 - Gd - Nb 0 0,010 0 0,100 9,5 3,50×10 -7 Example 140 - Gd - Ta 0 0,100 0 0,800 12,7 5,71×10 -9 Example 141 - Sc - - 0 0,100 0 0 10,4 7,33×10 -9 Example 142 Mn Tb - - 0,050 0,100 0 0 9,7 4,56×10 -7 Example 143 No Eu - - 0,100 0,100 0 0 12,3 5,32×10 -7 Example 144 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 14,2 6,09×10 -7

[0286] In the table, Comparative Examples 1 to 3 each correspond to the oxide represented by the general formula: Li 6+a-c-2d Y 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 .

[0235] [Table 3] The 6+a-c-2d Er 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 mean diameter [µm] Ionic conductivity [S / cm] M1 M2 M3 M4 a b c d Comparison example 1 - - - Nb 0 0 0 0,400 10,1 5,65×10 -10 Comparison example 2 - - This - 0 0 0,300 0 21,3 2,66×10 -8 Comparison example 3 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 15,1 8,73×10 -8 Example 201 - - - Nb 0 0 0 0,400 13,3 1,66×10 -7 Example 202 - - This - 0 0 0,300 0 10,5 4,01×10 -7 Example 203 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 17,2 5,68×10 -7 Example 204 - - - - 0 0 0 0 9,4 2,45×10 -7 Example 205 - - Hf - 0 0 0,100 0 10,1 2,02×10 -6 Example 206 - - Zr:Ce=4:1 - 0 0 0,125 0 5,5 2,03×10 -5 Example 207 - - Zr Nb 0 0 0,100 0,025 2,8 2,01×10 -5 Example 208 - In Sn - 0 0,500 0,400 0 6,7 2,77×10 -7 Example 209 - In Hf - 0 0,300 0,100 0 11,0 6,28×10 -6 Example 210 - Fe Ti - 0 0,100 0,800 0 7,5 1,31×10 -8 Example 211 - Fe Zr:Hf=4:1 - 0 0,400 0,100 0 12,3 1,59×10 -6 Example 212 Mg - This - 0,025 0 0,025 0 6,5 5,33×10 -7 Example 213 Mg:Ca=1:1 La - - 0,100 0,800 0 0 10,4 4,15×10 -8 Example 214 Mn Lu - - 0,800 0,100 0 0 5,1 7,96×10 -8 Example 215 Mn Tb - - 0,050 0,100 0 0 23,4 1,44×10 -7 Example 216 Mn Tm - - 0,050 0,100 0 0 13,0 1,82×10 -7 Example 217 - - Sn Nb 0 0 0,100 0,400 16,1 6,93×10 -8 Example 218 - In - Nb:Ta=1:1 0 0,300 0 0,100 6,4 4,54×10 -6 Example 219 - Pr - - 0 0,500 0 0 10,5 6,22x10 -8 Example 220 - Pr:La=1:1 - Nb 0 0,100 0 0,800 7,1 6,43×10 -9 Example 221 - Sm Hf Ta 0 0,500 0,050 0,050 10,2 3,26×10 -7 Example 222 Zn Nd:Sm=1:1 - - 0,100 0,200 0 0 5,8 4,20×10 -7 Example 223 - Nd Zr - 0 0,100 0,100 0 11,2 2,30×10 -6 Example 224 - Eu - - 0 0,100 0 0 9,8 2,77×10 -7 Example 225 No Eu - - 0,100 0,100 0 0 25,3 3,10×10 -7 Example 226 - Eu Zr:Hf=4:1 - 0 0,100 0,100 0 11,0 7,98×10 -6 Example 227 Ca Gd:Dy=1:1 - - 0,100 0,200 0 0 13,5 2,05×10 -7 Example 228 - Gd Zr - 0 0,100 0,100 0 5,1 8,81×10 -6 Example 229 - Dy Ti:Sn=1:1 - 0 0,100 0,100 0 14,8 2,67×10 -6 Example 230 - Dy - - 0 0,100 0 0 13,5 7,84×10 -8 Example 231 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 25,2 5,10×10 -7 Example 232 Sr Tb:Ho=1:1 - - 0,100 0,200 0 0 8,6 2,05×10 -7 Example 233 - Tb Hf Ta 0 0,100 0,050 0,050 11,4 7,33×10 -7 Example 234 - Tm - Nb 0 0,100 0 0,100 10,4 1,87×10 -7 Example 235 - Tm Zr Ta 0 0,100 0,100 0,100 9,1 4,65×10 -6 Example 236 Mg Gd This - 0,100 0,100 0,100 0 13,0 4,22×10 -7 Example 237 - Gd - Nb 0 0,010 0 0,100 5,8 1,23×10 -7 Example 238 - Gd - Ta 0 0,100 0 0,800 13,8 4,74×10 -9 Example 239 - Sc - - 0 0,100 0 0 10,2 8,56×10 -9 Example 240 Mn Tb - - 0,050 0,100 0 0 7,3 2,31×10 -7 Example 241 No Eu - - 0,100 0,100 0 0 17,4 3,79×10 -7 Example 242 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 11,3 5,88×10 -7

