JP6321443B2 - Capacitor and manufacturing method thereof - Google Patents

Description

  The present invention relates to a capacitor (capacitor) that stores and discharges electric charge, and more particularly, to a capacitor using a lithium ion conductive solid electrolyte material and a method for manufacturing the same.

  Conventionally, as a capacitor using an electrolyte material, a capacitor using an electrolytic solution is known, but in recent years, apart from this, a pair of electrodes are provided on the surface of the solid electrolyte body, and the solid electrolyte body As a material, an electric double layer capacitor technology using an inorganic solid electrolyte has been proposed (see Patent Document 1).

Patent Document 1 discloses an inorganic solid electrolyte containing a lithium (Li) ion conductive compound or a sodium (Na) ion conductive compound.
Separately, in order to manufacture a solid electrochemical device having excellent characteristics such as conductivity, Li _1-x Zr _2-x L _x (PO ₄ ) ₃ (L : V, Nb, Ta, 0.1 ≦ x ≦ 0.9) is disclosed (see Patent Document 2).

  Furthermore, a technique for manufacturing an all-solid battery having a low internal resistance and a large capacity by defining an atmosphere during firing of a lithium ion conductive solid electrolyte is also disclosed (see Patent Document 3).

JP 2008-130844 A JP-A-2-250264 JP 2007-227362 A

However, the above-described prior art has the following problems, and improvements are desired.
When manufacturing a new solid capacitor using a lithium ion conductive solid electrolyte material, in order to reduce the cost, an inexpensive electrode material is used and the lithium ion conductive solid electrolyte material and the electrode material are stacked. A method of forming a body and firing the laminate is conceivable.

  Inexpensive electrode materials include, for example, base metals such as Ni, Fe, and Cu. However, these base metal materials are easily oxidized during firing, and therefore need to be fired at a low oxygen partial pressure so as not to be oxidized during firing. . Therefore, the lithium ion conductive solid electrolyte material constituting the laminate also needs to be excellent in sinterability at a low oxygen partial pressure.

By the way, as a general material of an oxide-based lithium ion conductive solid electrolyte, Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ [LAGP], Li _1.3 Al _0.3 Ti _1.3 (PO ₄ ) ₃ [LATP], Li _3x La _{2 / 3-x} Ti _{1 / 3-x} O ₃ [LLT], Li ₇ La ₃ Zr ₂ O ₁₂ [LLZ] and the like.

However, since LAGP has a decomposition oxygen partial pressure of GeO ₂ close to the oxidation-reduction oxygen partial pressure of Ni, GeO ₂ may be decomposed when firing is performed so that Ni is not oxidized.
Moreover, since LATP and LLT contain Ti which is inferior in reduction resistance, there is a problem that firing at a low oxygen partial pressure is difficult.

Furthermore, since LLZ is highly reactive with water, there is a problem that firing in a humidified atmosphere for adjusting the oxygen partial pressure during firing and improving binder removal properties is difficult.
Although Patent Documents 1 and 2 describe firing in an air atmosphere, there is no description regarding simultaneous firing of a lithium ion conductive solid electrolyte material and an electrode material in a reducing atmosphere.

Patent Document 3 describes oxygen partial pressure during firing, but the solid electrolyte material is Li _{1 + x} MIII _x TiIV _2-x (PO ₄ ) ₃ (MIII: Al, Y, Ga, In , At least one selected from La, 0 ≦ x ≦ 0.6), and includes Ti which is inferior in resistance to reduction, and therefore, firing at a low oxygen partial pressure is difficult. The specified oxygen partial pressure is such that the average oxygen partial pressure (P1) atm and the firing temperature (T) ° C. satisfy −0.0310T + 33.5 ≦ log P1 ≦ −0.0300T + 38.1, and 900 At the firing temperature of 0 ° C., the oxygen partial pressure is as high as 5.6 ≦ logP1 ≦ 11.1. Therefore, the electrode material may be oxidized during simultaneous firing with Ni or Fe.

