WO2016067592A1

WO2016067592A1 - Lithium-air battery and lithium-air battery device

Info

Publication number: WO2016067592A1
Application number: PCT/JP2015/005387
Authority: WO
Inventors: 鈴木　洋介; 謙一郎加美; 平田　和希
Original assignee: 株式会社デンソー
Priority date: 2014-10-30
Filing date: 2015-10-27
Publication date: 2016-05-06

Abstract

This lithium-air battery (2) comprises: a negative electrode (4) comprising a negative electrode material (40) that is capable of absorbing and desorbing lithium ions; a positive electrode (3) which uses oxygen as a positive electrode active material and comprises a positive electrode material that is provided with a catalyst (31) for reducing oxygen; and a solid electrolyte layer (5) which is interposed between the negative electrode and the positive electrode and contains a solid electrolyte. At least one of charging and discharging is carried out in the presence of water in a gas phase. Namely, reduction of oxygen or an oxide is carried out in the presence of water in a gas phase. Due to this configuration, this air battery exhibits an effect of reducing the overvoltage.

Description

Lithium air battery and lithium air battery device

Cross-reference of related applications

This application is based on Japanese Patent Application No. 2014-221188 filed on October 30, 2014 and Japanese Patent Application No. 2015-192600 filed on September 30, 2015, which is described herein. Incorporate content.

The present disclosure relates to a lithium air battery and a lithium air battery device.

In recent years, with the development of portable devices such as personal computers and mobile phones, the demand for batteries as power sources has been greatly expanded. Research on lithium-air batteries using oxygen in the air as a positive electrode active material has been conducted with the aim of realizing a battery with a larger capacity. Lithium-air batteries have a high energy density.

It has been reported that lithium-air batteries exhibit a very large discharge capacity because they do not need to be filled with a positive electrode active material.

Lithium-air batteries include, for example, a positive electrode layer containing a conductive material, a catalyst, and a binder, a positive electrode current collector that collects current from the positive electrode layer, a negative electrode layer made of a metal or an alloy, and a collection of negative electrode layers. A negative electrode current collector for conducting electricity, and an electrolyte interposed between the positive electrode layer and the negative electrode layer. And it is thought that the following charge / discharge reaction advances in a lithium air battery.

[During discharge]
Negative electrode: Li → Li ⁺ + e ⁻
Positive electrode: 2Li ⁺ + O ₂ + 2e ⁻ → Li ₂ O ₂
[When charging]
Negative electrode: Li ⁺ + e ⁻ → Li
Positive electrode: Li ₂ O ₂ → 2Li ⁺ + O ₂ + 2e ⁻
Conventionally, an electrolytic solution in which a supporting electrolyte salt is dissolved in an organic solvent has been used as an electrolyte of a battery. An electrolytic solution using an organic solvent as a medium exhibits high ionic conductivity.

However, a lithium-air battery using an electrolytic solution needs to be improved in terms of structure and material to prevent a short circuit and to install a safety device that suppresses a temperature rise at the time of a short circuit in order to prevent burning of an organic solvent. In addition, since organic solvents are volatile, lithium air batteries that have a structure for taking air into the battery and that work by taking oxygen in the air into the positive electrode have problems with stability in long-term operation. It is thought that there is. That is, in the long-term operation of the lithium-air battery, the electrolyte solution may volatilize from the positive electrode. As the electrolytic solution volatilizes, it is expected that the battery performance of the lithium-air battery is increased and the battery performance is significantly reduced.

On the other hand, an all-solid-state air battery in which the electrolytic solution is changed to a solid electrolyte does not use an organic solvent in the battery. In addition, the ionic conductivity of the solid electrolyte is improved by increasing the temperature. Therefore, the safety device for preventing the temperature rise can be simplified, and the manufacturing cost and productivity are excellent. Further, in the all solid-state air battery, there is no possibility that the organic solvent volatilizes from the positive electrode. Accordingly, it is possible to prevent a decrease in battery performance due to volatilization of the organic solvent.

Patent Document 1 discloses a lithium-air battery including a negative electrode, a positive electrode including a catalyst for oxygen reduction and a first solid electrolyte layer, and a second solid electrolyte layer disposed between the negative electrode and the positive electrode. Patent Document 1 also discloses that the first solid electrolyte layer and the second solid electrolyte layer are continuous without being physically separated. However, since an organic electrolyte solution and an aqueous electrolyte solution are required on the surface of the air electrode, it has not been possible to prevent deterioration in performance due to volatilization.

In order to solve the problem of volatilization in these electrolytes, a battery having a configuration in which an aqueous solution or an electrolyte is not required has been studied.

And, it is known that a conventional lithium-air battery generates an overvoltage during charging after discharging. When overvoltage occurs, there is a problem in that the battery capacity is reduced, and as a result, the performance of the lithium-air battery is reduced.

JP 2011-96586 A

This disclosure is intended to provide a lithium-air battery and a lithium-air battery device that can suppress overvoltage and can charge and discharge a large current.

In a first aspect of the present disclosure, a lithium-air battery includes a negative electrode having a negative electrode material capable of occluding and releasing lithium ions, and a positive electrode having a positive electrode material having oxygen as a positive electrode active material and a catalyst that reduces oxygen. And a solid electrolyte layer including a solid electrolyte interposed between the negative electrode and the positive electrode. At least one of charging and discharging is performed in the presence of vapor phase water. That is, oxygen or oxide reduction is performed in the presence of vapor phase water. According to this configuration, the air battery exhibits an effect of reducing the overvoltage.

In a second aspect of the present disclosure, a lithium-air battery includes a negative electrode having a negative electrode material capable of occluding and releasing lithium ions, and a positive electrode having a positive electrode material having oxygen as a positive electrode active material and a catalyst that reduces oxygen. And a solid electrolyte layer including a solid electrolyte interposed between the negative electrode and the positive electrode. The reaction product by discharge contains an amorphous phase. That is, the reaction product resulting from the discharge contains the amorphous phase, thereby exhibiting the same effect as the first air battery.

In a third aspect of the present disclosure, a lithium-air battery includes a negative electrode having a negative electrode material capable of occluding and releasing lithium ions, and a positive electrode having a positive electrode material having oxygen as a positive electrode active material and a catalyst that reduces oxygen. And a solid electrolyte layer including a solid electrolyte interposed between the negative electrode and the positive electrode. The reaction product from the discharge contains hydrogen atoms. In other words, the reaction product resulting from the discharge contains hydrogen atoms, thereby exhibiting the same effect as the first and second air batteries. In addition, the hydrogen atom in a reaction product shows hydrogen of an atomic state. Atomic state hydrogen includes proton state (ionic) hydrogen.

