JPH0640495B2 - All solid state secondary battery - Google Patents

Description

TECHNICAL FIELD The present invention relates to an all solid state secondary battery.

2. Description of the Related Art Since a battery currently uses a liquid as an electrolyte, problems such as electrolyte leakage cannot be eliminated. In order to solve these problems and improve reliability, and to reduce the size and thickness of the device, attempts have been made in various fields to use a solid electrolyte instead of a liquid electrolyte to make the battery all solid.

The solid electrolyte used here includes those having copper ion conductivity, silver ion conductivity, lithium ion conductivity, and the like. For example, a RbCL-CuCl-CuI-based copper ion conductive solid electrolyte is used, and an electrode active material is used. As a positive electrode, a transition metal disulfide having a layered structure such as titanium disulfide (TiS ₂ ) or niobium disulfide (NbS ₂ ) or a copper chevrel phase compound represented by Cu _x Mo ₆ S ₉ is used as a positive electrode, and a metal copper is used as a negative electrode. An example thereof is an all-solid secondary battery using a copper chevrel phase compound or the like.

However, as described above, RbCl-Cu is used as the solid electrolyte.
When a device is constructed using a Cl-CuI-based copper ion conductive solid electrolyte, the solid electrolyte undergoes decomposition in the presence of moisture and oxygen in the atmosphere, and sulfide used as an electrode active substance is present in the presence of oxygen. Especially, it has a problem that it is easily oxidized at a high temperature.

In order to solve the above problems, a composite oxide of silver and a transition metal consisting of silver and a transition metal oxide is used as an electrode active material, and a silver ion conductive solid electrolyte is used as a solid electrolyte. The inventors have proposed a solid-state secondary battery that charges and discharges by an intercalation / deintercalation reaction.

However, when vanadium oxide is used as the transition metal oxide, the intercalation / deintercalation reaction of silver is electrochemical in the region where the content of silver in the composite oxide is low. Since a phase having a crystal structure that hardly occurs is generated, there is a problem that the energy density becomes low.

On the other hand, in the region where the silver content is high, metallic silver is mixed in the composite oxide. Therefore, there is a problem that the proportion of the phase having a crystal structure that electrochemically causes the intercalation / deintercalation reaction of silver in the weight of the electrode active material is small and the energy density is low. There is.

When a battery using a silver ion conductive solid electrolyte as the solid electrolyte and using the oxidation / reduction reaction of silver for the charge / discharge reaction is used, metallic silver produced by the reduction reaction of silver ions is more dendrite than copper or lithium. Therefore, there is a problem that dendrites grow particularly in the negative electrode during charging due to repeated charging and discharging, and short-circuiting of both electrodes is likely to occur eventually.

An object of the present invention is to solve the above problems and to provide an all-solid secondary battery having a high energy density and not causing a short circuit between both electrodes due to the growth of metallic silver dendrites.

Means for Solving the Problems The present invention provides Ag _x V ₂ O _5-y (0.
35 <x, y oxygen deficiency) and particularly silver and vanadium oxide represented by Ag _x V ₂ O _5-y (0.6 ≦ x ≦ 0.8, y is oxygen deficiency) Is used.

In addition, in order to prevent the growth of dendrites, the positive electrode is Ag _x V ₂
A composite oxide composed of silver and vanadium oxide represented by O _5-y (0.6 ≦ x ≦ 0.8, y is oxygen deficiency) is M ₁ m
and the negative electrode contains Ag _v V ₂ O _5-w (0.6 ≦ v ≦
0.8, w is an oxygen deficiency), and when M ₂ mol of a composite oxide composed of silver and vanadium oxide is included, 0.6 ≦
When x ≦ 0.7, Q ₁ = M ₁ (1.4x−0.55),
When 0.7 ≦ x ≦ 0.8, Q ₁ = M ₁ (0.6x + 0.0
1), when 0.6 ≦ v ≦ 0.7, Q ₂ = M ₂ (0.6v−
0.18), and 0.7 ≦ x ≦ 0.8, Q ₂ = M ₂ (−
0.6v + 0.66), the all-solid secondary battery is constructed so as to satisfy the condition of Q ₁ ≦ Q ₂ .