  The present invention has been made in order to solve the above-described problems, and its purpose is excellent even when an electrode material containing a base metal and a lithium ion conductive solid electrolyte material are baked and manufactured in a low oxygen atmosphere. It is an object to provide a capacitor having the above characteristics and a method for manufacturing the same.

(1) The present invention provides, as a first aspect, a capacitor including a solid electrolyte body and a plurality of electrodes formed on the solid electrolyte body and arranged to face each other with the solid electrolyte body interposed therebetween. The electrode includes at least one metal material selected from Cu, Ni, and Fe, and the solid electrolyte body is a lithium ion conductive solid electrolyte, Li _α Zr _β M _γ (PO ₄ ) ₃ (where M is at least one metal selected from Nb and Ta, and α, β, and γ are 0.5 ≦ α ≦ 1, 0.1 ≦ γ / β ≦ 0.5, α > 1-γ) is contained in an amount of 50% by volume or more.

In the capacitor according to the first aspect, the electrode includes at least one metal material selected from Cu, Ni, and Fe, and the solid electrolyte body is Li _α Zr that satisfies the above-described condition of being a lithium ion conductive solid electrolyte. _β M _γ (PO ₄ ) ₃ (hereinafter sometimes referred to as LZMP) is contained in an amount of 50% by volume or more.

As a result, even when Cu, Ni, or Fe, which is a base metal that is inexpensive but easily oxidized, is used as an electrode material, the oxygen material has a low oxygen partial pressure (for example, an oxygen partial pressure of 1 × 10 ⁻¹² MPa or less). Since the solid electrolyte body can be sufficiently sintered, a capacitor having high performance can be realized.

That is, as will be apparent from the experimental examples described later, a capacitor having a high ionic conductivity and a large capacitance can be realized.
Thus, according to the first aspect, a solid electrolyte body having good sinterability and high ionic conductivity can be obtained even in a reducing atmosphere having a low oxygen partial pressure that can be co-fired with a base metal such as Ni. This makes it possible to manufacture a solid capacitor having a large capacitance.

Here, the reason why the solid electrolyte body is employed will be described in more detail.
As a condition of the solid electrolyte body material that can obtain good sinterability even in a reducing atmosphere, it does not contain a compound that decomposes by its oxygen partial pressure, does not contain an element that causes a valence change by the oxygen partial pressure, etc. Conditions are mentioned.

Further, it is considered that the solid electrolyte body material needs to have low reactivity with water in order to have resistance to humidification for adjusting the oxygen partial pressure and improving the binder removal property.
On the other hand, LZMP (LZNbP, LZTaP), which is a solid electrolyte body used in the first embodiment, does not contain a compound (for example, Ge) that easily decomposes, and an element (for example, Ti) that easily changes its valence. Not included. Therefore, by controlling α and γ / β to satisfy the condition of α> 1-γ and controlling to the above-mentioned prescribed numerical values, even when fired in a reducing atmosphere with a low oxygen partial pressure, good sinterability is obtained. Since it is obtained and has excellent ionic conductivity, it is suitable as a solid electrolyte material for a solid capacitor.

Next, the meaning of numerical limitation in the first aspect will be described.
The reason why α is defined as 0.5 ≦ α ≦ 1 is that when α is less than 0.5, the sinterability in a reducing atmosphere with a low oxygen partial pressure is poor. This is because the compound is formed at the grain boundary and the ionic conductivity is deteriorated.

  The reason why γ / β is defined as 0.1 ≦ γ / β ≦ 0.5 is that when M is small with respect to Zr and γ / β is less than 0.1, the ionic conductivity is greatly deteriorated. Conversely, if M is large and γ / β is more than 0.5, the sinterability in a reducing atmosphere with a low oxygen partial pressure is deteriorated.

The reason for defining α> 1-γ is that if α is larger than 1-γ, the amount of Li is larger than the stoichiometric ratio, so that the sinterability is improved. This is because sex is greatly deteriorated.
The reason why the lithium ion conductive solid electrolyte is defined to be 50% by volume or more is that when it is 50% by volume or more, the function as a solid electrolyte can be sufficiently exerted, and high ion conductivity can be realized, and a high electrostatic capacity. This is because it can be secured.

