Oxygen reduction reaction catalyst and methods of synthesizing the same

Patent metadata

Field	Value
Publication number	US-2025079473-A1
Application number	US-202418821451-A
Country	US
Kind code	A1
Filing date	Aug 30, 2024
Priority date	Sep 5, 2023
Publication date	Mar 6, 2025
Grant date	—

Abstract

A composition includes a compound of the formula A x M y O z , wherein A is an A-site element and includes Ba, Ca, Cu, Dy, Er, Gd, La, Nd, Pr, Sm, Sr, Y, or Yb, or a combination thereof, M is an M-site element and includes Co, Cu, Fe, Mn, Ni, Ti, Sc, or P, or a combination thereof, and 0<x≤1, 0<y≤2, (3−δ)≤z≤(4−δ), and 1<δ<1. Use of the composition as a catalyst composition, for example an oxygen reduction reaction catalyst composition, in gas diffusion electrodes, and in metal-air batteries is also described.

First claim

1 . A composition comprising
a compound of the formula A X M y O Z , wherein A comprises Ba, Ca, Cu, Dy, Er, Gd, La, Nd, Pr, Sm, Sr, Y, or Yb, or a combination thereof, M comprises Co, Cu, Fe, Mn, Ni, Ti, Sc, or P, or a combination thereof, and 0<x≤1, 0<y≤2, (3−δ)≤z≤(4−δ), and 0≤δ≤1.

2 . The composition of claim 1 , wherein A is an A-site element, M is an M-site element, z is 3−δ, and wherein 0≤δ<1.

3 . The composition of claim 1 , wherein
A is A1 and A2, wherein A1 and A2 are each independently Ba, Ca, Cu, Dy, Er, Gd, La, Nd, Pr, Sm, Sr, Y, or Yb, M is M1 and M2, wherein M1 and M2 are each independently Co, Cu, Fe, Mn, Ni, Ti, Sc, or P, and the composition has the formula [A1 x1 A2 x2 ] a [M1 y1 M2 y2 ] b O 3-δ , wherein x1+x2=1, 0<x1≤1, 0≤x2≤1, 0<a≤1, and y1+y2=1, 0<y1≤1, 0≤y2≤1, 0<b≤1, and 0≤δ≤0.5.

4 . The composition of claim 3 , wherein A1 is a lanthanum group element, A2 is a Group 2 element, M1 is a Group 7 element, and y2=0.

5 . The composition of claim 4 , wherein the compound is of the formula La x1 Sr x2 MnO 3-δ , wherein 0.1≤x1≤0.9, 0.1≤x2≤0.9, and 0≤δ≤0.5.

6 . The composition of claim 5 , wherein the compound comprises La 0.1 Sr 0.9 MnO 3-δ , La 0.15 Sr 0.85 MnO 3-δ , La 0.2 Sr 0.8 MnO 3-δ , La 0.25 Sr 0.75 MnO 3-δ , La 0.3 Sr 0.7 MnO 3-δ , La 0.35 Sr 0.65 MnO 3-δ , La 0.4 Sr 0.6 MnO 3-δ , La 0.45 Sr 0.55 MnO 3-δ , La 0.5 Sr 0.5 MnO 3-δ , La 0.55 Sr 0.45 MnO 3-δ , La 0.6 Sr 0.4 MnO 3-δ , La 0.65 Sr 0.45 MnO 3-δ , La 0.7 Sr 0.3 MnO 3-δ , La 0.75 Sr 0.25 MnO 3-δ , La 0.8 Sr 0.2 MnO 3-δ , La 0.85 Sr 0.15 MnO 3-δ , or La 0.9 Sr 0.1 MnO 3-δ , wherein δ is each independently 0≤δ≤0.5.

7 . The composition of claim 3 , wherein A1 is La, A2 is Sr, a=0.95, M1 is Mn, and b=1, and wherein the compound is of the nominal formula [La x1 Sr x2 ] 0.95 MnO 3-δ , wherein 0.1≤x1≤0.9, 0.1≤x2≤0.9, and 0≤δ≤0.5.