In the composite oxide composed of silver and vanadium oxide represented by Ag _x V ₂ O _5-y (y is oxygen deficiency), the crystal structure of α phase, β phase, and δ phase appears depending on the content of silver. . Among these crystal phases, the crystal phase which shows the most electrochemical activity when combined with the silver ion conductive solid electrolyte is the δ phase. Therefore, Ag _x V ₂ O _5-y (0.35 <x, y is oxygen deficiency) having a δ-phase crystal structure is used as an electrode active material of an all solid state secondary battery using a silver ion conductive solid electrolyte. By using a composite oxide composed of silver and vanadium oxide having a composition represented by, an all-solid secondary battery having a high energy density can be constructed. Particularly, in the range represented by x ≧ 0.6, the phase represented by Ag _0.35 V ₂ O ₅ is hardly seen, and in the range represented by x ≦ 0.8, metallic silver is almost mixed in the composite oxide. It is particularly preferably used because it disappears.

The metallic silver dendrite proceeds by the reaction of Ag ⁺ + e ⁻ → Ag in the negative electrode during charging. In order to prevent the dendrite growth of metallic silver, it is necessary to completely intercalate the silver produced by the reduction reaction in the negative electrode into the complex oxide layer. The complex oxide represented by Ag _x V ₂ O _5-y (0.6 ≦ x ≦ 0.8, y is oxygen deficiency) is 0.6
When ≦ x ≦ 0.7, (1.4x−0.55) mol,
When 0.7 ≦ x ≦ 0.8 (0.6x + 0.01) mo
l silver can be deintercalated, 0.6 ≦
When x ≦ 0.7, (0.6x−0.18) mol, 0.
When 7 ≦ x ≦ 0.8 (−0.6x + 0.66) mol
Silver can be intercalated. When the reduced silver in the negative electrode during charging is completely intercalated between the layers of the composite oxide to prevent dendrite generation and to have a high energy density, the silver from the positive electrode is completely deintercalated. However, it is necessary that silver be intercalated in the negative electrode. Therefore, Ag _x V ₂ O is used as the positive electrode active material.
_5-y (0.6 ≤ x ≤ 0.8, y is oxygen deficiency), M ₁ mo
l, Ag _v V ₂ O _5-w (0.6 ≦ v ≦
0.8. When an all-solid secondary battery using M ₂ mol (where w is oxygen deficiency) is used, when 0.6 ≦ x ≦ 0.7, Q ₁ =
When M ₁ (1.4x−0.55) and 0.7 <x ≦ 0.8, Q ₁ = M ₁ (0.6x + 0.01), and 0.6 ≦ v ≦
When 0.7, Q ₂ = M ₂ (0.6v−0.18), 0.7
<V ≦ 0.8, Q ₂ = M ₂ (−0.6v + 0.66)
In the range of Q ₁ ≦ Q ₂ , even if silver is completely deintercalated from the positive electrode, silver is still able to intercalate to the negative electrode, and short circuit of both electrodes due to dendrite growth due to repeated charging and discharging. Can be prevented.

As the silver ion conductive solid electrolyte used for this electrode material, the element can be constituted by using any composition of the silver ion conductive solid electrolyte.
A compound selected from O ₃ , SiO ₂ , M ₀ O ₃ and V ₂ O ₅ and A
Since the solid electrolyte synthesized from gI and Ag ₂ O is all synthesized from a material that does not have hygroscopicity, it is not necessary to synthesize the material in a dry atmosphere. It is preferably used from the viewpoint of being stable against moisture and enabling the construction of the all-solid-state secondary battery to be performed in the atmosphere, and the weather resistance of the constructed all-solid-state secondary battery.