(2) As a second aspect of the present invention, the metal material is Ni.
In the second aspect, since the metal material of the electrode is Ni, the cost is low, the melting point is higher than that of Cu, and the advantage that it is difficult to oxidize (during manufacturing, etc.) compared to Fe. .

(3) As a third aspect of the present invention, the electrode includes the lithium ion conductive solid electrolyte.
In the third aspect, since the electrode material includes a metal material and a lithium ion conductive solid electrolyte (which is a solid electrolyte body material), the electrode material and the solid at the time of firing (at the time of simultaneous firing of the electrode and the solid electrolyte body) The shrinkage behavior with the electrolyte body material becomes closer. Therefore, there exists an advantage that the adhesiveness (joinability) of an electrode and a solid electrolyte body becomes high.

  The ratio of the lithium ion conductive solid electrolyte is preferably in the range of 5 to 30% by volume with respect to the entire electrode. If it is this range, sufficient electroconductivity as an electrode and high adhesiveness can be made compatible.

(4) The present invention provides, as a fourth aspect, the method for manufacturing a capacitor according to any one of the first to third aspects, wherein the unsintered electrolyte body is the solid electrolyte body, and the unsintered electrolyte body. Forming a green laminate having a plurality of green electrodes including the metal material to be the electrodes arranged to face each other via an oxygen partial pressure of 1 × 10 ^{− And} firing in an atmosphere of ¹² MPa or less.

In the fourth aspect, the unfired laminate is fired in an atmosphere (reducing atmosphere) having a low oxygen partial pressure of 1 × 10 ⁻¹² MPa or less while suppressing oxidation of the metal material of the electrode. The solid electrolyte body can be sufficiently sintered.

As a result, it is possible to easily manufacture a capacitor having high performance (for example, high ionic conductivity of the solid electrolyte body, large capacitance) while reducing the cost.

BRIEF DESCRIPTION OF THE DRAWINGS The capacitor of embodiment is shown, (a) is the perspective view, (b) is sectional drawing (AA sectional drawing) which fractures | ruptures and shows a capacitor in the thickness direction. The pellet-shaped sample produced by the experiment example is shown, (a) is the perspective view, (b) is sectional drawing (BB sectional drawing) which fractures | ruptures and shows the sample in the thickness direction.

Hereinafter, a capacitor and a manufacturing method thereof according to an embodiment of the present invention will be described.
[Embodiment]
In the present embodiment, a multilayer ceramic chip capacitor will be described as an example of the capacitor.

a) First, the configuration of the capacitor of this embodiment will be described.
As schematically shown in FIG. 1, the capacitor 1 of the present embodiment is a rectangular parallelepiped multilayer ceramic chip capacitor in which a plurality of (for example, 50) solid electrolyte layers 3 are stacked (a dielectric material of a base material). The solid electrolyte body 5, a plurality of electrodes (internal electrodes) 7 disposed between the solid electrolyte layers 3, and both ends of the solid electrolyte body 5 in the longitudinal direction (the left-right direction in FIG. 1B). A pair of external electrodes 9 is provided.

Hereinafter, a configuration other than the external electrode 9, that is, a sintered body in which the solid electrolyte layer 3 and the internal electrode 7 are alternately stacked is referred to as a capacitor body 11.
Among these, the plurality of internal electrodes 7 include a plurality of first internal electrodes 7a connected to one first external electrode 9a, and a plurality of second internal electrodes 7b connected to the other second external electrode 9b. The first internal electrode 7a and the second internal electrode 7b are arranged in a comb shape so as to intervene with each other.

The solid electrolyte body 5 is a lithium ion conductive solid electrolyte, Li _α Zr _β M _γ (PO ₄ ) ₃ (where M is at least one metal selected from Nb and Ta, and α, β Γ includes 0.5 ≦ α ≦ 1, 0.1 ≦ γ / β ≦ 0.5, α> 1-γ) of 50% by volume or more.

