Electrochemical cells with ionic sequestration provided by porous separators
Provided are electrochemical cells including separators permeable to some materials and impermeable to other materials in electrolytes. Also provide are methods of forming such separators. The selective permeability of a separator is achieved by its specific pore diameter and a narrow distribution of this diameter. Specifically, a species responsible for ion transport in an electrochemical cell are allowed to pass through the separator, while another species is blocked thereby preventing degradation of the cell. For example, a species containing lithium ions is allowed to pass in rechargeable cells, while one or more species containing transition metals are blocked. In some embodiments, a separator may include a membrane layer with at least 90% of pores of this having a diameter of between about 0.1 nanometers and 1.0 nanometer. The membrane layer may be a standalone layer or supported by a membrane support.
1. An electrochemical cell comprising:
a positive electrode;
a negative electrode;
a separator disposed between the positive electrode and the negative electrode, wherein the separator provides electronic isolation between the positive electrode and the negative electrode, wherein the separator comprises a first membrane layer; and
an electrolyte comprising a first species and a second species, wherein at least a portion of the electrolyte is disposed within the separator,
wherein the separator, with at least the portion of the electrolyte disposed within the separator, is permeable to the first species providing ionic communication between the positive electrode and the negative electrode,
wherein the separator, with at least the portion of the electrolyte disposed within the separator, is substantially impermeable to the second species comprising an element of the electrochemical active material of the positive electrode,
wherein the first species is selected from the group consisting of H + , Li + , Na + , K + , Rb + , Cs + , F − , Cl − , Br − , I − , BF 4 − , PF 6 − , AsF 6 − , ClO 4 − , methanesulfonate, trifluoromethanesulfonate, tris(pentafluoroethyl)trifluorophosphate, bis(fluorosulfonyl)imide, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide, bis(trifluoromethanesulfonylimide), bis(perfluoroethanesulfonyl)imide, bis(oxalate)borate, difluoro(oxalate)borate, bis(fluoromalonato)borate, tetracyanoborate, dicyanotriazolate, dicyano-trifuloromethyl-imidazolate, dicyano-pentafuoroethyl-imidazoleate, and ion pairs thereof,
wherein the second species comprises at least one of an atom, an ion, an ion pair, and a molecule, each independently selected from the group consisting of Mn, Fe, Cu, and Ni,
wherein the separator further comprises a membrane support laminated to the first membrane layer, and wherein the membrane support is permeable to the second species,
wherein the membrane support is a porous polymer selected from the group consisting of fluoro-polymeric fibers of polyethylene-co-tetrafluoroethylene (PETFE) and poly(ethylenechloro-co-trifluoroethylene) (e.g., a fabric woven from these used either by itself or laminated with a fluoropolymeric microporous film), polyvinylidene difluoride, polystyrenes, polyarylether sulfones, polyvinyl chlorides, polypropylene, polyethylene, polyamides, polyimides, polyacrylics, polyacetals, polycarbonates, polyesters, polyetherimides, polyimides, polyketones, polyphenylene ethers, polyphenylene sulfides, polymethylpentene, polysulfones non-woven glass, glass fiber materials, ceramics, metal oxides, and composites of organic and inorganic species, and
wherein an average pore diameter of the membrane support is at least about 10 nanometers.
2. The electrochemical cell of claim 1 , comprising:
the positive electrode;
the negative electrode;
the separator disposed between the positive electrode and the negative electrode, wherein the separator provides electronic isolation between the positive electrode and the negative electrode, wherein the separator comprises a first membrane layer; and
the electrolyte comprising the first species and the second species, wherein the first species is an ion having a charge of +1 or −1, wherein the first and second species are different, and wherein the electrolyte is in electrical contact with both the positive and negative electrodes,
wherein the first membrane layer is permeable to the first species and substantially impermeable to the second species.
3. The electrochemical cell of claim 1 , wherein the first membrane layer has an average pore diameter of from 0.1 nm to 10 nm.
4. The electrochemical cell of claim 1 , wherein the first membrane layer has an average pore diameter of from 0.1 nm to 1 nm.
