JP5652877B2 - Lithium air battery - Google Patents

Description

  The present invention relates to a lithium air battery.

  Conventionally, lithium-air batteries use oxygen in the air as a positive electrode active material, oxygen is always supplied from the outside of the battery, and a large amount of lithium metal, which is a negative electrode active material, can be filled in the battery. It has been reported to show discharge capacity.

For example, 1 mol / l lithium hexafluorophosphate (LiPF ₆ ) is used as a solute, and a mixed solvent of propylene carbonate (PC) and 1,2 dimethoxyethane (DME) is used as an organic solvent. Lithium-air batteries using the electrolytes are known.

In addition, for example, electrolysis using 1 mol / l LiN (CF ₃ SO ₂ ) ₂ as a solute and a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) as an organic solvent. A lithium-air battery using a liquid is known.

J. Read et al., Journal of The Electrochemical Society, Vol. 150, pp. A1351-A1356 (2003). A. K. Thapa, Nishiki Kazuki, Matsumoto Hiroshige, Ishihara Tatsumi, Proceedings of the 76th Annual Meeting of the Electrochemical Society, 3P23, pp. 383 (2009).

  However, with the above-described conventional technology, it has been difficult to stably discharge for a long time. Specifically, in the above-described prior art, the organic solvent used in the electrolytic solution has volatility. Therefore, in the case of a structure in which air is taken into the battery like a lithium air battery, the organic solvent is volatilized. Electrolyte will decrease. That is, when the above-described lithium-air battery is operated for a long time, the organic solvent volatilizes from the positive electrode side, thereby increasing battery resistance and remarkably reducing battery performance. Moreover, since the electrolyte solution mentioned above has volatility and flammability, there is a concern about safety such as a fire accident.

  Therefore, the present application has been made in view of the above-described problems of the prior art, and an object thereof is to provide a lithium-air battery that enables stable long-time discharge.

  In order to solve the above-described problems and achieve the object, a lithium-air battery of the present application includes a positive electrode including carbon, a catalyst, and a binder, and a negative electrode including a material capable of inserting and extracting metal lithium or lithium ions, A lithium-air battery in which an electrolyte is disposed between the positive electrode and the negative electrode, wherein the electrolyte contains Li and has at least one of Ge, P, Al, Si, and Zn. It is characterized by being a solid electrolyte containing.

  The lithium-air battery of the present application enables stable long-time discharge.

FIG. 1 is a battery cross-sectional view illustrating an example of the configuration of the lithium-air battery according to the first embodiment. FIG. 2 is a diagram showing test results of a discharge test of the lithium air battery according to Example 1. FIG. 3 is a diagram illustrating test results of a discharge test of the lithium-air battery according to Example 2. FIG. 4 is a diagram illustrating discharge curves of the lithium-air batteries of Examples 6 and 9 according to Example 2. FIG. 5 is a diagram showing test results of the comparative example and the lithium-air battery of Example 9 according to Example 2.

  Embodiments of the lithium-air battery of the present application will be described in detail below with reference to the accompanying drawings. In addition, the lithium air battery of this application is not limited by the following examples.

  First, an example of the configuration of the lithium air battery according to Example 1 will be described. FIG. 1 is a battery cross-sectional view illustrating an example of the configuration of the lithium-air battery 1 according to the first embodiment. As shown in FIG. 1, a lithium-air battery 1 according to Example 1 includes a positive electrode 2, a positive electrode support 3, a positive electrode fixing PTFE (Polytetrafluoroethylene) ring 4, a positive electrode terminal 5, and a negative electrode. It has a fixing PTFE ring 6, a negative electrode fixing washer 7, a negative electrode 8, an O-ring 9, an electrolyte 10, a negative electrode support 11, a cell fixing screw 12, and a negative electrode terminal 13.

The positive electrode 2 is an air electrode containing carbon, a catalyst, and a binder, and performs an oxidation-reduction reaction using oxygen contained in air taken in from air holes as a positive electrode active material. The carbon contained in the positive electrode 2 is, for example, carbon blacks such as ketjen black and acetylene black, activated carbons, graphites, and carbon fibers. Here, the carbon used for the positive electrode 2 is suitable to have a large surface area in order to sufficiently secure reaction sites in the air electrode. Specifically, the BET specific surface area has a value of 300 m ² / g or more. What you have is desirable. The BET specific surface area is a specific surface area calculated from the amount of nitrogen gas adsorbed.