  The solid electrolyte body 5 is preferably all composed of the lithium ion conductive solid electrolyte, but the other components are at least one selected from Nb, Ta, Li, Zr, and P. An oxide containing an element may be included. For example, lithium zirconate, zirconium phosphate, or the like may be included.

The internal electrode 7 includes at least one metal material selected from Cu, Ni, and Fe. For example, an electrode made of Ni can be employed.
The internal electrode 7 may contain the lithium ion conductive solid electrolyte in a range of, for example, 30% by volume or less.

Further, although not shown, the external electrode 9 is formed by forming a Ni plating layer and a Sn plating layer on the surface of a lower layer made of Ni in contact with each internal electrode 7.
b) Next, a method for manufacturing the capacitor 1 of the present embodiment will be described.

<Calcined powder production process>
First, in order to produce LZMP having the above composition that is the solid electrolyte body 5, for example, lithium carbonate, zirconium oxide, and so on to have a molar ratio of Li, Zr, and Nb (or Ta) shown in Tables 1 and 2 below. A predetermined amount of niobium oxide (or tantalum oxide) and diammonium hydrogen phosphate was weighed and mixed to prepare a mixed material, and the mixed material was mixed with ethyl alcohol using a nylon pot and zirconia cobblestone.

After the mixture was dried, it was calcined with a platinum crucible in an air atmosphere at a maximum temperature of 1000 ° C. for 2 hours to prepare a calcined powder of LZMP having a predetermined component ratio.
<Crushed powder preparation process>
Next, the calcined powder was pulverized with ethyl alcohol and a nylon pot and zirconia spherulite for 15 hours and dried to prepare a pulverized powder having a predetermined component ratio.

<Slurry production process>
Next, the pulverized powder, a binder (acrylic resin), and a plasticizer (dioctyl phthalate) were mixed in a methyl ethyl ketone / toluene mixed solvent to prepare a slurry.

<Sheet preparation process>
Next, the slurry was applied to a PET carrier film Si-treated on one side by a doctor blade method to produce a 30 μm thick sheet.

  And the material of Ni electrode used as the internal electrode 7 was printed on the one surface of this sheet with the predetermined pattern by screen printing. The material for the Ni electrode is a paste obtained by adding a binder and a solvent to Ni powder.

<Laminated body production process>
Next, a predetermined number (for example, 50 sheets) of the sheets on which the Ni electrode material is screen-printed are stacked so as to have a predetermined structure (laminated structure) of the solid electrolyte body 5, and the solid electrolyte body material and the Ni electrode material are stacked. A laminate was prepared.

<Baking process>
Next, the laminate was heated to 300 ° C. in an air atmosphere to perform a binder removal treatment, and then humidified through a wetter (30 ° C.) in a mixed gas atmosphere of 0.5 (volume)% H ₂ / N ₂ ( In a reducing atmosphere, firing was performed at a maximum temperature of 1000 ° C. for 2 hours.

The oxygen partial pressure during firing is 1 × 10 ⁻¹⁴ MPa. Note that oxygen in the firing atmosphere is derived from an equilibrium reaction between hydrogen and water vapor, and this oxygen partial pressure can be determined by, for example, a zirconia oxygen sensor.

As a result, a capacitor body 11 which is a sintered body in which the solid electrolyte layer 3 and the internal electrode 7 are laminated is obtained.
<External electrode manufacturing process>
Next, as in the conventional case, Ni paste is applied and baked as a material for the lower layer of the external electrode 9 at both ends in the longitudinal direction of the capacitor body 11, and then Ni plating and Sn plating are performed. 9 was formed.

Thereby, the capacitor 1 of this embodiment was completed.
c) Next, the effect of the capacitor 1 and the manufacturing method thereof according to the present embodiment will be described.
In the capacitor 1 of the present embodiment, the internal electrode 7 includes at least one metal material selected from Cu, Ni, and Fe, and the solid electrolyte body 5 satisfies the above-described condition of being a lithium ion conductive solid electrolyte. _li α Zr β M γ a (PO _{4) 3,} and includes more than 50 vol%.

