Protected active metal electrode and battery cell with ionically conductive protective architecture
Active metal and active metal intercalation electrode structures and battery cells having ionically conductive protective architecture including an active metal (e.g., lithium) conductive impervious layer separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers. Safety additives and designs that facilitate manufacture are also provided.
1. An electrochemical cell structure, comprising:
an anode comprising a material selected from the group consisting of an active metal, active metal-ion, active metal alloy, active metal alloying metal and active metal intercalating material; and
an ionically conductive protective architecture on a first surface of the anode, the architecture comprising,
an active metal ion conducting separator layer comprising a semi-permeable polymer membrane comprising a non-aqueous anolyte, the separator layer being chemically compatible with the active metal, and in contact with the anode, and
a substantially impervious ionically conductive layer chemically compatible with the separator layer, and in contact with the separator layer.
2. The structure of claim 1 , wherein the anolyte is in the liquid phase.
3. The structure of claim 1 , wherein the anolyte is in the gel phase.
4. The structure of claim 1 , wherein the substantially impervious ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.
5. The structure of claim 4 , wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:
Composition
mol %
P 2 O 5
26-55%
SiO 2
0-15%
GeO 2 + TiO 2
25-50%
in which
GeO 2
0-50%
TiO 2
0-50%
ZrO 2
0-10%
M 2 O 3
0-10%
Al 2 O 3
0-15%
Ga 2 O 3
0-15%
Li 2 O
3-25%
and containing a predominant crystalline phase composed of Li 1+x (M,Al,Ga) x (Ge 1−y Ti y ) 2−x (PO 4 ) 3 where X≦0.8 and 0≦Y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, and/or Li 1+x+y Q x Ti 2−x Si y P 3−y O 12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga.
6. The structure of claim 1 , wherein the protective architecture has an ionic conductivity of at least 10 −4 S/cm.
7. The structure of claim 1 , wherein the active metal anode is selected from the group consisting of lithium metal, lithium metal alloy and lithium intercalation material.
8. The structure of claim 7 , wherein the active metal anode is lithium metal.
9. The structure of claim 1 , wherein the anode comprises lithium metal-ions.
10. The structure of claim 1 , wherein the anode comprises lithium metal alloying metal.
11. The structure of claim 10 , wherein the lithium metal alloying metal is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb.
12. The structure of claim 1 , wherein the anode comprises lithium metal intercalating material.
13. The structure of claim 12 , wherein the lithium metal intercalating material comprises carbon.
14. A battery cell, comprising:
an electrochemical cell structure in accordance with claim 1 ; and
a cathode structure.
15. The cell of claim 14 , wherein the cathode structure comprises a catholyte selected from the group consisting of aqueous and non-aqueous electrolytes.
16. The cell of claim 15 , wherein the cathode structure further comprises electrochemically active material selected from the group consisting of solid, liquid and gaseous oxidizers.
17. The cell of claim 14 , wherein the cathode structure comprises seawater.
18. The cell of clam 14 , wherein the cathode structure comprises an air electrode.
19. The cell of claim 14 , wherein the cathode structure comprises an ionic liquid.
20. The cell of claim 14 , wherein the active metal anode is lithium metal.
21. The cell of claim 14 , wherein the anode comprises lithium metal-ions.
22. The cell of claim 14 , wherein the anode comprises lithium metal alloying metal.
23. The cell of claim 14 , wherein the anode comprises lithium metal intercalating material.
24. The cell of claim 22 wherein the lithium metal intercalating material comprises carbon.
25. The cell of claim 14 , wherein the anolyte is in the liquid phase.
26. The cell of claim 14 , wherein the anolyte is in the gel phase.
27. The cell of claim 14 , wherein the substantially impervious ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.
28. The structure of claim 22 , wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:
Composition
mol %
P 2 O 5
26-55%
SiO 2
0-15%
GeO 2 + TiO 2
25-50%
in which
GeO 2
0-50%
TiO 2
0-50%
ZrO 2
0-10%
M 2 O 3
0-10%
Al 2 O 3
0-15%
Ga 2 O 3
0-15%
Li 2 O
3-25%
and containing a predominant crystalline phase composed of Li 1+x (M,Al,Ga) x (Ge 1−y Ti y ) 2−x (PO 4 ) 3 where X≦0.8 and 0≦Y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, and/or Li 1+x+y Q x Ti 2−x Si y P 3−y O 12 where 0<X≦0.4 and 0<Y≦0.6, and where Q is Al or Ga.
29. The cell of claim 14 , wherein the protective architecture has an ionic conductivity of at least 10 −4 S/cm.