Stabilization of battery electrodes
View Patent ↗An electrochemical apparatus (e.g., a battery (cell)) including an aqueous electrolyte with electrode stabilizing additives and one or two electrodes (e.g., an anode and/or a cathode), one or both of which is a Prussian Blue analog material of the general chemical formula A x P[R(CN) 6-j L j ] z .nH 2 O, where: A is a cation; P is a metal cation; R is a transition metal cation, L is a ligand that may be substituted in the place of a CN − ligand; 0≦x≦2; 0≦z≦1; and 0≦n≦5 with the electrolyte including an additive to reduce capacity loss of the electrode(s).
1. An electrochemical apparatus, comprising:
an operating aqueous electrolyte including a quantity of water, a plurality of ions, and an electrolyte additive distributed in said quantity of water; and
a first electrode disposed in said operating aqueous electrolyte, said first electrode including a first Prussian Blue analogue material having a general chemical formula A x P y [R(CN) 6-j L j ] z .nH 2 O, where: A is a cation, P is a metal cation, R is a transition metal cation, and L is a ligand substitutable in the place of a CN − ligand, and 0≦j≦6, 0≦x≦2, 0<y≦4, 0<z≦1, and 0≦n≦5, wherein said first Prussian Blue analogue material has a first specific chemical formula conforming to said general chemical formula including a first particular cation P 1 and a first particular cation R 1 , wherein said first electrode has a first rate of electrochemical capacity loss when disposed in said operating aqueous electrolyte, and wherein said first Prussian Blue analogue material has a second rate of electrochemical capacity loss when disposed in a second aqueous electrolyte consisting of water and said plurality of ions without said electrolyte additive; wherein said first rate of electrochemical capacity loss is less than said second rate of electrochemical capacity loss.
2. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode, wherein x>0, wherein said first specific chemical formula includes a particular cation A, and wherein said electrolyte additive produces a concentration of said particular cation A greater than 1 M in said operating aqueous electrolyte.
3. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode, wherein x>0, wherein said first specific chemical formula includes a particular cation A, and wherein said electrolyte additive includes a first plurality of said particular cation A.
4. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode and wherein said electrolyte additive includes a first plurality of said first particular cation P 1 .
5. The electrochemical apparatus of claim 3 wherein said electrolyte additive includes a second plurality of said first particular cation P 1 .
6. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode and wherein said electrolyte additive includes a first plurality of said first particular cation R 1 .
7. The electrochemical apparatus of claim 3 wherein said electrolyte additive includes a second plurality of said first particular cation R 1 .
8. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode, wherein j<6, and wherein said electrolyte additive includes a first plurality of CN − ions.
9. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode, wherein j>0, wherein said first specific chemical formula includes a particular functional group L, and wherein said electrolyte additive includes a plurality of said functional group L.
10. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode, wherein x>0, wherein said first specific chemical formula includes a particular cation A, and wherein said electrolyte additive produces a concentration of said particular cation A greater than 1 M in said operating aqueous electrolyte.
11. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode, wherein x>0, wherein said first specific chemical formula includes a particular cation A, and wherein said electrolyte additive includes a first plurality of said particular cation A.
12. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode and wherein said electrolyte additive includes a first plurality of said first particular cation P 1 .
13. The electrochemical apparatus of claim 11 wherein said electrolyte additive includes a second plurality of said particular cation P 1 .
14. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode and wherein said electrolyte additive includes a first plurality of said first particular cation R 1 .
15. The electrochemical apparatus of claim 11 wherein said electrolyte additive includes a second plurality of said first particular cation R 1 .
16. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode, wherein j<6, and wherein said electrolyte additive includes a first plurality of CN − ions.
17. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode, wherein j>0, wherein said first specific chemical formula includes a particular functional group L, and wherein said electrolyte additive includes a first plurality of said functional group L.
18. The electrochemical apparatus of claim 1 including a second electrode disposed in said operating aqueous electrolyte with said second electrode including a second Prussian Blue analogue material, wherein said second Prussian Blue analogue material has a second specific chemical formula conforming to said general chemical formula different from said first specific chemical formula, wherein said second electrode has a third rate of electrochemical capacity loss when disposed in said operating aqueous electrolyte, wherein said second Prussian Blue analogue material has a fourth rate of electrochemical capacity loss when disposed in a second aqueous electrolyte, wherein said first electrode is configured as a cathode, wherein said second electrode is configured as an anode, and wherein said third rate of electrochemical capacity loss is less than said fourth rate of electrochemical capacity loss.