Thereby, as a material of the internal electrode 7, Cu is a base metal that is inexpensive but easily oxidized,
Even when Ni or Fe is used, since the solid electrolyte body 5 can be sufficiently sintered at a low oxygen partial pressure at the time of production, the capacitor 1 having high performance can be realized.

That is, as is clear from the experimental examples described later, the capacitor 1 having a high ionic conductivity and a large capacitance can be realized.
In particular, when Ni is used as the material for the internal electrode 7, the cost is low, the melting point is higher than that of Cu, and it is less likely to oxidize (during manufacture) than Fe. There is.

  In addition, when the metal material and the LZMP are included as the material of the internal electrode 7, the shrinkage behavior between the material of the internal electrode 7 and the material of the solid electrolyte body 5 becomes close at the time of simultaneous firing. There is an advantage that adhesion (bondability) between the solid electrolyte body 5 and the solid electrolyte body 5 is increased.

Further, when the capacitor 1 is manufactured, as described above, the unfired laminate is fired in a reducing atmosphere having an oxygen partial pressure of 1 × 10 ⁻¹² MPa or less, so that the metal material of the internal electrode 7 is oxidized. The solid electrolyte body 5 can be sufficiently sintered while being suppressed.

Thereby, it is possible to easily manufacture the capacitor 1 having high performance (for example, high ionic conductivity and large capacitance of the solid electrolyte body 5) while reducing the cost.
d) Next, experimental examples conducted to confirm the effects of the present invention will be described.

[Experimental Example 1]
In Experimental Example 1, the sintered body density and ionic conductivity of the solid electrolyte body constituting the capacitor were examined.

<Sample preparation method>
First, a method for manufacturing a sample used in Experimental Example 1 will be described.
First, lithium carbonate, zirconium oxide, niobium oxide (or tantalum oxide), and diammonium hydrogen phosphate are weighed in predetermined amounts so that the molar ratio of Li, Zr, and Nb (or Ta) shown in Tables 1 and 2 below is obtained. Thus, a mixed material was prepared, and the mixed material was mixed with ethyl alcohol using a nylon pot and zirconia spherulite.

Next, after drying the mixture, it was calcined with a platinum crucible in the air at a maximum temperature of 1000 ° C. for 2 hours to obtain a calcined powder of LZMP having a predetermined component ratio.
Next, the calcined powder was pulverized for 15 hours together with ethyl alcohol using a nylon pot and zirconia spherulite, and dried to obtain a pulverized powder having a predetermined component ratio.

  Next, the pulverized powder was uniaxially pressed at a pressure of 5 MPa using a cylindrical mold having a diameter of 12 mm, and further hydrostatically pressed (CIP) at a pressure of 150 MPa to produce a disk-shaped pellet.

Next, the pellets were fired in a mixed gas atmosphere (reducing atmosphere) of 0.5% H ₂ / N ₂ that was humidified through a wetter (30 ° C.) at a maximum temperature of 1000 ° C. for 2 hours. The oxygen partial pressure during firing is 1 × 10 ⁻¹⁴ MPa.

  Thereby, as shown in FIG. 2, the solid electrolyte body (23) which is a solid electrolyte sintered compact of (phi) 10 mm x thickness 1mm was obtained. That is, samples (Examples 1 to 10) of solid electrolyte bodies used for density measurement were obtained.

Further, a pair of electrodes (25) are formed on the surfaces of both main surfaces of the solid electrolyte body by Au sputtering.
, 27), a sample of the pellet-shaped capacitor (21) was obtained. That is, the sample (Examples 1-10) of the capacitor used for ion conductivity measurement was obtained.

Furthermore, as a comparative example, a sample outside the scope of the present invention was also produced by the sample production method described above.
In addition, Examples 1-10 of Table 1 and Table 2 are samples within the scope of the present invention, and Comparative Examples 1-11 are samples outside the scope of the present invention. Among these, Examples 1 to 5 and Comparative Examples 1 to 6 are examples in which M is Nb, and Examples 6 to 10 and Comparative Examples 7 to 11 are examples in which M is Ta.