As the catalyst contained in the positive electrode 2, a highly active catalyst for oxygen reduction / oxygen generation reaction is used. As the catalyst, an oxide containing at least one of transition metals such as Mn, Fe, Co, Ni, V, and W in the structure is suitable. For example, single oxides such as MnO ₂ , Mn ₃ O ₄ , MnO, FeO ₂ , Fe ₃ O ₄ , FeO, CoO, Co ₃ O ₄ , NiO, NiO ₂ , V ₂ O ₅ , WO ₃ , La _0.6 Perovskite structure such as Sr _0.4 MnO ₃ , La _0.6 Sr _0.4 FeO ₃ , La _0.6 Sr _0.4 CoO, La _0.6 Ca _0.4 CoO ₃ , Pr _0.6 Ca _0.4 MnO ₃ , LaNiO ₃ , La _0.6 Sr _0.4 Mn _0.4 Fe _0.6 O ₃ A composite oxide containing

Here, as a method for synthesizing these catalysts, a known process such as a solid phase method or a liquid phase method can be used, but it is important to generate a large amount of three-phase interface sites on the electrode catalyst surface. The catalyst to be produced preferably has a high surface area. Specifically, since the specific surface area after firing is preferably 10 m ² / g or more, the amorphous precursor is obtained by evaporating and drying a mixed aqueous solution of metal acetate or metal nitrate or by hydrolysis of metal alkoxide, for example. It is desirable to use a liquid phase method typified by a technique for obtaining the above.

  As the catalyst, a macrocyclic metal complex such as porphyrin or phthalocyanine containing at least one of transition metals such as Mn, Fe, Co, Ni, V, and W as a central metal can also be used. The activity of these metal complexes is increased by performing heat treatment in an inert gas atmosphere after mixing with carbon.

  Further, as the catalyst, not only the above compound system but also a noble metal such as Pt, Au and Pd and a transition metal such as Co, Ni and Mn can be used. High activity can be expressed by carrying these metals in high dispersion on carbon. Specifically, high dispersibility can be achieved by dispersing and dispersing the carbon in a colloidal solution in which these metals are dispersed, and vigorously stirring to adsorb and support the metal particles on the carbon.

  The binder contained in the positive electrode 2 is not particularly limited, and examples thereof include polytetrafluoroethylene (PTFE) powder and dispersion, polyethylene, polypropylene, polyvinylidene fluoride (PVDF), styrene butadiene rubber, and the like. Is used.

  As described above, the positive electrode 2 is a gas diffusion electrode mainly composed of carbon. For example, a mixture of a catalyst powder, a carbon powder, and a binder powder is formed on a support such as a titanium mesh by pressure bonding. Alternatively, it is formed by means such as dispersing the above-described mixture in a solvent such as an organic solvent to form a slurry, applying the mixture on a metal mesh or carbon cloth, and drying. As shown in FIG. 1, the formed positive electrode 2 is disposed in the lithium-air battery 1 so that one surface of the electrode is exposed to air and the other surface is in contact with the electrolyte 10. In addition, in order to increase the strength of the electrode and prevent leakage of the electrolyte, it is possible to produce an electrode with more stability by performing hot pressing as well as cold pressing.

  The positive electrode support 3 is a support that supports the positive electrode 2 and is covered with PTFE. In addition, in the positive electrode support 3, the part which contacts the positive electrode 2 is not coat | covered with PTFE in order to take an electrical contact. The positive electrode fixing PTFE ring 4 is a PTFE ring for fixing the positive electrode 2 to the positive electrode support 3. The positive electrode terminal 5 is a positive electrode side terminal.

The negative electrode fixing PTFE ring 6 is a PTFE ring for fixing the negative electrode 8. The negative electrode fixing washer 7 is a washer to which the negative electrode 8 is fixed. The negative electrode 8 performs a redox reaction with respect to lithium ions contained in the electrolyte 10. The negative electrode 8 is formed of metallic lithium or a material capable of occluding and releasing lithium ions (for example, silicon containing lithium, an alloy of lithium and tin, or lithium nitride such as Li _2.6 Co _0.4 N). . In addition, if it can be used for a lithium secondary battery negative electrode material, it can be used as a material of the negative electrode 8. Moreover, when using silicon, tin, etc. which do not contain lithium as a material of the negative electrode 8, it processes so that it may be in the state containing lithium with a chemical method or an electrochemical method beforehand. The O-ring 9 fills the gap between the positive electrode support 3 and the negative electrode support 11 and seals the inside of the lithium air battery 1.