In a fourth aspect of the present disclosure, a lithium-air battery device includes a negative electrode having a negative electrode material capable of occluding and releasing lithium ions, and a positive electrode having a positive electrode material including oxygen as a positive electrode active material and a catalyst for reducing oxygen. A lithium-air battery cell having a solid electrolyte layer including a solid electrolyte interposed between the negative electrode and the positive electrode, and a water supply unit that supplies gas-phase water to the positive electrode of the lithium-air battery cell. Have. The present lithium-air battery device exhibits an effect capable of obtaining the same effects as those of the first to third air batteries of the present invention described above.

The above and other objects, features and advantages of the present disclosure will become more apparent from the following detailed description with reference to the accompanying drawings. The drawing
FIG. 1 is a diagram illustrating a configuration of an air battery system according to Embodiment 1. FIG. 2 is a configuration diagram schematically showing the configuration of the air battery cell of Embodiment 1. FIG. 3 is a cross-sectional view showing a configuration of an air battery cell of a test example, FIG. 4 is a diagram showing a change in discharge voltage in the air battery system of the test example, FIG. 5 is a diagram showing a change in discharge / charge voltage in the air battery system of the comparative test example. FIG. 6 is a diagram showing a change in the discharge / charge voltage in the air battery system of the test example, FIG. 7 is a diagram showing a change in the discharge / charge voltage in the air battery system of the comparative test example. FIG. 8 is a SEM photograph of the solid electrolyte layer after discharge of the air battery cell of the test example. FIG. 9 is a graph showing a Raman spectroscopic analysis result of the solid electrolyte layer after the discharge of the air battery cell of the test example, FIG. 10 is an XRD of the solid electrolyte layer after the discharge of the air battery cell of the test example, FIG. 11 shows SIMS analysis results of the solid electrolyte layer after discharge of the air battery cell of the test example. FIG. 12 is a configuration diagram schematically showing the configuration of the air battery system of Embodiment 2. FIG. 13 is a configuration diagram schematically illustrating the configuration of the air battery system according to the third embodiment.

Hereinafter, the lithium-air battery and the lithium-air battery device of the present disclosure will be specifically described as embodiments.

[Embodiment 1]
As shown in FIG. 1, the lithium-air battery system 1 of this embodiment includes a lithium-air battery cell 2 and a humidifier 6. The air battery system 1 corresponds to the air battery device of the present disclosure. The air battery cell 2 also corresponds to the first to third air batteries of the present disclosure.

(Air battery cell 2)
As shown in FIG. 2, the air battery cell 2 of the present embodiment includes the positive electrode 3, the negative electrode 4, and the solid electrolyte layer 5 as chargeable / dischargeable elements. Here, in the air battery, the positive electrode 3 is also referred to as an air electrode.

The positive electrode 3 has a positive electrode material including oxygen as an active material and a catalyst that reduces oxygen. The positive electrode 3 includes an air introduction device for advancing a battery reaction with oxygen (or a gas containing oxygen) as an active material.

The negative electrode 4 has a negative electrode material capable of occluding and releasing lithium ions.

The solid electrolyte layer 5 is a layer containing a solid electrolyte interposed between the negative electrode 4 and the positive electrode 3. The solid electrolyte layer 5 functions as a transmission path through which lithium ions move between the positive electrode 3 and the negative electrode 4.

As shown in FIG. 2, the air battery cell 2 of the present embodiment can form a laminated body in which the positive electrode 3, the negative electrode 4, and the solid electrolyte layer 5 are laminated. In addition, the air battery cell 2 does not need to form the laminated body.

The air battery cell 2 of the present embodiment is not particularly limited as long as the shape of the outer shape thereof is a shape that allows the gas containing oxygen to contact the positive electrode 3. Examples of the shape (configuration) that allows gas to contact the positive electrode 3 include a shape having a gas intake port. As the outer shape, a desired shape such as a cylindrical shape, a square shape, a button shape, a coin shape, or a flat shape can be taken.

The air battery cell 2 of this embodiment may be either a primary battery or a secondary battery. Preferably, it is a chargeable / dischargeable secondary battery.

(Solid electrolyte layer 5)
The solid electrolyte layer 5 is interposed between the positive electrode 3 and the negative electrode 4 and is made of a solid electrolyte capable of conducting lithium ions. In particular, the solid electrolyte is preferably made of a material that has no electron conductivity and high lithium ion conductivity. The solid electrolyte is preferably an inorganic material (inorganic solid electrolyte) that can be fired at a high temperature in an air atmosphere.

The solid electrolyte layer 5 may be not only a single layer but also a plurality of layers so as to have a quasi-solid electrolyte layer 50 described later.

The inorganic solid electrolyte may be a crystal, glass, a mixture or a composite of both. The inorganic solid electrolyte may be any oxide-based inorganic solid electrolyte that is excellent in atmospheric stability and suitable for high-temperature firing, as long as it does not cause a significant decrease in performance due to contact with water vapor. .

Such an oxide-based inorganic solid electrolyte has at least a crystal structure selected from the group consisting of a perovskite type, NASICON type, LISICON type, thio-LISICON type, γ-Li ₃ PO ₄ type, garnet type, and LIPON type. It is preferable to include one or more inorganic solid electrolyte materials.

Examples of the perovskite oxide include oxides represented by Li _x La _1-x TiO ₃ (Li—La—Ti—O-based perovskite oxide).

As the NASICON type oxide, for example, Li _a _Xb Y _cP _d O _e (X is at least one selected from the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Sb and Se). Y is at least one selected from the group consisting of Ti, Zr, Ge, In, Ga, Sn and Al, and 0.5 <a <5.0, 0 ≦ b <2. 98, 0.5 ≦ c <3.0, 0.02 <d ≦ 3.0, 2.0 <b + d <4.0, and 3.0 <e ≦ 12.0. Oxides. In particular, in the above formula, an oxide where X = Al and Y = Ti (Li—Al—Ti—PO-based NASICON type oxide), and X = Al, Y = Ge or X = Ge, Y = An oxide that is Al (Li—Al—Ge—Ti—O-based NASICON-type oxide) is preferable. Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ (LATP), which is a Li—Al—Ti—P—O-based NASICON type oxide, is more preferable.