[0287] In the table, Comparative Examples 1 to 3 each correspond to the oxide represented by the general formula: Li 6+a-c-2d Y 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 .

[0236] [Table 4] <h2 style=";text-align:left;direction:ltr">Li<h2 style=";text-align:left;direction:ltr"> 6+a-c-2d <h2 style=";text-align:left;direction:ltr"> Tm<h2 style=";text-align:left;direction:ltr"> 1-a-b-c-d <h2 style=";text-align:left;direction:ltr"> M1<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> M2<h2 style=";text-align:left;direction:ltr"> b <h2 style=";text-align:left;direction:ltr"> M3<h2 style=";text-align:left;direction:ltr"> c <h2 style=";text-align:left;direction:ltr"> M4<h2 style=";text-align:left;direction:ltr"> d <h2 style=";text-align:left;direction:ltr"> B<h2 style=";text-align:left;direction:ltr"> 3 <h2 style=";text-align:left;direction:ltr"> O<h2 style=";text-align:left;direction:ltr"> 9 mean diameter [µm] Ionic conductivity [S / cm] M1 M2 M3 M4 a b c d Comparison example 1 - - - Nb 0 0 0 0,400 10,1 5.65×10 -10 Comparison example 2 - - This - 0 0 0,300 0 21,3 2,66×10 -8 Comparison example 3 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 15,1 8,73×10 -8 Example 301 - - - Nb 0 0 0 0,400 14,5 1,33×10 -7 Example 302 - - This - 0 0 0,300 0 9,2 1,06x10 -1 Example 303 - - Zr:Ce=1:1 Nb 0 0 0,200 0,100 18,4 8,12×10 -7 Example 304 - - - - 0 0 0 0 8,1 2,20×10 -7 Example 305 - - Hf - 0 0 0,100 0 11,3 1,95×10 -6 Example 306 - - Zr:Ce=4:1 - 0 0 0,125 0 7,3 2,32×10 -5 Example 307 - - Zr Nb 0 0 0,100 0,025 9,9 2,18×10 -5 Example 308 - In Sn - 0 0,500 0,400 0 6,8 1,42×10 -5 Example 309 - In Hf - 0 0,300 0,100 0 12,2 7,08×10 -6 Example 310 - Fe Ti - 0 0,100 0,800 0 6,2 1,40x10 -8 Example 311 - Fe Zr:Hf=4:1 - 0 0,400 0,100 0 13,5 1,69×10 -6 Example 312 Mg - This - 0,025 0 0,025 0 7,6 6,82×10 -7 Example 313 Mg:Ca=1:1 La - - 0,100 0,800 0 0 11,6 8,91×10 -8 Example 314 Mn Lu - - 0,800 0,100 0 0 9,5 5,31×10 -8 Example 315 Mn Tb - - 0,050 0,100 0 0 24,6 3,03×10 -7 Example 316 - - Sn Nb 0 0 0,100 0,400 17,3 9,32×10 -8 Example 317 - In - Nb:Ta=1:1 0 0,300 0 0,100 8,2 2,56×10 -6 Example 318 - Pr - - 0 0,500 0 0 11,7 4,70×10 -8 Example 319 - Pr:La=1:1 - Nb 0 0,100 0 0,800 7,7 8,22×10 -9 Example 320 - Sm Hf Ta 0 0,500 0,050 0,050 11,4 2,74×10 -7 Example 321 Zn Nd:Sm=1:1 - - 0,100 0,200 0 0 9,6 4,69×10 -7 Example 322 - Nd Zr - 0 0,100 0,100 0 12,4 2,18×10 -6 Example 323 - Eu - - 0 0,100 0 0 8,5 3,26×10 -7 Example 324 No Eu - - 0,100 0,100 0 0 26,5 4,05×10 -7 Example 325 - Eu Zr:Hf=4:1 - 0 0,100 0,100 0 9,7 8,83×10 -6 Example 326 Ca Gd:Dy=1:1 - - 0,100 0,200 0 0 14,7 1,88×10 -7 Example 327 - Gd Zr - 0 0,100 0,100 0 7,2 8,96×10 -6 Example 328 - Dy Ti:Sn=1:1 - 0 0,100 0,100 0 16,0 3,67×10 -6 Example 329 - Dy - - 0 0,100 0 0 12,2 8,21×10 -8 Example 330 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 26,4 5,07×10 -7 Example 331 Ba Tb:Ho=1:1 - - 0,100 0,200 0 0 7,3 1,35×10 -7 Example 332 - Tb Hf Ta 0 0,100 0,050 0,050 12,6 5,84×10 -7 Example 333 Sr He:Ho=1:1 - - 0,100 0,200 0 0 7,7 2,12x10 -7 Example 334 - Er Ti - 0 0,100 0,100 0 16,6 3,40x10 -7 Example 335 No Er Sn - 0,100 0,100 0,100 0 10,3 2,06×10 -7 Example 336 Mg Gd This - 0,100 0,100 0,100 0 14,2 4,66×10 -7 Example 337 - Gd - Nb 0 0,010 0 0,100 10,7 3,13×10 -7 Example 338 - Gd - Ta 0 0,100 0 0,800 15,0 4,25×10 -9 Example 339 - Sc - - 0 0,100 0 0 11,0 8,84×10 -9 Example 340 Mn Tb - - 0,050 0,100 0 0 11,1 3,79×10 -7 Example 341 No Eu - - 0,100 0,100 0 0 18,6 4,93×10 -7 Example 342 Ba:Ni=1:1 Tb - - 0,100 0,100 0 0 10,0 3,40×10 -7