In addition, a compound selected from CrO ₃ , P ₂ O ₅ , B ₂ O ₃ and AgI, A
The solid electrolyte synthesized from g ₂ O contains a hygroscopic material as a raw material, but the synthesized solid electrolyte is also preferably used because it is stable against humidity.

Embodiments Embodiments of the present invention will be described below with reference to the drawings.

Example 1 First, AgI, Ag ₂ O and WO ₃ were weighed so that the molar ratio was 4: 1: 1 and mixed in an alumina mortar. This mixture was pressure-molded into pellets, which were then sealed in a Pyrex tube under reduced pressure and melted and reacted at 400 ° C. for 17 hours.
Grind the reaction product to less than 200 mesh in a mortar and
A silver ion conductive solid electrolyte represented by I · Ag ₂ WO ₄ was obtained.

Next, using vanadium oxide as silver and a transition metal oxide, a composite oxide of silver and vanadium was synthesized by the following method. Vanadium oxide represented by V ₂ O ₅ and metallic silver were weighed out in a molar ratio of 1: 0.7 and mixed in a mortar. The mixture was similarly pressure-molded into pellets, sealed in a quartz tube under reduced pressure, reacted at 600 ° C. for 48 hours, pulverized to 200 mesh or less, and a composite of silver and vanadium represented by Ag _0.7 V ₂ O _5. An oxide was obtained.

In order to evaluate the characteristics of the composite oxide composed of silver and vanadium oxide thus obtained as a positive electrode active material, an all solid state secondary battery was constructed by the following method.

The solid electrolyte obtained as described above and each composite oxide were mixed at a weight ratio of 1: 1 to obtain a positive electrode material for an all solid state secondary battery. 200 mg of this electrode material is weighed and 4
A positive electrode pellet was obtained by pressure molding to 10 mmφ at ton / cm ² .

Further, metallic silver was used as the negative electrode active material, metallic silver powder and the solid electrolyte obtained as described above were mixed at a weight ratio of 1: 1, and 200 mg was weighed in the same manner as above.
A negative electrode pellet was obtained by pressure molding to 10 mmφ at ton / cm ² .

The positive and negative electrode pellets obtained as described above were placed through 400 mg of solid electrolyte, and the whole was 4 ton / c.
A solid battery element was obtained by press-contacting with m ² . A lead of a tin-plated copper wire was adhered to this solid battery element with a carbon paste, and the whole was sealed with an epoxy resin to obtain an all-solid secondary battery A.

Similarly, the vanadium oxide represented by V ₂ O ₅ and metallic silver are used in a molar ratio of 1: 0.3, 1: 0.5, 1: 0.6,
Weigh it so that it becomes 1: 0.65, 1: 0.8, 1: 1.0, 1: 1.2, and in the same manner as above, Ag _0.3 V ₂ O ₅ ,
Ag _0.5 V ₂ O ₅ , Ag _0.6 V ₂ O ₅ , Ag _0.65 V ₂ O ₅ , Ag
A composite oxide of silver and vanadium represented by _0.8 V ₂ O ₅ , Ag _1.0 V ₂ O ₅ , and Ag _1.2 V ₂ O ₅ was obtained, and an all solid state secondary battery B (Ag _0.3 V as an electrode active material) was obtained by the same method. ₂ O ₅ ), all-solid secondary battery C (Ag as electrode active material)
_0.5 V ₂ O ₅ ), all-solid secondary battery D (using Ag _0.6 V ₂ O ₅ as an electrode active material), all-solid secondary battery E (Ag _0.65 V ₂ O as an electrode active material) ₅ ), all-solid secondary battery F (Ag _0.8 V ₂ as an electrode active material)
O ₅ ), all-solid secondary battery G (using Ag _1.0 V ₂ O ₅ as electrode active material), all-solid secondary battery H (using Ag _1.2 V ₂ O ₅ as electrode active material) I got).