As the LISICON type oxide, thio-LISICON type oxide, or γ-Li ₃ PO ₄ type oxide, for example, Li ₄ XO ₄ -Li ₃ YO ₄ (X is at least one selected from Si, Ge, and Ti) Y is at least one selected from P, As and V), Li ₄ XO ₄ -Li ₂ AO ₄ (X is at least one selected from Si, Ge and Ti. A Is at least one selected from Mo and S), Li ₄ XO ₄ —Li ₂ ZO ₂ (X is at least one selected from Si, Ge, and Ti. Z is from Al, Ga, and Cr) And at least one selected from Li ₄ XO ₄ -Li ₂ BXO ₄ (X is at least one selected from Si, Ge, and Ti. B is selected from Ca and Zn). Li ₃ DO ₃ -Li ₃ YO ₄ (D is B, Y is at least one selected from P, As and V). In particular, Li _3.25 Ge _0.25 P _0.75 S ₄ , Li ₄ SiO ₄ —Li ₃ PO ₄ , Li ₃ BO ₃ —Li ₃ PO _{4 and the} like are preferable.

An example of the garnet-type oxide is an oxide represented by Li _{3 + x} A _y G _z M _{2 -v} B _v O ₁₂ . Here, A, G, M and B are metal cations. A is preferably an alkaline earth metal cation such as Ca, Sr, Ba and Mg, or a transition metal cation such as Zn. G is preferably a transition metal cation such as La, Y, Pr, Nd, Sm, Lu, or Eu. Examples of M include transition metal cations such as Zr, Nb, Ta, Bi, Te, and Sb. Among these, Zr is preferable. B is preferably In, for example. It is preferable to satisfy 0 ≦ x ≦ 5, and it is more preferable to satisfy 4 ≦ x ≦ 5. It is preferable to satisfy 0 ≦ y ≦ 3, and it is more preferable to satisfy 0 ≦ y ≦ 2. It is preferable to satisfy 0 ≦ z ≦ 3, and it is more preferable to satisfy 1 ≦ z ≦ 3. It is preferable to satisfy 0 ≦ v ≦ 2, and it is more preferable to satisfy 0 ≦ v ≦ 1. O may be partially or completely exchanged with a divalent anion and / or a trivalent anion, for example, N ³⁻ . As the garnet-type oxide, Li—La—Zr—O-based oxides such as Li ₇ La ₃ Zr ₂ O ₁₂ (LLZ) are preferable.

Examples of the LiPON type oxide include Li _2.88 PO _3.73 N _0.14 and Li _3.0 PO _2.0 N _1.2 .

The solid electrolyte layer 5 may further include an electrolyte layer made of a quasi-solid (referred to as a quasi-solid electrolyte layer 50). The semi-solid electrolyte layer 50 is an electrolyte layer (an elastically deformable electrolyte layer) that can change the shape of the gel, and can be exemplified by a layer made of a non-aqueous electrolyte. The nonaqueous electrolyte forming the quasi-solid electrolyte layer 50 is, for example, impregnated in an insulating porous body such as a porous film such as polyethylene or polypropylene, a nonwoven fabric such as a resin nonwoven fabric or a glass fiber nonwoven fabric, and the solid electrolyte layer 5 And the negative electrode 4.

The nonaqueous electrolyte can be used by adding a polymer such as polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), etc. and gelling. From the viewpoint of ion conductivity of the nonaqueous electrolyte, the nonaqueous electrolyte is preferably used without being gelled.

(Positive electrode 3)
The positive electrode 3 includes a positive electrode material including a catalyst 31, a solid electrolyte 30, and a conductive material, and a positive electrode current collector (not shown). The positive electrode material has a solid electrolyte 30 as a base material and has pores into which a gas (a gas containing oxygen) can be introduced. A catalyst 31 is disposed on the surface of the solid electrolyte 30 (inner surface of the hole).

The solid electrolyte 30 can be selected from solid electrolytes that can be used for the solid electrolyte layer 5 described above. As the solid electrolyte 30, it is preferable to use the same inorganic solid electrolyte as the solid electrolyte selected for the solid electrolyte layer 5 described above. Since the solid electrolyte 30 is made of the same electrolyte as the solid electrolyte constituting the solid electrolyte layer 5 described above, the solid electrolyte layer 5 and the positive electrode material (the positive electrode 3) can be combined with the same solid electrolyte, and manufacturing is easy. An air battery having low interface resistance can be obtained.

Catalyst 31 promotes a reaction (reduction reaction) of oxygen, which is a positive electrode active material, in positive electrode 3. Catalysts include silver, palladium, gold, platinum, aluminum, nickel, titanium, platinum, iridium oxide, ruthenium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, and metal phthalocyanines. 1 type or 2 types or more selected from the group which consists of can be illustrated.

As the oxygen of the positive electrode active material, oxygen (oxygen contained in the atmosphere) existing around the air battery cell 2 (positive electrode 3) is used.

Conductive material is used as needed. The conductive material is not particularly limited as long as it has conductivity. The conductive material needs to have necessary stability under the atmosphere in the air battery cell 2. In addition, the conductive material used when integrating with the positive electrode 3 or the negative electrode 4 is preferably a material suitable for firing. For example, it is preferable to use a metal or alloy having high oxidation resistance. If the metal or alloy having high oxidation resistance is a metal, it is preferably silver, palladium, gold, platinum, aluminum, nickel, titanium or the like. If it is an alloy, it is preferable that it is an alloy which consists of 2 or more types of metals chosen from silver, palladium, gold | metal | money, platinum, copper, aluminum, and nickel. These oxides may also be used.

The positive electrode current collector may have any electrical conductivity. Since the positive electrode 3 requires a device for introducing a gas containing oxygen into the positive electrode material, the positive electrode current collector is preferably formed to transmit oxygen. For example, the positive electrode current collector is preferably a porous material composed of a metal such as stainless steel, nickel, aluminum, or copper, a net, or a punching metal. Moreover, when using a porous material etc., it is preferable to employ | adopt the form with which the hole was filled with the electrically conductive material, the catalyst, etc.

(Negative electrode 4)
The negative electrode 4 includes a negative electrode material 40 including a negative electrode active material capable of occluding and releasing lithium ions, and a negative electrode current collector (not shown). The negative electrode material 40 can contain a solid electrolyte and a conductive material in addition to the negative electrode active material. As a negative electrode collector, copper, nickel, etc. can be made into forms, such as a net | network, a punched metal, foam metal, plate shape, foil shape, for example. A battery casing can also be used as the negative electrode current collector.