<Evaluation method>
Next, an evaluation method using the sample will be described.
-Density measurement About each sample of the said solid electrolyte body, the density measurement was performed by the Archimedes method using the pure water. The results are shown in Tables 1 and 2 below.

-Ionic conductivity measurement About each sample of the said capacitor, the ionic conductivity (ionic conductivity) of each sample was measured by the alternating current impedance method. The impedance was measured using an Agilent impedance analyzer 4294A at a measurement voltage of 100 mV and a measurement frequency of 40 Hz to 110 MHz, and the ionic conductivity was calculated from the resistance value obtained from the arc of the Cole-Cole plot and the sample dimensions. The results are shown in Tables 1 and 2 below.

[Experiment 2]
In this experimental example 2, the capacitance of the capacitor (multilayer ceramic chip capacitor) of the above embodiment was examined.

<Sample preparation method>
The method for producing a capacitor sample is basically the same as the method for producing a capacitor in the above-described embodiment, so that the molar ratio of Li, Zr, and Nb (or Ta) shown in Tables 1 and 2 below is obtained. In addition, lithium carbonate, zirconium oxide, niobium oxide (or tantalum oxide), and diammonium hydrogen phosphate are weighed in predetermined amounts, and the same “calcined powder preparation step”, “pulverized powder preparation step”, “slurry preparation step” ”,“ Sheet manufacturing process ”,“ Laminate manufacturing process ”,“ Baking process ”,“ External electrode manufacturing process ”, a capacitor sample was prepared.

That is, samples of Examples 1 to 10 within the scope of the present invention shown in Tables 1 and 2 were prepared.
Samples of Comparative Examples 1 to 11 outside the scope of the present invention shown in Tables 1 and 2 were prepared.
<Evaluation method>
The capacitance of the capacitor sample was measured by a DC constant potential method. The capacitance is measured by using an ADC ultrahigh resistance / microammeter R8340A and an Agilent digital multimeter 34410A, charging for 1 hour at a charging voltage of 2.5 V and 1.0 V, discharging, and discharging charge. The capacitance was calculated from the amount. The results are shown in Tables 1 and 2 below.

  In Tables 1 and 2, for the samples of Experimental Example 1 and Experimental Example 2, samples having the same composition of the solid electrolyte body are indicated by the same Example and Comparative Example numbers. That is, the sintered body density and ionic conductivity are experimental results using pellet samples, and the capacitance is the experimental results using multilayer ceramic chip capacitor samples (the same applies to other tables below). Is).

この表１、表２から明らかなように、本発明の範囲のキャパシタは、焼結体密度が高く、しかも、イオン伝導度が高く、特に静電容量が大きく好適であった。

As is apparent from Tables 1 and 2, capacitors within the scope of the present invention were suitable because of their high sintered body density, high ionic conductivity, and particularly high capacitance.

[Experiment 3]
In this Experimental Example 3, the samples (Example 11) shown in Table 3 below were prepared in the same manner as in the above Experimental Examples 1 and 2, and evaluated in the same manner. The results are shown in Table 3 below.

However, in this Experimental Example 3, a material containing both Nb and Ta metals was used as M in Li _α Zr _β M _γ (PO ₄ ) ₃ which is a lithium ion conductive solid electrolyte. The mass ratio of Nb and Ta was 1: 1.

この表３から明らかなように、本発明の範囲のキャパシタは、Ｍとして、Ｎａ及びＴａの両方を用いた場合でも、焼結体密度が高く、しかも、イオン伝導度が高く、特に静電容量が大きく好適であった。

As is apparent from Table 3, the capacitors in the range of the present invention have a high sintered body density and high ionic conductivity even when both Na and Ta are used as M. Was suitable.

[Experimental Example 4]
In Experimental Example 4, the samples (Examples 12 and 13) shown in Table 4 below were prepared in the same manner as in Experimental Example 1 and Experimental Example 2, and evaluated in the same manner. The results are shown in Table 4 below.