8 . The composition of claim 7 , wherein the compound comprises a nominal stoichiometry of: [La 0.1 Sr 0.9 ] 0.95 MnO 3-δ , [La 0.15 Sr 0.85 ] 0.95 MnO 3-δ , [La 0.2 Sr 0.8 ] 0.95 MnO 3-δ , [La 0.25 Sr 0.75 ] 0.95 MnO 3-δ , [La 0.3 Sr 0.7 ] 0.95 MnO 3-δ , [La 0.35 Sr 0.65 ] 0.95 MnO 3-δ , [La 0.4 Sr 0.6 ] 0.95 MnO 3-δ , [La 0.45 Sr 0.85 ] 0.95 MnO 3-δ , [La 0.5 Sr 0.5 ] 0.95 MnO 3-δ , [La 0.85 Sr 0.45 ] 0.95 MnO 3-δ , [La 0.6 Sr 0.4 ] 0.95 MnO 3-δ , [La 0.65 Sr 0.35 ] 0.95 MnO 3-δ , [La 0.7 Sr 0.3 ] 0.95 MnO 3-δ , [La 0.7 5Sr 0.25 ] 0.95 MnO 3-δ , [La 0.8 Sr 0.2 ] 0.95 MnO 3-δ , [La 0.85 Sr 0.15 ] 0.95 MnO 3-δ , [La 0.9 Sr 0.1 ] 0.95 MnO 3-δ , wherein δ is each independently 0≤δ≤0.5.

9 . The composition of claim 3 , wherein A1 is La, A2 is Sr, a=0.9, M1 is Mn, and b=1, and the compound is of the nominal formula [La x1 Sr x2 ] 0.9 MnO 3-δ , wherein 0.1≤x1≤0.9, 0.1≤x2≤0.9, and 0≤δ≤0.5.

10 . The composition of claim 9 , wherein the compound comprises a nominal stoichiometry of: [La 0.1 Sr 0.9 ] 0.9 MnO 3-δ , [La 0.15 Sr 0.85 ] 0.9 MnO 3-δ , [La 0.2 Sr 0.8 ] 0.9 MnO 3-δ , [La 0.25 Sr 0.75 ] 0.9 MnO 3-δ , [La 0.3 Sr 0.7 ] 0.9 MnO 3-δ , [La 0.35 Sr 0.65 ] 0.9 MnO 3-δ , [La 0.4 Sr 0.6 ] 0.9 MnO 3-δ , [La 0.45 Sr 0.85 ] 0.9 MnO 3-δ , [La 0.5 Sr 0.5 ] 0.9 MnO 3-δ , [La 0.85 Sr 0.45 ] 0.9 MnO 3-δ , [La 0.6 Sr 0.4 ] 0.9 MnO 3-δ , [La 0.65 Sr 0.35 ] 0.9 MnO 3-δ , [La 0.7 Sr 0.3 ] 0.9 MnO 3-δ , [La 0.7 5Sr 0.25 ] 0.9 MnO 3-δ , [La 0.8 Sr 0.2 ] 0.9 MnO 3-δ , [La 0.85 Sr 0.15 ] 0.9 MnO 3-δ , [La 0.9 Sr 0.1 ] 0.9 MnO 3-δ , wherein δ is each independently 0≤δ≤0.5.

11 . The composition of claim 3 , wherein A1 is a lanthanum group element, A2 is a Group 2 element, M1 is a Group 7 element, and M2 is a Group 8 element.

12 . The composition of claim 11 , wherein the compound is of the nominal formula [La x1 Sr x2 ] a [Mn y1 Fe y2 ]O 3-δ , wherein x1+x2=1, 0.1≤x1≤0.9, 0.1≤x2≤0.9, 0.9≤a≤1, y1+y2=1, 0.05≤y1≤0.95, 0.05≤y2≤0.95, and 0≤δ≤0.5.

13 . The composition of claim 3 , wherein A1 is a lanthanum group element, A2 is a Group 2 element, M1 is a Group 7 element, and M2 is a Group 9 element.

14 . The composition of claim 13 , wherein the compound is of the nominal formula [La x1 Sr x2 ] a [Mn y1 Co y2 ]O 3-δ , wherein x1+x2=1, 0.1≤x1≤0.9, 0.1≤x2≤0.9, 0.9≤a≤1, y1+y2=1, 0.05≤y1≤0.95, 0.05≤y2≤0.95, and 0≤δ≤0.5.