The negative electrode active material includes metal lithium, lithium alloy, metal material capable of inserting and extracting lithium, alloy material capable of inserting and extracting lithium (not only alloys consisting of metals but also alloys of metals and metalloids). The structure consists of a solid solution, a eutectic (eutectic mixture), an intermetallic compound or a compound in which two or more of them coexist), and a compound capable of inserting and extracting lithium. One or more materials selected from the group. However, as described later, since the positive electrode part, the solid electrolyte part, and the negative electrode part are formed by integral firing, the negative electrode active material is preferably a material suitable for firing. Moreover, when using Li metal, it can introduce | transduce by inserting in the negative electrode in which the Li metal melt | dissolution precipitation part was formed, or making it deposit electrochemically.

Metal elements and metalloid elements that can constitute metal materials and alloy materials include tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si), zinc (Zn), and antimony (Sb). ), Bismuth (Bi), cadmium (Cd), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), zirconium (Zr), yttrium (Y ) And hafnium (Hf). Examples of these alloy materials or compounds include those represented by the chemical formula Ma _f Mb _g Li _h or the chemical formula Ma _s Mc _t Md _u . In these chemical formulas, Ma represents at least one of a metal element and a metalloid element capable of forming an alloy with lithium, Mb represents at least one of a metal element and a metalloid element other than lithium and Ma, Mc represents at least one of non-metallic elements, and Md represents at least one of metallic elements and metalloid elements other than Ma. Further, f> 0, g ≧ 0, h ≧ 0, s> 0, t> 0, u ≧ 0.

Among them, the negative electrode material is preferably a simple substance, alloy or compound of a group 4B metal element or metalloid element in the short-period type periodic table, particularly preferably silicon (Si) or tin (Sn), or an alloy or compound thereof. It is. These may be crystalline or amorphous.

Examples of the material capable of inserting and extracting lithium include oxides, sulfides, and other metal compounds such as lithium nitrides such as LiN ₃ . Examples of the oxide include MnO ₂ , V ₂ O ₅ , V ₆ O ₁₃ , NiS, and MoS. In addition, examples of the oxide that has a relatively low potential and can occlude and release lithium include iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide. Examples of the sulfide include NiS and MoS.

The solid electrolyte contained in the negative electrode material is used as necessary. As the solid electrolyte contained in the negative electrode material, the same solid electrolyte as that used in the solid electrolyte layer 5 is used.

The solid electrolyte contained in the negative electrode material can be selected from the solid electrolytes that can be used for the solid electrolyte layer 5 described above. As the solid electrolyte contained in the negative electrode material, it is preferable to use the same inorganic solid electrolyte as the solid electrolyte selected for the solid electrolyte layer 5 described above. Since the solid electrolyte contained in the negative electrode material is made of the same electrolyte as the solid electrolyte constituting the solid electrolyte layer 5 described above, the solid electrolyte layer 5 and the negative electrode material 40 (negative electrode 4) can be combined with the same solid electrolyte, An air battery that is easy to manufacture and has low interface resistance is possible.

When the positive electrode 3 (positive electrode material) and the negative electrode 4 (negative electrode material 40) contain a solid electrolyte, the solid electrolyte contained in both is the same inorganic solid electrolyte as the solid electrolyte selected for the solid electrolyte layer 5 described above. Is most preferred.

Conductive material is used as needed. As the conductive material, those exemplified in the column of the positive electrode 3 can be used.

The negative electrode current collector may have any electrical conductivity. For example, materials such as copper, stainless steel, and nickel can be cited. Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh (grid) shape.

(Humidifying device 6)
The humidifier 6 humidifies the gas containing oxygen introduced into the positive electrode 3 of the air battery cell 2. The humidifier 6 supplies vapor phase water to the positive electrode 3. The humidifier 6 causes the reduction of oxygen introduced into the positive electrode 3 to proceed in the presence of vapor phase water. The humidifier 6 corresponds to a water supply unit and a humidifier.

The humidifier 6 is not particularly limited as long as it can supply vapor phase water around the air battery cell 2 (positive electrode 3). In this embodiment, as shown in FIG. 1, the storage tank 60 is arranged around the air battery cell 2 in the case 7.

The humidification of the gas containing oxygen introduced into the positive electrode 3 by the humidifier 6 is not limited with respect to the humidity of the gas. The gas humidity should be higher than 0% (not 0%).

In addition, it is preferable that the temperature of the positive electrode 3 is equal to or higher than the dew point of water (moisture) contained in the gas.

(Other configurations)
As shown in FIG. 1, the air battery system 1 of the present embodiment includes a case 7 that houses the air battery cell 2 and the

humidifying devices

6 and 60, and an atmosphere adjusting device 8 that adjusts the atmosphere in the case 7. . The atmosphere adjusting device 8 adjusts to a gas atmosphere containing oxygen. Moreover, although it is not shown in figure, it has the member (For example, the conducting wire connected to the

electrodes

3 and 4 of the air battery cell 2, and an electrode terminal) required for the structure of an air battery system.

The case 7 forms a sealed space in which the air battery cell 2 can be accommodated. The configuration of the case 7 is not limited. A chamber can be used.

The atmosphere adjusting device 8 adjusts the atmosphere in the case 7. The atmosphere is adjusted by adjusting the gas supplied into the case 7 and the gas discharged from the case 7. That is, the atmosphere control device 8 includes a gas supply device 80 that supplies gas into the case 7 and a gas discharge device 81 that discharges the gas in the case 7.

The gas supply device 80 is a device capable of controlling the type (composition) of gas supplied into the case 7 and the inflow amount. For example, an apparatus having a gas cylinder, a pipe line that communicates between the gas cylinder and the case 7, and a valve that controls the flow rate of the gas flowing through the pipe line can be given.

The gas supplied by the gas supply device 80 is not limited as long as it contains oxygen. For example, gas, such as air and pure oxygen gas, can be mentioned.

The gas discharge device 81 is a device capable of controlling the discharge amount of the gas discharged from the case 7. For example, a device having a conduit that communicates the inside of the case 7 with the outside and a valve that controls the flow rate of the gas flowing in the conduit can be mentioned.

The atmosphere control device 8 may have a control device that controls the gas supply device 80 and the gas discharge device 81.

[Test example]
The air battery system 1 of Embodiment 1 is demonstrated more concretely using a test example. The structure of the air battery cell of a test example is shown in FIG.

In the air battery cell 2 in the test example, the positive electrode 3 (the solid electrolyte 30) and the solid electrolyte layer 5 are integrally formed. The negative electrode 4 is disposed via a quasi-solid electrolyte layer 50 in contact with a portion of the solid electrolyte layer 5 where the positive electrode 3 is not formed (portion facing away from the positive electrode 3). And these laminated bodies are accommodated in the exterior body 20 which consists of laminate films.

