Electrode for metal-air battery
View Patent ↗The present invention provides a novel and improved metal-air battery in which a lot of catalyst can be disposed in a triple phase boundary, and further, battery properties can be improved. In the metal-air battery according to the present invention, a catalyst layer of an air electrode of a metal-air battery contains a catalyst element and a carbon material, the carbon material comprises two materials of a carbon material A supporting thereon the catalyst element and a carbon material B not supporting the catalyst element, the catalyst layer comprises an agglomerate X containing the catalyst element, the carbon material A and the carbon material B as main components and an agglomerate Y containing the carbon material B as a main component, and the agglomerate X is a continuum and the agglomerate Y is dispersed in the agglomerate X.
1. An electrode for a metal-air battery, wherein:
a catalyst layer of an air electrode of a metal-air battery contains a catalyst element and a carbon material,
the carbon material comprises two materials of a hydrophilic carbon material A having supported thereon the catalyst element and a hydrophobic carbon material B not supporting the catalyst element,
the catalyst layer comprises a hydrophilic agglomerate X containing more than 50 mass % in total of the catalyst element, the carbon material A and the carbon material B, and a hydrophobic agglomerate Y containing more than 50 mass % of the carbon material B,
the agglomerate X is a continuum and the agglomerate Y is dispersed in the agglomerate x,
the carbon material A satisfies the following characteristic feature (i) or (ii), and
in the carbon material B, a water vapor adsorption amount is less than 0.1 cm 3 /g in an environment of 25° C. and a relative pressure of 0.1 and a ratio (X/S BET ) of the DBP absorption (X) (cm 3 /100 g) to a specific surface area (S BET ) by BET evaluation is 0.5 or more, and wherein
an interface between an aqueous electrolyte solution and an air is formed in the catalyst layer;
(i) in the carbon material A, the water vapor adsorption amount is 0.1 cm 3 /g or more in an environment of 25° C. and a relative pressure of 0.1, a ratio S micro /S total of a micropore surface area S micro as determined by t-plot analysis of a nitrogen adsorption isotherm to a total surface area S total is 0.90 or more, an average particle diameter d50 is less than 1.5 μm, and a ratio (d90−d10)/d50 of the difference between d90 and d10 (d90−d10) to d50 is less than 1.0; or
(ii) in the carbon material A, the water vapor adsorption amount is 0.1 cm 3 /g or more in an environment of 25° C. and a relative pressure of 0.1 and the ratio S micro /S total of the micropore surface area S micro as determined by t-plot analysis of a nitrogen adsorption isotherm to the total surface area S total is 0.90 or less.
2. The electrode for a metal-air battery according to claim 1 , wherein:
in the carbon material A, the water vapor adsorption amount is 0.1 cm 3 /g or more in an environment of 25° C. and a relative pressure of 0.1, the ratio S micro /S total of the micropore surface area S micro as determined by t-plot analysis of a nitrogen adsorption isotherm to the total surface area S total is 0.90 or more, the average particle diameter d50 is less than 1.5 μm, and the ratio (d90−d10)/d50 of the difference between d90 and d10 (d90−d10) to d50 is less than 1.0, and
the content of the carbon material B in the catalyst layer is from more than 10 mass % to less than 50 mass %.
3. The electrode for a metal-air battery according to claim 1 , wherein:
in the carbon material A, the water vapor adsorption amount is 0.1 cm 3 /g or more in an environment of 25° C. and a relative pressure of 0.1 and the ratio S micro /S total of the micropore surface area S micro as determined by t-plot analysis of a nitrogen adsorption isotherm to the total surface area S total is 0.90 or less, and
the content of the carbon material B in the catalyst layer is from 5 mass % to less than 50 mass %.
4. The electrode for a metal-air battery according to claim 1 , wherein one or more carbon material agglomerates each having a size of 300 nm or more in terms of an equivalent-circle diameter and not supporting a catalyst element are present in a visual field of 10 μm×10 μm in a cross-section of the catalyst layer.
5. The electrode for a metal-air battery according to claim 2 , wherein one or more carbon material agglomerates each having a size of 300 nm or more in terms of an equivalent-circle diameter and not supporting a catalyst element are present in a visual field of 10 μm×10 μm in a cross-section of the catalyst layer.
6. The electrode for a metal-air battery according to claim 3 , wherein one or more carbon material agglomerates each having a size of 300 nm or more in terms of an equivalent-circle diameter and not supporting a catalyst element are present in a visual field of 10 μm×10 μm in a cross-section of the catalyst layer.
7. The electrode for a metal-air battery according to claim 1 , wherein:
the percentage content a of the carbon material B on a metal electrode-facing side in the catalyst layer is from 0 mass % to less than 20 mass %,
a percentage content β of the carbon material B on an open-to-air side in the catalyst layer is from more than 10 mass % to less than 50 mass %, and α<β is satisfied.
8. The electrode for a metal-air battery according to claim 2 , wherein:
the percentage content a of the carbon material B on a metal electrode-facing side in the catalyst layer is from 0 mass % to less than 20 mass %,
a percentage content β of the carbon material B on an open-to-air side in the catalyst layer is from more than 10 mass % to less than 50 mass %, and
α<β is satisfied.
9. The electrode for a metal-air battery according to claim 3 wherein:
the percentage content a of the carbon material B on a metal electrode-facing side in the catalyst layer is from 0 mass % to less than 20 mass %,
a percentage content β of the carbon material B on an open-to-air side in the catalyst layer is from more than 10 mass % to less than 50 mass %, and
α<β is satisfied.
10. The electrode for a metal-air battery according to claim 4 , wherein:
the percentage content a of the carbon material B on a metal electrode-facing side in the catalyst layer is from 0 mass % to less than 20 mass %,
a percentage content β of the carbon material B on an open-to-air side in the catalyst layer is from more than 10 mass % to less than 50 mass %, and
α<β is satisfied.
11. The electrode for a metal-air battery according to claim 5 , wherein:
the percentage content a of the carbon material B on a metal electrode-facing side in the catalyst layer is from 0 mass % to less than 20 mass %,
a percentage content β of the carbon material B on an open-to-air side in the catalyst layer is from more than 10 mass % to less than 50 mass %, and
α<β is satisfied.
12. The electrode for a metal-air battery according to claim 6 , wherein:
the percentage content a of the carbon material B on a metal electrode-facing side in the catalyst layer is from 0 mass % to less than 20 mass %,
a percentage content β of the carbon material B on an open-to-air side in the catalyst layer is from more than 10 mass % to less than 50 mass %, and
α<β is satisfied.