These all solid state secondary batteries A, B, C, D, E, F, G, H
1mA at 0.25V to 0.5V, 20 ° C
Was charged and discharged at a constant current. The results are shown in FIGS. 1 and 2.

In the all-solid-state secondary battery B using Ag _0.3 V ₂ O ₅ as the positive electrode active material, almost no charge and discharge can be performed, whereas all-solid-state secondary batteries A, C, D according to the present invention,
E, F, G, H can be charged and discharged, especially A
In all solid state secondary batteries A, D, E and F using a composite oxide composed of silver and vanadium oxide represented by g _x V ₂ O _5-y (0.6 ≦ x ≦ 0.8) as a positive electrode active material Has a high charge / discharge capacity, and it can be seen that when such a composite oxide is used as a positive electrode active material, an all solid state secondary battery having a high energy density can be constructed.

(Example 2) Next, in order to evaluate the characteristics of the composite oxide composed of silver and vanadium oxide obtained in Example 1 as a negative electrode active material, an all-solid secondary battery was constructed by the following method.

The silver ion conductive solid electrolyte was synthesized by the following method. AgI and Ag ₂ M ₀ O ₄ were weighed in a molar ratio of 3: 1 and mixed in an alumina mortar. This mixture was melted and reacted in a Pyrex tube at 500 ° C. for 10 hours, and then the melt was directly poured into liquid nitrogen and quenched. The reaction product obtained as described above was crushed to 200 mesh or less in a mortar to obtain a silver ion conductive solid electrolyte represented by 3AgI.Ag ₂ M ₀ O ₄ .

An all solid state secondary battery I was prepared in the same manner as in Example 1 except that the silver ion conductive solid electrolyte obtained as described above was used.
(Using Ag _0.7 V ₂ O ₅ as the electrode active material), all-solid secondary battery J (using Ag _0.3 VV ₂ O ₅ as the electrode active material), all-solid secondary battery K (electrode active material) As A
g _0.5 V ₂ O ₅ ), all solid state secondary battery L (using Ag _0.6 V ₂ O ₅ as an electrode active material), all solid state secondary battery M (Ag _0.65 V ₂ as an electrode active material) O ₅ ), all-solid secondary battery N (Ag _0.8 V ₂ as electrode active material)
O ₅ ), all-solid secondary battery O (using Ag _1.0 V ₂ O ₅ as an electrode active material), all-solid secondary battery P
(Ag _1.2 V ₂ O ₅ was used as the electrode active material) was obtained.

These all solid state secondary batteries I, J, K, L, M, N, O, P
Was charged and discharged at a constant current of 1 mA at 0.1 V to 0 V and 20 ° C. The results are shown in FIGS. 3 and 4.

In the all-solid-state secondary battery J using Ag _0.3 V ₂ O ₅ as the negative electrode active material, almost no charge and discharge can be performed, whereas all-solid-state secondary batteries I, K, L according to the present invention,
Charge, discharge can be performed with M, N, O, and P.
In all solid state secondary batteries I, L, M and N using a composite oxide composed of silver and vanadium oxide represented by g _x V ₂ O _5-y (0.6 ≦ x ≦ 0.8) as a negative electrode active material Has a high charge / discharge capacity, and it can be seen that when such a composite oxide is used as a negative electrode active material, an all-solid secondary battery with high energy density can be constructed.

(Example 3) First, AgI, Ag ₂ O, the SiO ₂ in a molar ratio of 3: 2: 1
Were weighed and mixed in an alumina mortar. This mixture was heated, melted and reacted in a glassy carbon crucible, and then the melt was directly poured into liquid nitrogen and quenched.
The reaction product obtained as described above was crushed to 200 mesh or less in a mortar to obtain a silver ion conductive solid electrolyte represented by 3AgI.Ag ₄ SiO ₄ .