By sputtering the entire surface of Pt in a range of 10 mm × 10 mm on LATP (LICAGC manufactured by OHARA; φ19 mm (diameter), t = 0.15 mm (thickness)), which is an inorganic solid electrolyte, and patterning by photolithography, The positive electrode 3 and the solid electrolyte layer 5 were produced integrally.

The pattern formation of the catalyst 31 may be performed using a mask during sputtering.

The catalyst 31 made of Pt was provided on the inorganic solid electrolyte 30 in a Pt thickness of 50 nm and in lines and spaces at intervals of 3 to 100 μm.

In addition, a tab (not shown) serving as a current collector was provided in a part of the catalyst 31. The tab was produced by sputtering Pt on the solid electrolyte 30 in the same manner as the catalyst 31. The catalyst 31 and the tab are electrically connected.

As the negative electrode material 40 (negative electrode active material), metallic lithium was used.

The exterior body 20 was formed from two laminated films. The laminate film has a size of 40 mm × 40 mm. One laminate film was a positive electrode side laminate film, and a hole having a diameter of 14.5 mm for introducing oxygen into Pt as the catalyst 31 was provided. The other laminate film is a negative electrode-side laminate film and has no holes. The hole of the positive electrode side laminate film was sealed with a sealing film (not shown) from the outside and the inside. Moreover, the nickel lead wire (not shown) used as a negative electrode terminal was attached to the negative electrode side laminated film.

In a glove box in an inert dry atmosphere, a laminate was formed by laminating LATP sputtered with Pt, polyethylene oxide (PEO), and metallic lithium in this order. Next, these laminates were sandwiched between positive and negative side laminate films. When the laminate is sandwiched between the positive electrode side and negative electrode side laminate films, the catalyst layer appears in the holes of the positive electrode side laminate film, and the metal lithium is disposed in contact with the nickel lead wires of the negative electrode side laminate film. Finally, the inside of the laminate film is evacuated and sealed using a vacuum sealing machine to produce the air battery cell 2. And cell 2 was left still overnight in a 60 ° C thermostat.

Thereafter, the sealing film was removed so that the catalyst layer was entirely exposed from the hole in the positive laminate film. Moreover, the tab which is a part of a catalyst layer, and the nickel lead wire were piled up, and the positive electrode terminal was provided by joining with a silver paste.

Thus, the air battery cell 2 of the test example was obtained.

The manufactured air battery cell 2 was accommodated in the case 7. In addition, the water tank 60 was placed in the case 7 and the gas supply device 80 and the gas discharge device 81 were used to create a pure oxygen atmosphere in the case 7, and the gas supply device 80 and the gas discharge device 81 were closed and sealed. The pure oxygen atmosphere in the case 7 includes water evaporated from the water storage tank 60. Thereafter, the case 7 was kept at 60 ° C. At this time, the humidity in the case 7 was 100%.

Thus, the air battery system 1 of the test example was obtained.

In addition, as a comparative test example, an air battery system in which a molecular sieve (a hygroscopic agent) was arranged instead of the water in the water storage tank 60 was also manufactured.

(Evaluation)
As an evaluation of each air battery system 1 in the test example and the comparative test example, a discharge charge test was performed on each air battery system 1.

(Discharge test)
Each air battery system 1 of the test example and the comparative test example was subjected to constant current and constant voltage charge (charge after discharge) at a voltage range of 2.0 to 4.0 V and a current density of 1 μA / cm ² . . The change in the voltage of the air battery cell 2 of the test example at the time of this discharge is shown in FIG. Moreover, the change of the voltage of the air battery cell of the comparative test example is shown in FIG.

As shown in FIG. 4, it can be confirmed that the air battery system 1 of the test example can be charged and discharged with a capacity of 1.0 μAh. On the other hand, as shown in FIG. 5, in the comparative test example, when charging after discharging is performed, it can be seen that the voltage greatly increases in the middle of the battery capacity (about 0.6 μAh in FIG. 5) ( Overvoltage occurrence). That is, it can be seen that the charge after discharge is about 0.4 μAh, and the charge capacity is reduced.

(Discharge test)
The battery voltage of each air battery cell was measured when discharging was performed at a current density of 1, 5, 10, 20, 50, 100 (μA / cm ² ). The change in voltage of the air battery cell 2 of the test example is shown in FIG. Moreover, the change of the voltage of the air battery cell of the comparative test example is shown in FIG.

As shown in FIG. 6, it can be confirmed that the air battery system 1 of the test example can discharge at 2.9 V or more. On the other hand, as shown in FIG. 7, in the comparative test example, the maximum voltage is 2.6V. That is, in the air battery cell 2 of the test example, it can be confirmed that the overvoltage is significantly reduced as compared with that of the comparative test example.

(Cycle test)
The change in the voltage of the air battery cell 2 in the test example was observed when the above-described discharge / discharge test was repeated 6 cycles. This test corresponds to the repetition of FIG. 4 described above.

It can be confirmed that the air battery cell 2 of the air battery system 1 of the test example shows almost the same voltage change. That is, even if the charging / discharging is repeated, the discharge characteristics of the air battery cell 2 are not deteriorated. On the other hand, in the comparative test example, as shown in FIG. 5, the voltage (battery capacity) of the air battery cell 2 does not return to the same state as before the discharge even after charging after discharging. Can't show. That is, when the charge / discharge is repeated, the charge / discharge characteristics of the air battery cell 2 are degraded.

As described above, the air battery system 1 of the test example has the air battery cell 2 in an atmosphere in which a gas containing oxygen is humidified. That is, the reduction of oxygen in the air battery cell 2 proceeds in the presence of gas-phase water. According to this structure, the air battery cell 2 exhibits the effect which can reduce an overvoltage in charging / discharging.

Furthermore, in the air battery cell 2 of the test example, the positive electrode 3 is made of the same (integral) solid electrolyte as the solid electrolyte layer 5. That is, a decrease in ionic conductivity due to the interface resistance at the boundary between the positive electrode 3 and the solid electrolyte layer 5 is suppressed. That is, the air battery cell 2 can enable charging / discharging of a large current. As a result, the air battery system 1 of the test example can also exhibit the effect of enabling charging / discharging of a large current.

In addition, since each of the positive electrode 3, the negative electrode 4, and the solid electrolyte layer 5 is made of a solid electrolyte, the all-solid-state air battery cell 2 that functions as a support that supports each other is formed. The all-solid-type air battery cell 2 exhibits an effect of suppressing a decrease in performance. Furthermore, since no organic solvent is used in the electrolyte or the like, combustion does not occur and an effect of excellent safety can be exhibited.