The electrolyte 10 is a solid electrolyte containing a sulfide containing Li and having at least one of Ge, P, Al, Si, and Zn. For example, Li _3.25 Ge _0.25 P _0.75 S ₄ is preferable as the electrolyte 10 because of its high conductivity and the most improved battery performance.

Here, when a solid electrolyte is used for a lithium-air battery, a material having a conductivity of mS / cm order at room temperature can be used. Specifically, a nitride material such as Li ₃ N, an oxide system such as Li ₃ P (O, N) ₄ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₃ PO ₄ , La _0.5 Li _0.5 TiO ₃ Sulfide systems such as Li ₂ S and Li ₃ PS ₄ can be used. In this example, the lithium air battery of the present application using a sulfide containing Li and containing at least one of Ge, P, Al, Si, and Zn among these solid electrolyte materials, The point that stable long-time discharge is possible compared with a lithium-air battery using other materials will be described using some examples. Detailed description will be given later.

  The negative electrode support 11 is a support that supports the negative electrode 8. The cell fixing screw 12 is a screw that fixes the positive electrode support 3 and the negative electrode support 11 to form the lithium-air battery 1, and is covered with PTFE. The negative electrode terminal 13 is a negative electrode side terminal.

  The configuration of the lithium air battery 1 according to Example 1 has been described above. Hereafter, the detailed example of the lithium air battery 1 actually produced is demonstrated. First, the positive electrode 2 and the electrolyte 10 will be described. In addition, the example shown below is an example to the last, and an Example is not limited to this.

For the positive electrode 2 according to Example 1, the weight of the electrode catalyst La _0.6 Sr _0.4 Fe _0.6 Mn _0.4 O ₃ (LSFM) powder, ketjen black powder and polytetrafluoroethylene (PTFE) powder is 50:30:20. The sheet electrode (thickness: 0.5 mm) was prepared by sufficiently crushing and mixing using a rough machine. The sheet electrode was cut into a circle having a diameter of 15 mm and pressed onto a titanium mesh to obtain a gas diffusion electrode. The La _0.6 Sr _0.4 Fe _0.6 Mn _0.4 O ₃ powder was synthesized by a known method using metal nitrate as a starting material.

For the electrolyte 10 according to Example 1, the materials of the following six examples (Example 1) to (Example 6) were synthesized using a known technique, and each synthesized powder was pressed into a disk shape (diameter 16 mm). And a thickness of 0.2 mm). The material of the electrolyte 10 according to Example 1 is (Example 1) La _0.5 Li _0.5 TiO ₃ , (Example 2) Li ₃ PO ₄ , (Example 3) Li ₄ SiS ₄ , (Example 4) Li ₅ AlS ₄ , ( Example 5 Li ₂ ZnGeS ₄ (Example 6) Li _3.25 Ge _0.25 P _0.75 S ₄ was used. That is, in Example 1, six types of lithium-air batteries having different materials for the electrolyte 10 were produced, and (Example 1) and (Example 2) are comparative examples using an oxide-based material (Example 3). (Example 6) is an example using a sulfide-based material containing Li and containing at least one of Ge, P, Al, Si and Zn.

  And the lithium air battery 1 shown in FIG. 1 was formed as described below using each part mentioned above. First, the positive electrode 2 was disposed in the concave portion of the positive electrode support 3 coated with PTFE, and fixed with the PTFE ring 4 for positive electrode fixing. Then, four metal lithium foils (diameter: 15 mm) having a thickness of 150 μm as the negative electrode 8 were stacked on the concentric circle and pressure-bonded to the negative electrode fixing washer 7. After that, the negative electrode fixing PTFE ring 6 was disposed in the concave portion opposite to the concave portion in which the positive electrode 2 was installed, and the negative electrode fixing washer 7 having metal lithium bonded thereto was further disposed in the central portion. Then, an O-ring 9 is set as shown in the figure, and is filled with a disk of an electrolyte 10 so as to be sandwiched between the positive electrode 2 and the negative electrode 8 inside the cell, and covered with a negative electrode support 11 to fix the cell. The entire cell was fixed with screws 12. In Example 1, six types of lithium-air batteries were produced by changing the electrolyte 10 to (Example 1) to (Example 6) by the method described above. The battery was produced in dry air having a dew point of −60 ° C. or lower.