Next, Ag _0.7 obtained in Example 1 as an electrode active material was used.
A composite oxide of silver and vanadium represented by V ₂ O ₅ and the silver ion conductive solid electrolyte obtained as described above are mixed at a weight ratio of 1: 1 to prepare an electrode for an all solid state secondary battery. Got the material.

100 mg of this electrode material was weighed and pressure-molded to 10 mmφ at 4 ton / cm ² to obtain a positive electrode pellet. As the negative electrode pellet, 200 mg of the same electrode material was weighed,
Similarly, what was pressure-molded to 10 mmφ at 4 ton / cm ² was used.

The positive and negative electrode pellets obtained as described above were placed through 100 mg of solid electrolyte, and the whole was 4 ton / c.
m ² at applied pressure contact to obtain a solid battery element. A lead of a tin-plated copper wire was adhered to this solid battery element with a carbon paste, and the whole was sealed with an epoxy resin to obtain an all-solid secondary battery Q.

In the thus obtained all-solid secondary battery Q,
x = v = 0.7, M ₁ = 1.9 × 10 ⁻⁴ mol, M ₂ =
3.9 × 10 ⁻⁴ mol, Q ₁ = 8.3 × 10 ⁻⁵ ,
Q ₂ = 9.3 × 10 ⁻⁵ , which satisfies the condition of Q ₁ ≦ Q ₂ according to the present invention.

As a comparative example, an all-solid secondary battery R was obtained by the same method except that 100 mg of the same electrode material as the above was pressed and molded as the negative electrode pellet.

In the thus-obtained all-solid-state secondary battery R,
x = v = 0.7, M ₁ 1.9 × 10 ⁻⁴ mol, M ₂ = 1.
9 × 10 ⁻⁴ mol, Q ₁ = 8.3 × 10 ⁻⁵ , Q ₂ =
The result is 4.7 × 10 ⁻⁵ , which does not satisfy the condition of Q ₁ ≦ Q ₂ according to the present invention.

Using the thus obtained all-solid-state secondary batteries Q and R, the charge / discharge characteristics of the battery were measured in the same manner as in Example 1. As a result of repeated charging and discharging, 1 was obtained for the all-solid-state secondary battery R.
At the 82nd cycle, a minute short circuit occurred inside the battery, and charging was not possible. On the other hand, in the all solid state secondary battery Q according to the present invention, there was no abnormality in charge / discharge characteristics even after 300 cycles.

Example 4 First, AgI, Ag ₂ O and V ₂ O ₅ were weighed so that the molar ratio was 5: 3: 2, and mixed in an alumina mortar. This mixture was heated, melted and reacted in a glassy carbon crucible, and then the melt was directly poured into liquid nitrogen and quenched. To obtain a more way ground to below 200 mesh in a mortar and the reaction product obtained 55AgI · 3Ag ₂ 0 · 2V silver ion conductive solid electrolyte represented by ₂ O _5.

Next, Ag _0.8 obtained in Example 1 as an electrode active material was used.
A composite oxide of silver and vanadium represented by V ₂ O ₅ and the silver ion conductive solid electrolyte obtained as described above are mixed in a weight ratio of 1: 3 to prepare a positive electrode material for an all solid state secondary battery. Were mixed at a ratio of 3: 1 to obtain a negative electrode material for an all-solid secondary battery.

200m each of the positive electrode material and the negative electrode material thus obtained
g was weighed and pressure-molded at 4 ton / cm ² to 10 mmφ to obtain positive and negative electrode pellets.

The positive electrode and negative electrode pellets obtained as described above were placed through 100 mg of the solid electrolyte as in Example 3, and the whole was pressed and pressed at 4 ton / cm ² to obtain a solid battery element. A lead of a tin-plated copper wire was adhered to this solid battery element with a carbon paste, and the whole was sealed with an epoxy resin to obtain an all-solid secondary battery S.