5. The electrochemical cell of claim 1 , wherein the first membrane layer has a surface area of from 100 m 2 /g to 3000 m 2 /g, as measured by nitrogen adsorption BET.
6. The electrochemical cell of claim 1 , wherein the first membrane layer comprises a polymer of intrinsic microporosity.
7. The electrochemical cell of claim 1 , wherein the first membrane layer comprises a planar species and a linker having a site of contortion, wherein the linker is selected from the group consisting of a spiro group, a bridged ring moiety, and a sterically congested single covalent bond.
8. The electrochemical cell of claim 7 , wherein the planar species is represented by a formula:
9. The electrochemical cell of claim 1 , wherein the first species comprises an ion having a charge of +1.
10. The electrochemical cell of claim 1 , wherein the first species is selected from the group consisting of H + , Li + , Na + and K + .
11. The electrochemical cell of claim 1 , wherein the first species is selected from the group consisting of F − , Cl − , Br − , I − , BF 4 − , PF 6 − , AsF 6 − , ClO 4 − , methanesulfonate, trifluoromethanesulfonate, tris(pentafluoroethyl)trifluorophosphate, bis(fluorosulfonyl)imide, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide, bis(trifluoromethanesulfonylimide), bis(perfluoroethanesulfonyl)imide, bis(oxalate)borate, difluoro(oxalate)borate, bis(fluoromalonato)borate, tetracyanoborate, dicyanotriazolate, dicyano-trifuloromethyl-imidazolate, and dicyano-pentafuoroethyl-imidazoleate.
12. The electrochemical cell of claim 1 , wherein the ion is a metal ion, wherein the second species further comprises a ligand binding the metal ion.
13. The electrochemical cell of claim 12 , wherein the ligand is selected from the group consisting of methanesulfonate, trifluoromethanesulfonate, tris(pentafluoroethyl)trifluorophosphate, bis(fluorosulfonyl)imide, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, cyclo-hexafluoropropane-1,1-bis(sulfonyl)imide, bis(trifluoromethanesulfonylimide), bis(perfluoroethanesulfonyl)imide, bis(oxalate)borate, difluoro(oxalate)borate, bis(fluoromalonato)borate, tetracyanoborate, dicyanotriazolate, dicyano-trifuloromethyl-imidazolate, dicyano-pentafuoroethyl-imidazoleate, acetylacetonate, acetylacetone, and a β-ketoester of the formula RC═OCH 2 COOR′, where R and R′ are each independently C 1-6 alkyl, C 6-12 aryl, or C 1-6 alkoxy-C 1-6 alkyl.
14. The electrochemical cell of claim 1 , wherein the second species is selected from the group consisting of manganese (II) bis(trifluoromethanesulfonyl)imide (Mn(TFSI) 2 ), and nickel(II) bis(trifluoromethanesulfonyl)imide (Ni(TFSI) 2 ).
15. The electrochemical cell of claim 1 , wherein the membrane support is adjacent to the first membrane layer.
16. The electrochemical cell of claim 1 , wherein the first membrane layer is disposed between the membrane support and the positive electrode.
17. The electrochemical cell of claim 16 , wherein the separator further comprises a second membrane layer laminated to the membrane support.
18. The electrochemical cell of claim 17 , wherein the membrane support is disposed between the first membrane layer and the second membrane layer.
19. The electrochemical cell of claim 17 , wherein the second membrane layer is permeable to the first species providing ionic communication between the positive electrode and the negative electrode, and wherein the second membrane layer is substantially impermeable to the second species comprising the element of the electrochemical active material of the positive electrode.
20. The electrochemical cell of claim 17 , wherein the second membrane layer comprises a ceramic material selected from the group consisting of aluminum oxide, silicon oxide, silicon carbide, titanium dioxide, magnesium oxide, tin oxide, cerium oxide, zirconium oxide, barium titanite, yttrium oxide, boron nitride, and/or an ion conducting ceramic.
21. The electrochemical cell of claim 1 , wherein the first membrane layer directly interfaces the negative electrode and/or the positive electrode.