Hereinafter, the test result of the discharge test of six types of lithium air batteries produced by the above-described method will be described. In the discharge test, the positive electrode terminal 5 and the negative electrode terminal 13 were used for each of the six types of lithium-air batteries. In the discharge test of the lithium air battery, a charge / discharge measurement system was used, and a current density per effective area of the positive electrode 2 of 1.25 μA / cm ² was applied, and the battery voltage was changed to 1.0 V from the open circuit voltage. Measurement was carried out until the value decreased. In addition, the discharge test of the battery measured in the atmosphere which does not control humidity at 25 degreeC.

  FIG. 2 is a diagram showing test results of a discharge test of the lithium air battery according to Example 1. In FIG. 2, the test result which matched solid electrolyte, open circuit voltage (V), average discharge voltage (V), and discharge time (h) for every example is shown. Here, “solid electrolyte” in FIG. 2 indicates the material of the electrolyte 10 used in each example. Further, “open circuit voltage (V)” in FIG. 2 indicates a potential difference between the electrodes when the current is “0”. In addition, “average discharge voltage (V)” in FIG. 2 indicates an average voltage from the start of energization until the voltage drops from the open circuit voltage to “1.0 V”. Further, “discharge time (h)” in FIG. 2 indicates the time until the voltage drops from the open circuit voltage to “1.0 V”.

  As shown in FIG. 2, the open circuit voltages in (Example 1) and (Example 2) using an oxide-based material are “1.9” and “2”, respectively, but contain Li. The open circuit voltages of (Example 3) to (Example 6) using a sulfide-based material containing at least one of Ge, P, Al, Si, and Zn are “2.3” to “2.3”. 2.6 ". Further, as shown in FIG. 2, the average discharge voltages in (Example 1) and (Example 2) are “1.5” and “1.4”, respectively, whereas (Example 3) to (Example) The average discharge voltages of 6) were all “2.2”.

  Further, as shown in FIG. 2, the discharge times in (Example 1) and (Example 2) are “40” and “75”, respectively, whereas the discharge times in (Example 3) to (Example 6). Were “135” to “220”. Thus, the use of a sulfide-based material containing Li in the electrolyte 10 and containing at least one of Ge, P, Al, Si, and Zn is more stable than using an oxide-based material. It was revealed that a lithium-air battery that can discharge for a long time can be produced.

Further, comparing (Example 3) to (Example 6), the performance of (Example 6) using “Li _3.25 Ge _0.25 P _0.75 S ₄ ” as the material of the electrolyte 10 is the highest, and the “open circuit voltage (V ): 2.6 ”and“ discharge time (h): 220 ”. That is, “Li _3.25 Ge _0.25 P _0.75 S ₄ ” is used as the material of the electrolyte 10 among the sulfide-based materials containing Li and containing at least one of Ge, P, Al, Si, and Zn. Thus, it became clear that a lithium-air battery capable of more stable long-time discharge can be produced.

  As described above, according to Example 1, the positive electrode 2 including carbon, a catalyst, and a binder, and the negative electrode 8 including a metal lithium or a substance capable of occluding and releasing lithium ions are provided. A lithium-air battery in which an electrolyte 10 is disposed between the electrolyte 10 and the electrolyte 10 is a solid electrolyte containing a sulfide containing Li and having at least one of Ge, P, Al, Si, and Zn. is there. Therefore, the lithium-air battery 1 according to Example 1 can improve the conductivity of the solid electrolyte, and enables stable long-time discharge.

Moreover, according to Example 1, the electrolyte is Li _3.25 Ge _0.25 P _0.75 S ₄ . Therefore, the lithium-air battery 1 according to the first embodiment uses a material having higher conductivity among sulfides containing Li and containing at least one of Ge, P, Al, Si, and Zn. By using this, it is possible to discharge more stably for a long time.

  Moreover, according to Example 1, it is possible to produce a lithium-air battery only by pressing the solid electrolyte material and the negative electrode material, which is advantageous in terms of cost.

  In the above-described first embodiment, the case where a sulfide containing Li and containing at least one of Ge, P, Al, Si, and Zn is used only for the electrolyte 10 has been described. In Example 2, a case where the material used for the electrolyte 10 is mixed with the positive electrode 2 will be described. Note that the method for producing the lithium-air battery according to Example 2 differs from Example 1 only in the method for producing the positive electrode. Therefore, in Example 2, the positive electrode mixed with the material used for the electrolyte 10 is referred to as a positive electrode 2a.

