Chemically stabilized ionomers containing inorganic fillers
Ionomeric polymers that are chemically stabilized and contain inorganic fillers are prepared, and show reduced degradation. The ionomers care useful in membranes and electrochemical cells.
1. A composition comprising a chemically stabilized, fluorinated ionomer having an inorganic filler incorporated therein, wherein the inorganic filler is a metal oxide, metal hydroxide, metal phosphate, or mixture thereof, and wherein the ionomer has been fluorinated by subjecting it to a fluorinating agent until the ionomer contains less than 200 unstable groups per 1,000,000 carbon atoms, wherein fluoride ion release in a third cycle of a Fenton Test using an acid form of the composition is in the range of 0.4 to 0.5 mgF/g of a membrane incorporating the composition, wherein in each cycle of a Fenton Test 0.6 g of dried composition is soaked in a glass tube containing 0.0029 g of FeSO 4 .7H 2 O dissolved in 50 ml of 30% hydrogen peroxide and heated at 85° C. for 18 hours.
2. The composition of claim 1 that contains less than 70 unstable groups per 1,000,000 carbon atoms.
3. The composition of claim 1 wherein the inorganic filler is present at about 1% to about 40% by weight, based on the total weight of the ionomer after incorporation.
4. The composition of claim 3 wherein the inorganic filler is present at about 3% to about 20% by weight, based on the total weight of the ionomer after incorporation.
5. The composition of claim 1 wherein the metal in the metal oxide, metal hydroxide, metal phosphate is titanium, zirconium, or hafnium, or mixture thereof.
6. The composition of claim 1 wherein the inorganic filler is a zirconium phosphate.
7. The composition of claim 1 wherein the fluorinated ionomer comprises a highly fluorinated carbon backbone and a side chain represented by the formula: —(O—CF 2 CFR f ) a —(O—CF 2 ) c —(CFR′ f ) b SO 3 M wherein R f and R′ f are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a=0 to 2, b=0 to 1, c=0 to 6, and M is hydrogen or one or more univalent cations.
8. A membrane comprising the composition of claim 1 .
9. An electrochemical cell comprising the membrane of claim 8 .
10. An electrode for use in an electrochemical cell comprising the composition of claim 1 .
11. An electrochemical cell comprising the ionomer of claim 1 .
12. The electrochemical cell of claim 11 that is a fuel cell.
13. A membrane comprising a porous support having interconnecting pores, a chemically stabilized fluorinated ionomer, and an inorganic filler, wherein:
the inorganic filler is from the group of metal oxides, metal hydroxides, metal phosphates, and mixtures thereof;
the ionomer has been chemically stabilized by subjecting it to a fluorinating agent until it contains less than 200 unstable groups per 1,000,000 carbon atoms; and
the inorganic filler is distributed throughout the ionomer forming a composition, and the composition is distributed throughout the pores of the porous support,
wherein fluoride ion release in a third cycle of a Fenton Test of an acid form of the composition is in the range of 0.4 to 0.5 mgF/g of the membrane incorporating the composition.
14. The membrane of claim 13 wherein the porous support is microporous PTFE in expanded or fibrillar form.
15. The membrane of claim 13 wherein the ionomer and inorganic filler substantially fill the pores of the porous support.
16. An electrochemical cell comprising the membrane of claim 13 .