[0288] In the table, Comparative Examples 1 to 3 each correspond to the oxide represented by the general formula: Li 6+a-c-2d Y 1-a-b-c-d M1 a M2b M3 c M4 d B 3 O 9 .

[0289] Table 1, Table 2, Table 3, and Table 4 show the results in which the ionic conductivities of the ionic conductive solids prepared in Examples 1, 101, 201, and 301 were improved compared to those of Comparative Example 1, and the results in which higher ionic conductivities were obtained by substituting Y with at least one metal element selected from the group consisting of Lu, Ho, Er, and Tm. It can be seen that higher ionic conductivities are obtained by substituting Y in the composition disclosed in the related art with at least one metal element having small ionic radii selected from the group consisting of Lu, Ho, Er, and Tm.

[0290] Table 1 shows the result in which the ionic conductivities of the ionic conductive solids prepared in Examples 1 to 3 were improved compared to those in Comparative Examples 1 to 3, and the results in which higher ionic conductivities were achieved by substituting Y with Lu. It can be seen that higher ionic conductivity is achieved by substituting Y in the composition disclosed in the related art with Lu, which has a small ionic radius.

[0291] The results are also demonstrated in which the ionic conductivities of the ion-conductive solids prepared in Examples 44 to 46 were improved compared to those in Examples 16, 26, and 32, respectively. Since the compositions of the substituted elements are different from those disclosed in the related art, the influences of differences between melting points and the like on the densities after firing may lead to different suitable ranges of particle diameters.

[0292] Table 2 shows the result in which the ionic conductivities of the ionic conductive solids prepared in Examples 101 to 103 were improved compared to those in Comparative Examples 1 to 3, and the results in which higher ionic conductivities were achieved by substituting Y with Ho. It can be seen that higher ionic conductivity is achieved by substituting Y in the composition disclosed in the related art with Ho, which has a small ionic radius.

[0293] The results are also demonstrated in which the ionic conductivities of the ion-conductive solids prepared in Examples 142 to 144 were improved compared to those in Examples 115, 125, and 131, respectively. Since the compositions of the substituted elements are different from those disclosed in the related art, the influences of differences between melting points and the like on the densities after firing may lead to different suitable ranges of particle diameters.

[0294] Table 3 shows the result in which the ionic conductivities of the ionic conductive solids prepared in Examples 201 to 203 were improved compared to those in Comparative Examples 1 to 3, and the results in which higher ionic conductivities were obtained by substituting Y with Er. It can be seen that higher ionic conductivity is achieved by substituting Y in the composition disclosed in the related art with Er, which has a small ionic radius.

[0295] The results are also demonstrated in which the ionic conductivities of the ion-conductive solids prepared in Examples 240 to 242 were improved compared to those in Examples 215, 225, and 231, respectively. Since the compositions of the substituted elements are different from those disclosed in the related art, the influences of differences between melting points and the like on the densities after firing may lead to the various suitable ranges of particle diameters.