The positive electrode 2a contains a sulfide contained in the electrolyte. For example, the positive electrode 2a includes Li _3.25 Ge _0.25 P _0.75 S ₄ . In Example 2, the positive electrode 2a was produced by the following method. When mixing the carbon, catalyst, and PTFE, the positive electrode 2a is added with Li _3.25 Ge _0.25 P _0.75 S ₄ , sufficiently pulverized and mixed with a rake machine, roll-formed, and sheet-shaped electrode (thickness: 0.5 mm). _{Incidentally, Li 3.25 Ge 0.25 P 0.75 S} 4 are as highly dispersed in the positive electrode 2a, were pulverized and mixed.

Here, in Example 2, five types of lithium air batteries of (Example 7) to (Example 11) in which the amount of addition of Li _3.25 Ge _0.25 P _0.75 S ₄ was variously changed were prepared, and a discharge test was performed. . FIG. 3 is a diagram illustrating test results of a discharge test of the lithium-air battery according to Example 2. In FIG. 3, the air electrode composition (%) LSFM: Li _3.25 Ge _0.25 P _0.75 S ₄ , the open circuit voltage (V), the average discharge voltage (V), and the discharge time (h) are shown for each example. The associated test results are shown. Here, “air electrode composition (%) LSFM: Li _3.25 Ge _0.25 P _0.75 S ₄ ” in FIG. 3 means the electrode catalyst La _0.6 Sr _0.4 Fe _0.6 Mn _0.4 O ₃ (LSFM) and Li _3.25 Ge _0.25 P _0.75. It indicates the ratio contained in the positive electrode 2a of S _4. In all the examples, the ratio of ketjen black and PTFE contained in the positive electrode 2a is “Ketjen black: PTFE = 30: 20” in the same manner as in example 1. FIG. 3 also shows the result of not adding Li _3.25 Ge _0.25 P _0.75 S ₄ to the positive electrode (Example 6).

As shown in “Air electrode composition (%) LSFM: Li _3.25 Ge _0.25 P _0.75 S ₄ ” in FIG. 3, in Example 2, the ratio of Li _3.25 Ge _0.25 P _0.75 S ₄ contained in the positive electrode 2 a is ( Example 7) Five types of lithium air batteries of 0.5%, (Example 8) 1%, (Example 9) 10%, (Example 10) 20%, and (Example 11) 21% were prepared and subjected to a discharge test. It was. As a result, as shown in FIG. 3, as compared to no addition of Li _3.25 Ge _0.25 P _0.75 S ₄ to the positive electrode (Example 6) was added Li _3.25 Ge _0.25 P _0.75 S ₄ at a ratio of 0.5% In Example 7, almost no improvement effect was observed.

However, Li _3.25 Ge _0.25 P _0.75 S ₄ was added at a rate of 1% (Example 8), Li _3.25 Ge _0.25 P _0.75 S ₄ was added at a rate of 10% (Example 9), and Li at a rate of 20%. _{In the case where 3.25} Ge _0.25 P _0.75 S ₄ was added (Example 10), the discharge time was “285” to “320”, which was significantly improved as compared with “220” in (Example 6). Also, regarding the average discharge voltage, (Example 8) to (Example 10) show “2.3” to “2.4”, and an improvement in performance is seen compared to “2.2” in (Example 6). It was. This is presumably because the contact interface site of the positive electrode 2a / electrolyte 10 increased and the contact resistance decreased by adding a predetermined amount or more of the solid electrolyte material to the positive electrode.

Here, focusing on (Example 8) to (Example 10), Li _3.25 Ge _0.25 P _0.75 S ₄ was added at a rate of 10% (Example 9), but the average discharge voltage compared to (Example 6). And the maximum performance improvement in the discharge time. FIG. 4 is a diagram illustrating discharge curves of the lithium-air batteries of Examples 6 and 9 according to Example 2. In FIG. 4, the vertical axis represents voltage, and the horizontal axis represents discharge time. As shown in FIG. 4, in the lithium air battery of (Example 9), it is apparent that the battery performance is improved with respect to the average discharge voltage and discharge time as compared with the lithium air battery of (Example 6).

Returning to FIG. 3, when (Example 8) to (Example 11) are compared, in (Example 10), the average discharge voltage and the discharge time are lower than (Example 9). Furthermore, compared with (Example 10), when Li _3.25 Ge _0.25 P _0.75 S ₄ was added at a rate of 21% (Example 11), the battery performance was significantly lowered. This is presumably because the addition of a large amount of solid electrolyte material to the positive electrode increases the resistance of the positive electrode itself or inhibits the diffusion of air in the positive electrode.