19. The electrochemical apparatus of claim 18 wherein said specific chemical formulae include x>0, wherein said specific chemical formulae include a particular cation A, and wherein said electrolyte additive includes a first plurality of said particular cation A.
20. The electrochemical apparatus of claim 18 wherein said second specific chemical formula includes said first particular cation P 1 , and wherein said electrolyte additive includes a first plurality of said first particular cation P 1 .
21. The electrochemical apparatus of claim 18 wherein said second specific chemical formula includes said first particular cation R 1 , and wherein said electrolyte additive includes a first plurality of said first particular cation R 1 .
22. The electrochemical apparatus of claim 18 wherein said specific chemical formulae include j<6, and wherein said electrolyte additive includes a first plurality of CN− ions.
23. The electrochemical apparatus of claim 18 wherein said specific chemical formulae include j>0, wherein said specific chemical formulae include a particular functional group L, and wherein said electrolyte additive includes a first plurality of said functional group L.
24. The electrochemical apparatus of claim 18 wherein said second specific chemical formula includes a second particular cation P 2 different from said first particular cation P 1 , and wherein said electrolyte additive includes a first plurality of said first particular cation P 1 and a second plurality of said second particular cation P 2 .
25. The electrochemical apparatus of claim 18 wherein said second specific chemical formula includes a second particular cation R 2 different from said first particular cation R 1 , and wherein said electrolyte additive includes a first plurality of said first particular cation R 1 and a second plurality of said second particular cation R 2 .
26. The electrochemical apparatus of claim 4 further comprising a second electrode disposed in said operating aqueous electrolyte wherein said second electrode is configured as an anode including elemental metal P 1 .
27. The electrochemical apparatus of claim 4 further comprising a second electrode disposed in said operating aqueous electrolyte wherein said second electrode is configured as an anode including an alloy of P 1 .
28. The electrochemical apparatus of claim 1 wherein said general chemical formula includes:
A is one or more cations selected from the group consisting of Na + , K + , Li + , NH 4 + , Mg2 + , or Ca2 + and combinations thereof;
P is one or more metal cations selected from the group consisting of V 2+ , V 3+ , Cr 2+ , Cr 3+ , Mn 2+ , Mn 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ni 2+ , Cu + , Cu 2+ , Zn 2+ , Al 3+ , Sn 2+ , In 3+ , or Pb 2+ and combinations thereof;
R is one or more transition metal cations selected from the group consisting of V 2+ , V 3+ , Cr 2+ , Cr 3+ , Mn 2+ , Mn 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Ru 2+ , Ru 3+ , Os 2+ , Os 3+ , Ir 2+ , Ir 3+ , Pt 2+ , or Pt 3+ and combinations thereof; and
L is one or more ligands that may be substituted in the place of a CN − ligand selected from the group consisting of CO (carbonyl), NO (nitrosyl), or Cl − and combinations thereof.
29. The electrochemical apparatus of claim 1 wherein said first electrode is configured as a cathode and wherein said electrolyte additive includes a first plurality of a second particular cation P 2 different from said first particular cation P 1 .
30. The electrochemical apparatus of claim 1 wherein said first electrode is configured as an anode and wherein said electrolyte additive includes a first plurality of a second particular cation P 2 different from said first particular cation P 1 .
31. The electrochemical apparatus of claim 29 further comprising a second electrode disposed in said operating aqueous electrolyte wherein said second electrode is configured as an anode including elemental metal P 2 .
32. The electrochemical apparatus of claim 29 wherein said first electrode is configured as a cathode, further comprising a second electrode disposed in said operating aqueous electrolyte wherein said second electrode is configured as an anode including an alloy of P 2 .
33. The electrochemical apparatus of claim 1 wherein said operating aqueous electrolyte further includes an amine or an oxide of an amine.
34. The electrochemical apparatus of claim 33 wherein said amine or said oxide of an amine includes pyridine-n-oxide.
35. The electrochemical apparatus of claim 1 wherein said aqueous electrolyte includes one or more additives selected from the group consisting of a simple thiol or a complex thiol group, and combinations thereof.
36. The electrochemical apparatus of claim 35 wherein said simple thiol includes decanethiol.
37. The electrochemical apparatus of claim 35 wherein said complex thiol group includes cysteine.