In the all solid state secondary battery S thus obtained,
x = v = 0.8, M ₁ = 1.9 × 10 ⁻⁴ mol, M ₂ =
5.6 × 10 ^-4 mol, Q ₁ = 9.1 × 10 ^-5 ,
Q ₂ = 1.0 × 10 ⁻⁴ , which satisfies the condition of Q ₁ ≦ Q ₂ according to the present invention.

As a comparative example, the composite oxide of silver and vanadium represented by Ag _0.8 V ₂ O ₅ obtained in Example 1 as the electrode active material, and the silver ion conductive solid electrolyte obtained as described above in a weight ratio of 1 In the same manner as above, except that the mixture in the ratio of 1 was used as the positive electrode material for the all-solid secondary battery,
An all-solid secondary battery T was obtained.

In the all-solid-state secondary battery T thus obtained,
x = v = 0.7, M ₁ = 3.7 × 10 ⁻⁴ mol, M ₂ =
5.6 × 10 ⁻⁴ mol, Q ₁ = 1.8 × 10 ⁻⁴ ,
Since Q ₂ = 1.0 × 10 ⁻⁴ , the condition of Q ₁ ≦ Q ₂ according to the present invention is not satisfied.

Using the thus obtained all-solid-state secondary batteries S and T, the charge / discharge characteristics of the battery were measured in the same manner as in Example 1. As a result, for the all-solid-state secondary battery T, a minute short circuit occurred inside the battery after the 107th cycle, whereas for the all-solid-state secondary battery S according to the present invention, there was no abnormality in the charge / discharge characteristics even after 300 cycles. .

Example 5 First, AgI, Ag ₂ O and B ₂ O ₃ were weighed so that the molar ratio was 1: 1: 2 and mixed in an alumina mortar. This mixture was melted and reacted in a quartz tube at 600 ° C. for 1 hour, then cast on a stainless plate and rapidly cooled. The reaction product obtained as described above was crushed to 200 mesh or less in a mortar to obtain a silver ion conductive solid electrolyte represented by AgI · Ag ₂ O · 2B ₂ O ₃ .

Next, as an electrode active material, the Ag _0.6 obtained in Example 1 was used.
A composite oxide of silver and vanadium represented by V ₂ O ₅ and the silver ion conductive solid electrolyte obtained as described above are mixed at a weight ratio of 1: 1 to obtain a positive electrode for an all solid state secondary battery. Got the material. 150 mg of this electrode material is weighed and 4 ton /
A positive electrode pellet was obtained by pressure molding into 10 mmφ in cm ² .

As the negative electrode material, Ag _0.7 obtained in Example 1 was used.
200 mg of a composite oxide of silver and vanadium represented by V ₂ O ₅ and the silver ion conductive solid electrolyte obtained as described above were mixed at a weight ratio of 1: 1 and weighed 200 mg. Negative electrode pellets were obtained by pressure molding at 4 ton / cm ² to 10 mmφ.

The positive and negative electrode pellets obtained as described above were placed through 100 mg of solid electrolyte, and the whole was 4 ton / c.
m ² at applied pressure contact to obtain a solid battery element. A lead of a tin-plated copper wire was adhered to this solid battery element with a carbon paste, and the whole was sealed with an epoxy resin to obtain an all-solid secondary battery U.

In the all-solid secondary battery U thus obtained, x
= 0.6, v = 0.7, M ₁ = 3.0 × 10 ⁻⁴ mol,
M ₂ = 3.9 × 10 ⁻⁴ mol and Q ₁ = 8.8 × 10
^-5 , Q ₂ = 9.3 × 10 ^-5 , and Q ₁ ≤Q according to the present invention.
Meet condition ₂

As a comparative example, as a negative electrode material, the composite oxide of silver and vanadium represented by Ag _0.8 V ₂ O ₅ obtained in Example 1 and the silver ion conductive solid electrolyte obtained as described above are used in a weight ratio of 1: 1. An all-solid secondary battery V was obtained in the same manner as above except that the mixture of 1: 1 was used.