(Observation of reaction products)
The solid electrolyte layer 5 was observed about the air battery cell 2 of the test example in which the discharge / charge test was performed. Reaction products at the positive electrode were observed on the surface of the solid electrolyte layer 5. The observation of the solid electrolyte layer 5 was performed by disassembling and taking out the air battery cell 2 of the test example after discharging for 2 hours at a current density of 100 (μA / cm ² ).

(SEM)
The surface of the solid electrolyte layer 5 in contact with the positive electrode 3 was observed with an SEM. The result of SEM imaging is shown in FIG.

As shown in FIG. 8, it can be confirmed that the reaction product of the positive electrode 3 is present on the surface of the solid electrolyte layer 5.

(Raman spectroscopy)
The surface of the solid electrolyte layer 5 was observed by Raman spectroscopic analysis. The Raman spectroscopic analysis was performed using a Raman spectrophotometer (trade name: LabRAM HR-800, manufactured by HORIBA, Ltd.). The measurement results are shown in FIG.

As shown in FIG. 9, the peak derived from the solid electrolyte of the solid electrolyte layer 5 can be confirmed, but the peak of the reaction product itself cannot be confirmed. This confirms that the reaction product at the positive electrode 3 does not have a crystal structure, that is, is in an amorphous state.

Furthermore, since the peak of the reaction product itself cannot be confirmed, it can be confirmed that the reaction product itself is essentially composed of an amorphous state. That is, it can be confirmed that almost all reaction products (90% or more, 90 vol% or more) are amorphous.

Note that when crystalline LiOH is present instead of amorphous, a peak can be confirmed in the vicinity of 2500 (cm ⁻¹ ). Similarly, in the vicinity of crystalline _Li 2 _{O 2} in 790 ^{(cm -1),} in the vicinity of crystalline Li ₂ O in 515 ^{(cm -1),} peak respectively can be confirmed. These lithium compounds are compounds that are chemically estimated as reaction compounds.

(XRD)
The surface of the solid electrolyte layer 5 was observed by XRD. XRD was performed using an X-ray diffractometer (manufactured by Rigaku, trade name: RINT-2500). The measurement results are shown in FIG.

As shown in FIG. 10, the peak derived from the solid electrolyte of the solid electrolyte layer 5 can be confirmed, but the peak of the reaction product itself cannot be confirmed. This also confirms that the reaction product at the positive electrode 3 does not have a crystal structure, that is, is in an amorphous state.

According to each analysis described above, in the air battery cell 2 of the air battery system 1 of the test example, the reaction product generated by the discharge at the positive electrode 3 contains an amorphous phase. By this structure, the effect which can enable charging / discharging of said large electric current can be exhibited.

In the air battery cell 2 of the air battery system 1 of the test example, it is confirmed that the reaction product of the positive electrode 3 has a crystal structure, not an amorphous state.

(SIMS)
The surface of the solid electrolyte layer 5 was subjected to surface analysis by SIMS. In SIMS, a surface analysis was performed on D (deuterium), O, Li, and Ti using a secondary ion mass spectrometer (trade name: NANO-SIMS, manufactured by CAMECA). The measurement results are shown in FIG.

The result of the surface analysis for D is shown in the upper left of FIG. 11, and it can be confirmed that D exists in the area indicated by the broken line. This D is an isotope of hydrogen and indicates the presence of substantially atomic hydrogen. That is, it can be confirmed that the solid electrolyte layer 5 contains hydrogen atoms.

The result of the surface analysis for O is shown in the upper right of FIG. 11, and it can be confirmed that O exists in the area indicated by the broken line. That is, it can be confirmed that the solid electrolyte layer 5 contains oxygen.

The result of the surface analysis for Li is shown in the lower left of FIG. 11, and it can be confirmed that Li is present in the region indicated by the broken line. That is, it can be confirmed that the solid electrolyte layer 5 contains lithium.

The results of the surface analysis for Ti are shown in the lower right of FIG. 11, and it can be confirmed that Ti is present in the area indicated by the broken line. That is, it can be confirmed that the solid electrolyte layer 5 contains Ti.

Each figure shown in FIG. 11 is an area analysis of the same part of the surface of the solid electrolyte layer 5, and the areas indicated by broken lines in each figure overlap. That is, it can be confirmed that the reaction product exists in the region indicated by the broken line. Then, as shown in FIG. 11, it can be confirmed that the solid electrolyte layer 5 contains hydrogen atoms.

That is, in the air battery cell 2 of the air battery system 1 of the test example, the reaction product generated by the discharge at the positive electrode 3 contains hydrogen atoms. By this structure, the effect which can enable charging / discharging of said large electric current can be exhibited.

In addition, in the air battery cell 2 of the air battery system 1 of the test example, the reaction product of the positive electrode 3 does not contain hydrogen atoms because it has a crystal structure rather than an amorphous state.

[Embodiment 2]
The present embodiment is an air battery system 1 similar to that of the first embodiment except that the configurations of the humidifying device 6 and the atmosphere adjusting device 8 are different.

In the air battery system 1, as shown in FIG. 12, a humidifier 6 and an atmosphere controller 8 are integrally formed.

Specifically, a water storage part 82 for storing water is provided in a gas flow path (pipe) of the gas supply device 80 of the atmosphere control device 8, and the gas is bubbled into the water stored in the water storage part 82. It is configured to pass through. In this embodiment, the gas supplied into the case 7 is supplied in a humidified state.

This embodiment has the same configuration as that of the first embodiment except that the gas supplied into the case 7 is supplied in a humidified state, and exhibits the same effect.

In this embodiment, when the gas supplied from the gas supply device 80 contains water-soluble impurities, the impurities can also be removed. Examples of the water-soluble impurities include components such as carbon dioxide contained in the atmosphere when the gas supplied from the gas supply device 80 is the atmosphere.

[Embodiment 3]
The present embodiment is an air battery system 1 similar to that of the first embodiment except that the configurations of the humidifying device 6 and the atmosphere adjusting device 8 are different.

Battery system 1 houses humidifier 6 in case 7 as shown in FIG. Further, the atmosphere adjusting device 8 is not provided.

The humidifier 6 includes a raw material reservoir 61 and a humidified gas supply unit 62.