[0296] Table 4 shows the result in which the ionic conductivities of the ionic conductive solids prepared in Examples 301 to 303 were improved compared to those in Comparative Examples 1 to 3, respectively, and the results in which higher ionic conductivities were achieved by substituting Y with Tm. It can be seen that higher ionic conductivity is achieved by substituting Y in the composition disclosed in the related art with Tm, which has a small ionic radius.

[0297] The results are also demonstrated in which the ionic conductivities of the ion-conductive solids prepared in Examples 340 to 342 were improved compared to those in Examples 315, 324, and 330, respectively. Since the compositions of the substituted elements are different from those disclosed in the related art, the influences of differences between melting points and the like on the densities after firing may lead to different suitable ranges of particle diameters. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] JP 6948676

[0008] Cited non-patent literature

[0000] Solid State Ionic 288 (2016) 248-252

[0007] Acta Crystallographica Section A 32 (1976) 751

[0007] NACALAI TESQUE, INC., purity 99.0% by mass [0087, 0088, 0090, 0093, 0095, 0097, 0098, 0099, 0100, 0101, 0102, 0104, 0105, 0107, 0108, 0110, 0111, 0113, 0117, 0118, 0120, 0128, 0136, 0140, 0141, 0155, 0157, 0169, 0171, 0179, 0183, 0187, 0188, 0190, 0193, 0195, 0197, 0198, 0199, 0200, 0201, 0203, 0204, 0206, 0207, 0209, 0210, 0212, 0216, 0217, 0224, 0228, 0232, 0233, 0235, 0238, 0240, 0243, 0244, 0245, 0247, 0248, 0253, 0254, 0256, 0260, 0261, 0263, 0269] KANTO CHEMICAL CO., INC., Purity 99.5% [0087, 0088, 0090, 0093, 0098, 0099, 0101, 0102, 0104, 0105, 0107, 0110, 0111, 0113, 0118, 0128, 0136, 0140, 0141, 0155, 0171, 0179, 0183, 0187, 0188, 0190, 0193, 0198, 0199, 0200, 0203, 0204, 0206, 0207, 0209, 0212, 0216, 0217, 0224, 0232, 0233, 0235, 0238, 0240, 0243, 0244, 0247, 0248, 0253, 0254, 0256, 0263, 0269] Kojundo Chemical Laboratory Co., Ltd., Purity 99.9% by mass [0087, 0088, 0090, 0093, 0097, 0099, 0102, 0105, 0110, 0113, 0117, 0118, 0120, 0128, 0136, 0140, 0141, 0169, 0171, 0179, 0199, 0201, 0217, 0224, 0228, 0232, 0233, 0235, 0243, 0244, 0248, 0253, 0256, 0260, 0261, 0263, 0269] Shin-Etsu Chemical Co., Ltd., Purity 99.9% [0087, 0088, 0093, 0098, 0141, 0187, 0188, 0197, 0232, 0233] NIPPON DENKO CO., LTD., Purity 99.9% [0088, 0141, 0188, 0233] MITSUI MINING & SMELTING CO., LTD., Purity 99.9% [0088, 0136, 0141, 0188, 0233] New Metals and Chemicals Corporation, Ltd., Purity 99.9% [0090, 0190, 0235] Shinko Chemical Co., Ltd., Purity 99% by mass [0093, 0104, 0193, 0203, 0238, 0247] Mitsuwa Chemicals Co., Ltd., Purity 99.9% [0093, 0155, 0193, 0238] KANTO CHEMICAL CO., INC., Purity 99.5 mass% [0095, 0100, 0108, 0117, 0169, 0195, 0197, 0201, 0210, 0228, 0245, 0260, 0261] Kojundo Chemical Laboratory Co., Ltd., Purity 99.9 mass% [0095, 0098, 0100, 0101, 0102, 0111, 0155, 0240, 0244, 0245, 0254] Wako Pure Chemical Industries, Ltd., Purity 95.0 mass% [0095, 0195, 0240] TOHO TITANIUM CO., LTD., Purity 99% [0095, 0195, 0240] Wako Pure Chemical Industries, Ltd., Purity 99.9%