15 . The composition of claim 3 , wherein A1 is a lanthanum group element, A2 is a Group 2 element, M1 is a Group 7 element, and M2 is a Group 10 element.

16 . The composition of claim 15 , wherein the compound is of the nominal formula [La x1 Sr x2 ] a [Mn y1 Ni y2 ]O 3-δ , wherein x1+x2=1, 0.1≤x1≤0.9, 0.1≤x2≤0.9, 0.9≤a≤1, y1+y2=1, 0.05≤y1≤0.95, 0.05≤y2≤0.95, and 0≤δ≤0.5.

17 . The composition of claim 1 , wherein the composition has a perovskite structure.

18 . The composition of claim 16 , wherein the composition has peaks centered at 2θ values of 31.6° to 33.9°, 39.4° to 41.6°, and 46.2° to 48.2°, when analyzed by X-ray diffraction using CuKα radiation.

19 . The composition of claim 1 , wherein the compound has a specific surface area of greater than 0.1 m 2 /g, when determined by the Brunauer-Emmett-Teller adsorption method (“BET”).

20 . An oxygen reduction reaction catalyst comprising the composition of claim 1 , optionally further comprising a support, wherein the composition is on the support.

21 . The oxygen reduction reaction catalyst of claim 20 , wherein the catalyst has peaks centered at 2θ values of 31.6° to 33.9°, 39.4° to 41.6°, and 46.2° to 48.2°, when analyzed by X-ray diffraction using CuKα radiation.

22 . The oxygen reduction reaction catalyst of claim 20 , wherein the catalyst has a specific surface area of greater than 0.1 m 2 /g, when determined by the Brunauer-Emmett-Teller adsorption method (“BET”).

23 . The oxygen reduction reaction catalyst of claim 20 , wherein the support comprises carbon.

24 . The oxygen reduction reaction catalyst of claim 20 , further comprising an alkaline electrolyte contacting the catalyst.

25 . A gas diffusion electrode comprising an oxygen reduction reaction catalyst comprising the composition of claim 1 .

26 . The gas diffusion electrode of claim 25 ,
wherein the gas diffusion electrode is effective to operate for 1000 hours or greater with an electrode voltage of at least 0.65 V vs reversible hydrogen electrode (RHE) at a cell temperature of 10 to 80° C. in an alkaline electrolyte with pH>14; or wherein the gas diffusion electrode is effective to operate at a current density of 200 mA/cm 2 or less with an electrode voltage of at least 0.65 V vs reversible hydrogen electrode (RHE) at a cell temperature of 10 to 80° C. in an alkaline electrolyte with pH>14.

27 . A metal-air battery comprising:
a negative electrode comprising a metal; a positive electrode comprising a gas diffusion electrode; and an electrolyte contacting at least one of the negative electrode or the positive electrode, wherein the positive electrode comprises the composition of claim 1 .

28 . The battery of claim 27 , wherein the metal of the negative electrode comprises an alkali metal, an alkaline earth metal, a transition metal, a Group 13 metal, or a combination thereof.

29 . The battery of claim 27 , wherein the metal of the negative electrode comprises a transition metal, preferably aluminum, iron, or zinc.

30 . A method of preparing the composition of claim 1 , the method comprising:
providing an A-site precursor comprising a compound comprising Ba, Ca, Cu, Dy, E

Assignees

• Form Energy Inc

Inventors

• Paz Mauricio
• Butts Danielle Marie
• Su Liang
• Tarasov Vlad
• Donahey Glenn

Classifications

• C01G51/68

  containing rare earths, e.g. (La0.3Sr0.7)CoO3 · CPC title

• C01G51/70

  containing rare earths, e.g. LaCoO3  (C01G51/68 takes precedence) · CPC title

• C01G45/1264

  containing rare earths, e.g. (La1-xCax)MnO3 or LaMnO3 · CPC title

• H01M4/9083

  on carbon or graphite · CPC title

• H01M4/9016 Primary

  Oxides, hydroxides or oxygenated metallic salts · CPC title