The raw material storage unit 61 stores a compound containing oxygen and water. The compound containing oxygen and water stored in the raw material storage unit 61 is not limited. In this embodiment, hydrogen peroxide (liquid phase hydrogen peroxide) is used. This compound may be an organic or inorganic compound other than hydrogen peroxide.

The humidified gas supply unit 62 decomposes the compound stored in the raw material storage unit 61 and supplies the generated oxygen and water into the case 7 in a gas phase state. The humidified gas supply unit 62 of this embodiment is decomposed by adding a catalyst to hydrogen peroxide. Then, the generated oxygen and gas-phase water are supplied into the case 7.

In the humidified gas supply unit 62 of this embodiment, the compound stored in the raw material storage unit 61 is decomposed to generate a reaction that generates oxygen and water, but it is preferable that this reverse reaction can be generated. The humidified gas supply unit 62 can cause a reverse reaction during charging, and the air battery system 1 can be moved in this closed system.

This embodiment has the same configuration as that of the first embodiment except that the atmosphere in the case 7 is directly humidified, and exhibits the same effect.

In this embodiment, the gas supply device 80 is not provided, and an effect that can be independently formed in a system in which the battery system 1 is closed is also exhibited.

[Modification 1]
In each of the above-described embodiments, the air battery cell 2 has a single cell configuration, but is not limited to this configuration. As long as the reduction of oxygen proceeds in the presence of water, a stacked air battery in which a large number of cells are stacked may be used.

[Modification 2]
In each embodiment described above, the air battery cell 2 has a configuration in which the positive electrode 3 and the solid electrolyte layer 5 are integrated, but the configuration is not limited to this configuration. The negative electrode 4 may also be integrally formed.

The air battery cell 2 of this embodiment can be specifically exemplified by those manufactured by the following manufacturing method.

(Air battery cell manufacturing method)
For the production of the solid electrolyte layer, first, a solid electrolyte powder, a binder and an appropriate dispersion medium are prepared, and these are mixed to prepare a solid electrolyte slurry. Next, a solid electrolyte green sheet is produced from the solid electrolyte slurry.

Here, the green sheet indicates an unsintered body such as a crystal powder formed into a thin plate shape. Specifically, a mixed slurry of crystal powder, a conductive material, a binder, a solvent, and the like is used for a doctor blade, a calendar method, A molded product formed into a thin plate by a coating method such as spin coating or dip coating, a printing method such as ink jet and offset, a die coater method, or a spray method is shown.

The binder exhibits an action of connecting the constituent elements contained in the solid electrolyte. Although it does not specifically limit as a binder, A thermoplastic resin, a thermosetting resin, etc. are mentioned. For example, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene butadiene rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer (ETFE resin) , Polychlorotrifluoroethylene (PCTFE), vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrif Examples include ethylene copolymer (ECTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, and ethylene-acrylic acid copolymer. . These materials may be used alone or in combination.

The solid electrolyte layer 5 is preferably provided with a hole for introducing a negative electrode material in a part thereof. That is, the solid electrolyte green sheet is divided into a portion (solid electrolyte portion) that becomes a solid electrolyte layer after subsequent integral firing and a portion (negative electrode portion) that becomes a negative electrode. The negative electrode part is provided at the other end opposite to one end of the solid electrolyte part on which the positive electrode green sheet is laminated later.

Also, the negative electrode part may be formed separately from the solid electrolyte layer green sheet and later integrated.

It is preferable to include a pore former in the negative electrode portion of the solid electrolyte green sheet. As will be described in detail later, after the positive electrode green sheet and the negative electrode green sheet are integrally fired, the negative electrode portion is vacated by the action of the pore former. The negative electrode is produced by introducing liquefied metallic lithium into the pores at a predetermined pressure or by depositing Li metal through a solid electrolyte.

The pore former forms pores in the negative electrode part of the fired body of the solid electrolyte green sheet. The pore former forms holes for introducing the negative electrode active material. The pore former is desired to be a material that can be vaporized by firing to form pores. For example, the pore former is made of theobromine, graphite, wheat flour, starch, phenol resin, polymethyl methacrylate, polyethylene, polyethylene terephthalate, foamed resin (acrylonitrile plastic balloon, etc.), etc. Can be mentioned.

The pore former is preferably used together with a conductive material. Thereby, the negative electrode part can form the void | hole provided with the electrically conductive material after baking.

As the manufacture of the positive electrode, first, catalyst powder, pore former powder, conductive material powder, binder and appropriate dispersion medium are prepared, and these are mixed to prepare a positive electrode slurry. Next, a positive electrode green sheet is produced from this positive electrode slurry.

The pore-forming material powder is for providing holes for introducing oxygen into the positive electrode material. The pore former is preferably a material that can be vaporized by firing to form pores. It is preferable to use the same material as the pore former described above as the pore former.

When the produced solid electrolyte green sheet and positive electrode green sheet, and the negative electrode part are formed as separate sheets, the negative electrode green sheets are laminated to form a laminate. At this time, the positive electrode green sheet is laminated on one end of the solid electrolyte sheet opposite to the other end (negative electrode part) of the solid electrolyte green sheet containing the pore former. And the produced laminated body is integrally baked.

In the firing step, the atmosphere is not particularly limited, but it is preferably performed under conditions that do not change the valence of the transition metal contained in the electrode active material. More desirable is an oxidizing atmosphere, particularly an air atmosphere. In firing, it is only necessary to reduce the interface resistance between the positive electrode and the solid electrolyte and between the negative electrode and the solid electrolyte. The firing temperature when using the inorganic solid electrolyte is, for example, 600 to 1100 ° C.

Thus, the solid electrolyte green sheet and the positive electrode green sheet are bonded (sintered) and integrated. That is, the solid electrolyte and the solid electrolyte layer 5 of the positive electrode 3 are combined and integrated.

After the green sheet laminate is integrally fired, pores are formed in the portion (the other end) corresponding to the negative electrode portion of the fired body. The negative electrode 4 is formed by introducing liquefied metallic lithium into the pores at a predetermined pressure. Moreover, you may form by making a metal lithium electrodeposit on this hole by charging / discharging.

Thus, a charge / discharge element in which the positive electrode 3, the solid electrolyte layer 5, and the negative electrode 4 are integrally formed is manufactured.

Also in this embodiment, the positive electrode 3 and the solid electrolyte layer 5 are based on the same solid electrolyte. For this reason, the fall of the ionic conductivity resulting from the interface resistance in the boundary of the positive electrode 3 and the solid electrolyte layer 5 is suppressed. That is, the same effects as those of the above embodiments can be exhibited.

