Sodium layered oxides as cathode materials for sodium ion batteries and method of manufacturing the same
US-12030786-B2 · Jul 9, 2024 · US
US10109855B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-10109855-B2 |
| Application number | US-201514619549-A |
| Country | US |
| Kind code | B2 |
| Filing date | Feb 11, 2015 |
| Priority date | Feb 11, 2015 |
| Publication date | Oct 23, 2018 |
| Grant date | Oct 23, 2018 |
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Hydrogen storage alloys comprising a metal oxide containing ≥60 at % oxygen; and/or comprising a metal region adjacent to a boundary region, which boundary region comprises at least one channel; and/or comprising a metal region adjacent to a boundary region, where the boundary region has a length and an average width, where the average width is from about 12 nm to about 1100 nm; and/or comprising a metal oxide zone comprising a metal oxide, which oxide zone is aligned with at least one channel; and/or comprising a Ni/Cr metal oxide have improved electrochemical properties, for instance improved low temperature electrochemical performance.
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The invention claimed is: 1. A hydrogen storage alloy comprising i) at least one main phase and ii) a secondary phase comprising La and Ni, wherein the alloy comprises a bulk metal region adjacent to a metal oxide boundary region, which boundary region comprises at least one channel capable of allowing transport of electrolyte to the bulk metal region, wherein the alloy comprises about 11 at % to about 13 at % Ti, about 18 at % to about 23 at % Zr, about 9 at % to about 11 at % V, about 6 at % to about 9 at % Cr, about 6 at % to about 9 at % Mn, about 31 at % to about 34 at % Ni, about 0.3 at % to about 0.6 at % Al, about 2 at % to about 8 at % Co and about 1 at % to about 7 at % La, based on the total alloy, and wherein the alloy exhibits a charge transfer resistance (R) at −40° C. of from about 5 to about 20 Ω·g; and/or a surface catalytic ability for the main phase or main phases at −40° C. of from about 1 to about 5 seconds; and/or a charge transfer resistance for the main phase or main phases (R) at −40° C. of ≤10 Ω·g. 2. A hydrogen storage alloy according to claim 1 , where the boundary region comprises a Ni/Cr metal oxide. 3. An alloy according to claim 2 where the Ni/Cr oxide contains 60 at % oxygen. 4. An alloy according to claim 2 where the Ni/Cr oxide contains from about 2 at % to about 8 at % Cr. 5. An alloy according to claim 2 where the Ni/Cr oxide contains from about 16 at % to about 23 at % Ni. 6. An alloy according to claim 2 where the Ni/Cr oxide contains from about 64 at % to about 71 at % oxygen, from about 3 at % to about 8 at % Cr and from about 16 at % to about 21 at % Ni. 7. An alloy according to claim 2 where the Ni/Cr oxide contains oxygen, Ni, Cr and one or more further elements selected from the group consisting of Al, Ti, V, Mn, Co and Zr. 8. An alloy according to claim 1 where the boundary region has a length and an average width and comprises at least one channel which runs along the length of the boundary region. 9. An alloy according to claim 1 where the boundary region comprises at least one channel which has an average width of from about 4 nm to about 40 nm. 10. An alloy according to claim 1 where the boundary region has a length and an average width and further comprises a transition oxide zone adjacent to a metal region which transition zone runs along the length of the boundary region. 11. An alloy according to claim 10 where the transition zone has an average width of from about 4 nm to about 30 nm. 12. An alloy according to claim 1 where the boundary region has a length and an average width and comprises a metal oxide zone which runs along the length of the boundary region. 13. An alloy according to claim 12 where the metal oxide zone which has an average width of from about 5 nm to about 500 nm. 14. An alloy according to claim 1 where the boundary region has a length and an average width and comprises across the width a first transition oxide zone, a metal oxide zone and a second transition oxide zone, each running along the length of the boundary region. 15. An alloy according to claim 1 where the boundary region has a length and an average width and comprises across the width a first transition oxide zone, a channel and a second transition oxide zone, each running along the length of the boundary region. 16. An alloy according to claim 1 where the boundary region has a length and an average width and comprises across the width a first transition oxide zone, a metal oxide zone, a channel and a second transition oxide zone, each running along the length of the boundary region. 17. An alloy according to claim 1 where the boundary region has a length and an average width, where the length is ≥4 times the average width and where the width is substantially uniform along the length. 18. An alloy according to claim 1 where the boundary region has an average width of from about 17 nm to about 600 nm. 19. An alloy according to claim 1 comprising from about 1.5 at % to about 7.0 at % La. 20. An alloy according to claim 1 comprising a C14 or C15 main Laves phase or comprising C14 and C15 main Laves phases. 21. An alloy according to claim 1 comprising a C14 or C15 main Laves phase or C14 and C15 main Laves phases, >0.5 wt % of a storage secondary phase comprising La and Ni and from about 0.3 wt % to about 15 wt % of a catalytic secondary phase comprising Ti and Ni. 22. A metal hydride battery, a solid hydrogen storage media, an alkaline fuel cell or a metal hydride air battery comprising a hydrogen storage alloy according to claim 1 . 23. An alloy according to claim 1 , which exhibits a charge transfer resistance (R) at −40° C. of from about 5 to about 20 Ω·g; and a surface catalytic ability for the main phase or main phases at −40° C. of from about 1 to about 5 seconds. 24. An alloy according to claim 1 , which exhibits a surface catalytic ability for the main phase or main phases at −40° C. of from about 1 to about 5 seconds; and a charge transfer resistance (R) at −40° C. for the main phase or main phases of ≤10 Ω·g. 25. An alloy according to claim 1 , which exhibits a charge transfer resistance (R) at −40° C. of from about 5 to about 20 Ω·g; a surface catalytic ability for the main phase or main phases at −40° C. of from about 1 to about 5 seconds; and a charge transfer resistance (R) at −40° C. for the main phase or main phases of ≤10 Ω·g. 26. An alloy according to claim 1 , comprising from about 2.0 to about 7.0 atomic percent La. 27. An alloy according to claim 1 , comprising from about 4.0 to about 7.0 atomic percent La.
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