  However, in Experimental Example 4, Nb is used as M of the lithium ion conductive solid electrolyte (LZMP), and the ratio of LZMP in the solid electrolyte body as the base material is 50% by volume and 70% by volume. is there. The component other than LZMP is an oxide composed of any one of Li, Zr, Nb, and P.

この表４から明らかなように、本発明の範囲のキャパシタは、ＭとしてＮｂを用い、ＬＺＭＰの割合を、５０体積％及び７０体積％とした場合でも、焼結体密度が高く、しかも、イオン伝導度が高く、特に静電容量が大きく好適であった。

As apparent from Table 4, the capacitors in the range of the present invention have high sintered body density even when Nb is used as M and the ratio of LZMP is 50% by volume and 70% by volume. The conductivity was high and the capacitance was particularly large, which was suitable.

[Experimental Example 5]
In Experimental Example 5, the samples (Examples 14 and 15) shown in Table 5 below were produced in the same manner as in Experimental Example 1 and Experimental Example 2, and evaluated in the same manner. The results are shown in Table 5 below.

However, in this Experimental Example 5, as M of the lithium ion conductive solid electrolyte (LZMP), T
In addition to using a, the ratio of LZMP in the solid electrolyte body as the base material is 50% by volume and 70% by volume. The component other than LZMP is an oxide composed of any one of Li, Zr, Ta, and P.

この表５から明らかなように、本発明の範囲のキャパシタは、ＭとしてＴａを用い、ＬＺＭＰの割合を、５０体積％及び７０体積％とした場合でも、焼結体密度が高く、しかも、イオン伝導度が高く、特に静電容量が大きく好適であった。

As can be seen from Table 5, the capacitors within the scope of the present invention have a high sintered body density even when Ta is used as M and the ratio of LZMP is 50% by volume and 70% by volume. The conductivity was high and the capacitance was particularly large, which was suitable.

[Experimental Example 6]
A sample of Example 16 was produced in the same manner as in the above embodiment. However, the composition of LZMP was the same as in Example 1, and the oxygen partial pressure during firing was 1 × 10 ⁻¹² MPa. And when the electrostatic capacitance was measured similarly to Experimental Example 2, a large electrostatic capacitance (4000 μF under the condition of a charging voltage of 2.5 V) was obtained.

[Experimental Example 7]
A sample of Example 17 was produced in the same manner as in the above embodiment. However, the composition of LZMP was the same as in Example 1, and the electrode materials were Ni and LZMP (where LZMP was 30% by volume). And when the electrostatic capacitance was measured similarly to Experimental Example 2, a large electrostatic capacitance (4500 μF under the condition of a charging voltage of 2.5 V) was obtained.

  In addition, this invention is not limited to the said embodiment and Example at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from this invention.

DESCRIPTION OF SYMBOLS 1, 21 ... Capacitor 3 ... Solid electrolyte layer 5, 23 ... Solid electrolyte body 7, 7a, 7b, 9, 9a, 9b, 25, 27 ... Electrode

Claims (4)

A solid electrolyte body;
A plurality of electrodes formed on the solid electrolyte body and arranged to face each other via the solid electrolyte body;
A capacitor comprising:
The electrode includes at least one metal material selected from Cu, Ni, and Fe;
The solid electrolyte body is a lithium ion conductive solid electrolyte, Li _α Zr _β M _γ (PO ₄ ) ₃ (where M is at least one metal selected from Nb and Ta, α, β, γ includes 0.5 ≦ α ≦ 1, 0.1 ≦ γ / β ≦ 0.5, α> 1-γ) by 50% by volume or more.   The capacitor according to claim 1, wherein the metal material is Ni.   The capacitor according to claim 1, wherein the electrode includes the lithium ion conductive solid electrolyte. It is a manufacturing method of the capacitor according to any one of claims 1 to 3,
An unsintered laminated body having an unsintered electrolyte body to be the solid electrolyte body and a plurality of unsintered electrodes including the metal material to be the electrodes disposed to face each other through the unsintered electrolyte body is formed. Process,
Firing the green laminate in an atmosphere having an oxygen partial pressure of 1 × 10 ⁻¹² MPa or less;
A method for producing a capacitor, comprising:

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