In addition, the negative electrode 4 may be formed by producing a negative electrode green sheet similarly to the positive electrode 3 and firing it integrally with the solid electrolyte part. In this case, the negative electrode part is not provided in the solid electrolyte layer. The negative electrode green sheet in this case can be manufactured by the same method as the positive electrode green sheet.

Then, a positive electrode green sheet, a solid electrolyte green sheet, and a negative electrode green sheet are laminated in this order to form a laminate, which is integrally fired.

In this configuration, the positive electrode 3, the solid electrolyte layer 5, and the negative electrode 4 have the same solid electrolyte as a base material. An effect similar to the effect at the boundary between the positive electrode 3 and the solid electrolyte layer 5 described above is also exhibited at the boundary between the solid electrolyte layer 5 and the negative electrode 4. That is, the air battery system 1 (and the air battery cell 2) of the test example can also exhibit an effect that enables charging / discharging of a large current.

This disclosure includes the following aspects.

As an alternative, the water supply unit may be a humidifier that humidifies a gas containing oxygen. In this case, by providing the humidifier, oxygen as the positive electrode active material can be supplied to the positive electrode of the air battery cell in the presence of gas-phase water, and the reduction of oxygen can be performed in the presence of this water.

As an alternative, the water supply unit may decompose the compound containing oxygen and water and supply the generated oxygen and water in a gas phase state. According to this configuration, the positive electrode active material oxygen can be supplied to the positive electrode of the air battery cell in the presence of water in the vapor phase, and the reduction of oxygen can be performed in the presence of this water.

As an alternative, at least one of the negative electrode material and the positive electrode material may include the solid electrolyte and be bonded in a state having an interface with the solid electrolyte layer. With this configuration, at least one of the positive electrode (generally also referred to as an air electrode) and the negative electrode is bonded to the solid electrolyte layer. A battery cell using at least one of the positive electrode, the negative electrode, and the solid electrolyte layer as a support can be constructed.

Alternatively, in the lithium-air battery cell, at least one of the solid electrolyte layer, the negative electrode, and the positive electrode may be a support that supports at least one remaining. Further, the positive electrode, the negative electrode, and the solid electrolyte layer may be supports that support each other. With this configuration, it is possible to construct the air battery cell with all solids (become an all solid type air battery cell). In the all-solid-type air battery cell, each component can be maintained (for example, the electrolyte does not flow), so that a decrease in performance can be suppressed. In addition, the all-solid-state air battery cell does not use an organic solvent in the electrolyte or the like, and therefore does not burn and is excellent in safety.

As an alternative, at least one of the positive electrode and the negative electrode and the solid electrolyte layer may form a fired body integrally bonded by firing. According to this configuration, at least one of the positive electrode and the negative electrode and the solid electrolyte layer form a fired body integrated by firing, and can suppress a decrease in ion conductivity due to interface resistance at the interface.

As an alternative, the solid electrolyte is at least one inorganic solid electrolyte material selected from the group consisting of perovskite type, NASICON type, LISICON type, thio-LISON type, γ-Li ₃ PO ₄ type, garnet type, and LIPON type May be included. By becoming this structure, the positive electrode (air electrode) which comprises the air battery apparatus of this invention does not contain an organic solvent, and the fall of the performance by the organic solvent volatilizing is suppressed.

Although the present disclosure has been described based on the embodiments, it is understood that the present disclosure is not limited to the embodiments and structures. The present disclosure includes various modifications and modifications within the equivalent range. In addition, various combinations and forms, as well as other combinations and forms including only one element, more or less, are within the scope and spirit of the present disclosure.

Claims

A negative electrode (4) having a negative electrode material (40) capable of occluding and releasing lithium ions;
A positive electrode (3) having a positive electrode material comprising oxygen as a positive electrode active material and a catalyst (31) for reducing oxygen;
A solid electrolyte layer (5) including a solid electrolyte interposed between the negative electrode and the positive electrode;
A lithium-air battery (2) having
A lithium-air battery in which at least one of charging and discharging is performed in the presence of vapor phase water.
A negative electrode (4) having a negative electrode material (40) capable of occluding and releasing lithium ions;
A positive electrode (3) having a positive electrode material comprising oxygen as a positive electrode active material and a catalyst (31) for reducing oxygen;
A solid electrolyte layer (5) including a solid electrolyte interposed between the negative electrode and the positive electrode;
A lithium-air battery (2) having
A lithium air battery in which a reaction product by discharge contains an amorphous phase.
The lithium air battery according to claim 2, wherein 90% or more of the reaction product is an amorphous phase.
A negative electrode (4) having a negative electrode material (40) capable of occluding and releasing lithium ions;
A positive electrode (3) having a positive electrode material comprising oxygen as a positive electrode active material and a catalyst (31) for reducing oxygen;
A solid electrolyte layer (5) including a solid electrolyte interposed between the negative electrode and the positive electrode;
A lithium-air battery (2) having
A lithium air battery in which a reaction product of discharge contains hydrogen atoms.
A negative electrode (4) having a negative electrode material (40) capable of occluding and releasing lithium ions, a positive electrode (3) having a positive electrode material comprising oxygen as a positive electrode active material and a catalyst (31) for reducing oxygen, A lithium-air battery cell (2) having a solid electrolyte layer (5) comprising a negative electrode and a solid electrolyte interposed between the positive electrode,
A water supply unit (6, 8) for supplying vapor phase water to the positive electrode of the lithium-air battery cell;
Lithium-air battery device having
The lithium-air battery device according to claim 5, wherein the water supply unit is a humidifier that humidifies a gas containing oxygen.
The lithium air battery device according to claim 5, wherein the water supply unit decomposes a compound containing oxygen and water and supplies the generated oxygen and water in a gas phase state.
The lithium-air battery device according to any one of claims 5 to 7, wherein at least one of the negative electrode material and the positive electrode material includes the solid electrolyte and is bonded to the solid electrolyte layer in an interface state. .
The lithium-air battery device according to any one of claims 5 to 8, wherein at least one of the positive electrode and the negative electrode and the solid electrolyte layer form a fired body integrally bonded by firing.
The solid electrolyte includes at least one inorganic solid electrolyte material selected from the group consisting of perovskite type, NASICON type, LISICON type, thio-LISON type, γ-Li 3 PO 4 type, garnet type, and LIPON type. Item 10. The lithium air battery device according to any one of Items 5 to 9.
The lithium-air battery cell according to any one of claims 5 to 10, wherein the lithium-air battery cell is a support that supports at least one of the solid electrolyte layer, the negative electrode, and the positive electrode. Battery device.