Ionic conductors
AssigneeUniversity of Warwick
InventorShanwen Tao
Life of this patent
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Abstract
A solid ionic conducting material for use in an electrochemical device comprises an oxyhydroxide or hydrated oxide derived from of an oxide with a perovskite, Brownmillerite, layered oxide, and/or K4CdCl6 structure, the elemental composition of the initial oxide being selected to provide suitable conduction properties for the derived anhydrous or hydrated oxyhydroxide or hydrated oxide. A method of making such a solid ionic conducting material, including treatment with water, and an electrochemical device incorporating such a solid ionic conducting material (optionally as an electrolyte) are also disclosed.
Claims20
An electrochemical device comprising a solid ionic conducting layer, the ionic conducting layer comprising an oxyhydroxide derived from of an oxide with a perovskite or Brownmillerite structure, the oxyhydroxide having the general formula:
- (A1−xA′x)1−aB1−yBy(O3−z−dCz)(OH)m·nH2O;
- wherein:
- A and A′ are selected from Ca, Sr, Ba, Ln, Y, Na, K, Rb, Cs, Pb, and Bi;
- B and B′ are selected from Ln, Y, Sc, Mg, Ca, Sr, Li, Na, Co, Fe, Mn, In, Ni, Cu, Zn, Sc, Ti, V, Cr, Ga, Ge, Al, Si, Sn, As, Sb, Zr, Hf, Nb, Mo, W, Cd, and Ta;
- C is selected from N, Cl, F, Br, S, Te, and Se;
- 0≤x≤1;
- a≤0.15;
- z≤0.2;
- y≤1;
- d≤2;
- m ≥0.01;
- n≥0,
- and wherein the electrochemical device is arranged such that, in use, the ionic conducting layer is exposed to liquid water or to gas with at least 5 vol. % water.
A solid ionic conducting layer for use in an electrochemical device, the solid ionic conducting layer comprising a hydrated oxide derived from of an oxide with a Brownmillerite structure, the hydrated oxide having the general formula:
- (A2−xA′x)1−aB2−yBy(O1−zCz)5±δ·n′H2O
- wherein:
- A and A′ are selected from Ca, Sr, Ba, Ln, Y, Na, K, Rb, Cs, Pb, and Bi;
- B and B′ are selected from Ln, Y, Sc, Mg, Ca, Sr, Li, Na, Co, Fe, Mn, In, Ni, Cu, Zn, Ti, V, Cr, Ga, Ge, Al, Si, Sn, Sb, Zr, Hf, Nb, Mo, W, Cd, As, and Ta;
- C is selected from N, Cl, F, Br, S, Te, and Se;
- a≤0.15;
- 0≤x≤1;
- 0≤y≤1;
- z≤0.04;
- and
- n′≥0.01.
A solid ionic conducting layer for use in an electrochemical device, the solid ionic conducting layer comprising a hydrated oxide derived from an oxide with a perovskite structure, the hydrated oxide having the general formula:
- (A1−xA′x)1−aB1−yB′yO3−z−d·Cz·n″H2O
- wherein:
- A and A′ are selected from Ca, Sr, Ba, Ln, Y, Na, K, Rb, Cs, Pb, and Bi;
- B and B′ are selected from Ln, Y, In, Sc, Sr, Ca, Mg, Li, Na, Co, Fe, Mn, Ni, Cu, Zn, Ti, V, Cr, Ga, Ge, Al, Si, Sn, Sb, Zr, Hf, Nb, Mo, W, Cd, As and Ta;
- C is selected from N, Cl, F, Br, S, and Se;
- 0≤x≤1;
- a≤0.15;
- z≤0.2;
- d≤2;
- n″≥0.01.
A solid ionic conducting layer for use in an electrochemical device, the solid ionic conducting layer comprising a hydrated oxide or a hydrated or non-hydrated oxyhydroxide derived from of an oxide with a K4CdCl6 structure, the oxide with the K4CdCl6 structure having the general formula:
- (A1−xA′x)3B2−yB′yO6−zCz
- wherein:
- A and A′ are selected from Ca, Sr, Ba, Na, K, Rb, Cs, Ln, Y, Pb, In, Tl and Bi;
- B and B′ are selected from Co, Fe, Mn, Ni, Cu, Ti, V, Cr, Mg, Ca, Sr, Ba, Ln, Y, Zn, Cd, Li, Na, B, Ga, Ge, Al, Si, Sn, Sb, Zr, Hf, Nb, Mo, W, Ta, Pt, Rh, Ir and Ru,
- C is selected from N, Cl, F, Br, I, S, Te, and Se;
- y is in the range from 0 to 2;
- z is in the range from 0 to 0.5;
- and
- x is in the range from 0 to 1.
A method of manufacturing a solid ionic conducting layer for use in an electrochemical device, the method comprising:
- acquiring a ceramic oxide material, wherein the ceramic oxide material is an oxide with a perovskite, Brownmillerite or K4CdCl6 structure and comprises A-site ions of one or more elements selected from Ca, Sr, Ba, Ln, Y, Na, K, Rb, Cs, Pb, and Bi and B-site ions of one or more elements selected from Ln, Y, Sc, Mg, Ca, Sr, Ba, Li, Na, Cd, Co, Fe, Mn, In, Ni, Cu, Zn, Ti, V, Cr, Ga, Ge, Al, Si, Sn, Sb, Zr, Hf, Nb, Mo, W, Ta, Pt, Rh, Ir and Ru;
- introducing additional oxygen vacancies into the acquired ceramic oxide material by:
- (i) firing the ceramic oxide material in air;
- (ii) firing the ceramic oxide material in an atmosphere with a lower partial pressure of oxygen than air;
- (iii) soaking the ceramic oxide material in a reducing liquid, or
- (iv) electrochemically reducing the fired ceramic oxide material;
- and
- treating the ceramic oxide material with water, the treatment comprising soaking the fired ceramic oxide material in water, or exposing it to an atmosphere with at least 5 vol. % water, to form a hydrated oxide or a hydrated or non-hydrated oxyhydroxide.
Dependencies are inferred from the claim text.