In the all-solid-state secondary battery V thus obtained,
x = v = 0.6, M ₁ = 3.0 × 10 ⁻⁴ mol, M ₂ =
4.1 × 10 ⁻⁴ mol, Q ₁ = 8.8 × 10 ⁻⁵ ,
Since Q ₂ = 7.3 × 10 ² , the condition of Q ₁ ≦ Q ₂ according to the present invention is not satisfied.

Using the thus obtained all-solid secondary batteries U and V, the charge / discharge characteristics of the battery were measured in the same manner as in Example 1. As a result, for the all-solid secondary battery U, a minute short circuit occurred inside the battery at the 216th cycle, while for the all-solid secondary battery V according to the present invention, there was no abnormality in the charge / discharge characteristics even after 300 cycles. .

As described above, according to the present invention, the energy density is high,
It is possible to obtain an all-solid-state secondary battery in which both electrodes are not short-circuited by the growth of metallic silver dendrite.

[Brief description of drawings]

1 to 4 are charge / discharge characteristic diagrams of the all solid state secondary battery according to the embodiment of the present invention.

Claims (5)

[Claims] 1. A silver ion conductive solid electrolyte layer and a pair of electrodes arranged via the solid electrolyte layer, wherein at least one of the electrodes is Ag _x V ₂ O _5-y (0 .35 <x, y is oxygen deficiency), and the all-solid-state secondary battery characterized by containing the compound oxide which consists of silver and vanadium oxide. 2. A silver ion conductive solid electrolyte layer and a pair of electrodes arranged via the solid electrolyte layer, at least one of the electrodes being Ag _x V ₂ O _5-y (0 6 ≦ x ≦ 0.8, y is oxygen deficiency)
An all-solid-state secondary battery comprising a composite oxide composed of silver and vanadium oxide represented by: 3. An Ag _x V ₂ O having a silver ion conductive solid electrolyte layer and a pair of electrodes arranged via the solid electrolyte layer, wherein the positive electrode of the electrodes has a δ-phase crystal structure. _5-y (0.6 ≦ x ≦ 0.8, y is oxygen deficiency)
And a negative electrode containing Ag _v V ₂ O _5-w (0.6 ≦ x ≦ 0.8, w
Is a oxygen deficiency), and an all-solid secondary battery comprising a composite oxide composed of silver and vanadium oxide. 4. A silver ion conductive solid electrolyte layer and a pair of electrodes arranged via the solid electrolyte layer, wherein the positive electrode of the electrodes is Ag _x V ₂ O _5-y (0.6 ≦ x ≦ 0.8, y
Is a oxygen deficiency) and contains M ₁ mol of a composite oxide composed of silver and vanadium oxide, and when 0.6 ≦ x ≦ 0.7, Q ₁ = M ₁ (1.4x−0.55), 0.7 <x ≦ 0.
In case of 8, Q ₁ = M ₁ (0.6x + 0.01), and the negative electrode is Ag _v V ₂ O _5-w (0.6 ≦ v ≦ 0.8, w is oxygen deficiency)
In the case of 0.6 ≦ v ≦ 0.7, M ₂ contains M ₂ mol of the complex oxide composed of silver and vanadium oxide, and Q ₂ = M
₂ (0.6v−0.18), when 0.7 <v ≦ 0.8, when Q ₂ = M ₂ (−0.6v + 0.66), Q ₁ ≦
An all solid state secondary battery characterized by satisfying Q ₂ . 5. A silver ion conductive solid electrolyte is WO ₃ , M.
at least one compound selected from oO ₃ , SiO ₂ , V ₂ O ₅ , CrO ₃ , P ₂ O ₅ , and B ₂ O ₃ and AgI and Ag ₂
O is comprised of O, Claims 1, 2, 3 or 4
The all-solid-state secondary battery described.