  From the above results, it was clarified that the battery performance is improved by adding the solid electrolyte material to the positive electrode, but the battery performance is greatly influenced by the amount of the solid electrolyte material to be added. That is, the addition amount of the solid electrolyte material added to the positive electrode has an appropriate addition amount for improving battery performance, which is 1 to 20% of the whole material constituting the positive electrode 2a, and more preferably It was found to be 1-10%.

  So far, the lithium-air battery, which is a solid electrolyte containing a sulfide containing Li and containing at least one of Ge, P, Al, Si, and Zn, enables stable long-term discharge. Explained what to do. Here, a battery using an organic electrolyte as a comparative example with the prior art will be described, and the results compared with the above-described (Example 9) will be described.

  The lithium-air battery of the comparative example has the same cell configuration as in FIG. 1, and is prepared by filling the cell with 1 mol / l LiPF6 / propylene carbonate (PC), which is an organic electrolyte instead of the solid electrolyte, together with the separator. did. Hereinafter, 5 lithium-air batteries of the comparative example and (Example 9) were prepared, and these cells were set in a thermostatic bath at 35 ° C., and measurements were made after 24, 72, 168, 240, and 480 hours, respectively. The results of comparison with the data measured at room temperature (0 hour) will be described.

  FIG. 5 is a diagram showing test results of the comparative example and the lithium-air battery of Example 9 according to Example 2. In FIG. 5, the vertical axis represents the discharge capacity retention rate (%), and the horizontal axis represents the standing time (h). Here, “discharge capacity maintenance ratio (%)” in FIG. 5 indicates the ratio of the discharge capacity of each standing time to the discharge capacity of 0 hours. In addition, “leaving time (h)” in FIG. 5 indicates the time during which the cell was set in a constant temperature bath at 35 ° C.

  As shown in FIG. 5, it can be seen that the discharge capacity of the lithium-air battery of the comparative example rapidly decreases with time. This is considered to be caused by a decrease due to volatilization of the organic electrolyte. On the other hand, in the lithium-air battery of Example 9 using a solid electrolyte, the discharge capacity was hardly reduced within the measured time. This result shows that the use of the solid electrolyte according to the present invention is very effective for long-term stable operation of the lithium-air battery.

  As described above, according to Example 2, the positive electrode 2 a includes the sulfide contained in the electrolyte 10. Therefore, the lithium air secondary battery 1 according to Example 2 can reduce the contact resistance by increasing the contact interface site, and enables more stable long-time discharge.

  Although the first and second embodiments have been described so far, the technique of the present application is not limited to the first and second embodiments. That is, Examples 1 and 2 can be implemented in various other forms, and various omissions, replacements, and changes can be made.

  In Examples 1 and 2 described above, the case of using a cylindrical lithium-air battery has been described. However, the embodiment is not limited to this, and a lithium-air battery having an arbitrary shape may be used. For example, a square prism lithium-air battery may be used.

  In Example 2 mentioned above, the case where the same material as the material mixed with electrolyte was mixed with a positive electrode was demonstrated. However, the embodiment is not limited to this, and may be a case where different materials are mixed in the electrolyte and the positive electrode. In such a case, different materials are mixed with a sulfide containing Li in each of the electrolyte and the positive electrode and containing at least one of Ge, P, Al, Si, and Zn.

  These embodiments and modifications thereof are included in the invention disclosed in the claims and equivalents thereof as well as included in the technology disclosed in the present application.

DESCRIPTION OF SYMBOLS 1 Lithium air battery 2 Positive electrode 3 Positive electrode support body 4 Positive electrode fixing PTFE ring 5 Positive electrode terminal 6 Negative electrode fixing PTFE ring 7 Negative electrode fixing washer 8 Negative electrode 9 O-ring 10 Electrolyte 11 Negative electrode support 12 Cell fixing screw 13 Negative electrode terminal

Claims (1)

Lithium air comprising a positive electrode which is an air electrode containing carbon, a catalyst and a binder, and a negative electrode containing a material capable of occluding and releasing metal lithium or lithium ions, and an electrolyte disposed between the positive electrode and the negative electrode A battery,
Arrangement wherein the electrolyte is a Li _3.25 Ge _0.25 P _0.75 S ₄ der Ru solid body electrolyte, the same electrolyte material and the electrolyte, wherein an amount of 1-10% of the total of the positive electrode mass dispersed in the positive electrode Lithium-air battery characterized by being made.

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