[0097] Ube Material Industries, Ltd., Purity 99.0 mass% [0098, 0099, 0197, 0198, 0243] Wako Pure Chemical Industries, Ltd., Purity 99.9% by mass [0099, 0100, 0107, 0108, 0198, 0206, 0207, 0243] KANTO CHEMICAL CO., INC., Purity 97.0 mass% [0099, 0198, 0243] KANTO CHEMICAL CO., INC., Purity 80.0 mass% [0100, 0101, 0102, 0199, 0200, 0201, 0244, 0245] Shin-Etsu Chemical Co., Ltd., Purity 99.9 mass% [0101, 0105, 0108, 0113, 0117, 0118, 0169, 0200, 0204, 0207, 0212, 0216, 0245, 0248, 0256, 0260, 0261] Kojundo Chemical Laboratory Co., Ltd., Purity 99.9% by mass [0104, 0107, 0118, 0120, 0171, 0247, 0261, 0263] MITSUI MINING & SMELTING CO., LTD, Purity 99.9% [0104, 0203, 0247] KANTO CHEMICAL CO., INC., Purity 99% by mass [0104, 0107, 0203, 0206, 0247] New Metals and Chemicals Corporation, Ltd., Purity 99.9% [0107, 0206] ojundo Chemical Laboratory Co., Ltd, Purity 99.9% by mass

[0108] Wako Pure Chemical Industries, Ltd., Purity 99% by mass [0108, 0207] Shin-Etsu Chemical Co., Ltd., Purity 95% by mass [0110, 0111, 0113, 0120, 0171, 0183, 0187, 0188, 0190, 0198, 0204, 0207, 0209, 0210, 0212, 0216, 0224, 0253, 0254, 0256] Wako Pure Chemical Industries, Ltd., Purity 99.0 mass% [0111, 0117, 0169, 0210, 0216, 0254, 0260] KANTO CHEMICAL CO., INC., Purity 99.0 mass% [0113, 0212, 0256] Wako Pure Chemical Industries, Ltd., Purity 90.0 mass% [0117, 0118, 0169, 0216, 0260, 0261] KANTO CHEMICAL CO., INC., Purity 99.5% by mass

[0120] Kojundo Chemical Laboratory Co., Ltd., Purity 98% by mass [0120, 0171, 0217, 0263] MITSUI MINING & SMELTING CO., LTD., Purity 99.9% [0155, 0183, 0228] Shin-Etsu Chemical Co., Ltd., Purity 95% by mass [0193, 0195, 0197, 0199, 0200, 0201, 0210] Shin-Etsu Chemical Co., Ltd., Purity 95% by mass [0203, 0212, 0217, 0263] Shin-Etsu Chemical Co., Ltd.) Purity 95 mass%

[0206] Shin-Etsu Chemical Co., Ltd., Purity 99.9% by mass

[0217] Kojundo Chemical Laboratory Co., Ltd., Purity 99.9% by mass

[0238]

Claims

[1] Ionic conductive solid having an oxide represented by a general formula: Li 6+a-c-2d X 1-a-b-c-d M1 a M2 b M3 c M4 d B 3 O 9 (in the formula, X is at least one metal element selected from the group consisting of Lu, Ho, Er and Tm, M1 is at least one metal element selected from the group consisting of Mg, Mn, Zn, Ni, Ca, Sr and Ba, M2 is at least one metal element selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu, In, Fe and Sc, M3 is at least one metal element selected from the group consisting of Zr, Ce, Hf, Sn and Ti, M4 is at least one metal element selected from the group consisting of Nb and Ta, and a is 0.000 ≤ a ≤ 0.800, b is 0.000 ≤ b ≤ 0.900, c is 0.000 ≤ c ≤ 0.800, d is 0.000 ≤ d ≤ 0.800, and a, b, c and d are real numbers satisfying 0.000 ≤ a + b + c + d < 1.000, provided that a case where X and M2 are the same metal elements is excluded). [2] The ion-conductive solid according to claim 1, wherein the 1-abcd is 0.300 ≤ 1-abcd. [3] The ion-conductive solid according to claim 1 or 2, wherein the 1-abcd is 0.500 ≤ 1-abcd. [4] The ion-conductive solid according to any one of claims 1 to 3, wherein a is 0.000 ≤ a ≤ 0.

400. [5] The ion-conductive solid according to any one of claims 1 to 4, wherein b is 0.000 ≤ b ≤ 0.

500. [6] The ion-conductive solid according to any one of claims 1 to 5, wherein c is 0.000 ≤ c ≤ 0.

400. [7] The ion-conductive solid according to any one of claims 1 to 6, wherein d is 0.000 ≤ d ≤ 0.

400. [8] The ion-conductive solid according to any one of claims 1 to 7, wherein the ion-conductive solid has a volume-average particle diameter of 0.1 µm or more and 28.0 µm or less. [9] Solid-state battery comprising at least: a cathode; an anode; and an electrolyte, wherein at least one selected from the group consisting of the cathode, the anode and the electrolyte comprises the ion-conductive solid according to any one of claims 1 to 8. [10] The solid-state battery according to claim 9, wherein at least the electrolyte comprises the ion-conductive solid.