Proton conducting membrane using a solid acid
A solid acid material is used as a proton conducting membrane in an electrochemical device. The solid acid material can be one of a plurality of different kinds of materials. A binder can be added, and that binder can be either a nonconducting or a conducting binder. Nonconducting binders can be, for example, a polymer or a glass. A conducting binder enables the device to be both proton conducting and electron conducting.
1 . A proton conducting membrane, formed of a solid acid material in a solid phase.
2 . A membrane as in claim 1 wherein said solid acid material is of a type that is capable of a superprotonic transition.
3 . A membrane as in claim 1 wherein said solid acid material is of the general form M a H b (XO t ) c .
4 . A membrane as in claim 3 wherein t is 3 or 4.
5 . A membrane as in claim 1 wherein said solid acid material is of the general form Cs a H b (XO t ) c .
6 . A membrane as in claim 3 where X is silicon.
7 . A membrane as in claim 4 wherein M is Cs.
8 . A membrane as in claim 4 wherein M is NH 4 .
9 . A membrane as in claim 4 wherein said solid acid is of the form M a H b (XO t ) c .nH 2 O.
10 . A membrane as in claim 4 wherein X is P.
11 . A membrane as in claim 3 , wherein said solid acid is CsH 2 PO 4 .
12 . A membrane as in claim 3 , wherein said solid acid is Cs 5 (HSO 4 ) 3 (H 2 PO 4 ) 2 .
13 . A membrane as in claim 3 , wherein said solid acid is Cs 2 (HSO 4 ) x (H 2 PO 4 ) y .
14 . A membrane as in claim 3 , wherein said solid acid is Cs 3 (HSO 4 ) 2 (H 1.5 (S 0.5 P 0.5 )O 4 ).
15 . A membrane as in claim 3 , wherein said solid acid is Cs 5 H 3 (SO 4 ) 4 .xH 2 O.
16 . A membrane as in claim 3 , wherein said solid acid is TlHSO 4 .
17 . A membrane as in claim 3 , wherein said solid acid is CsH(SeO 4 ) x .
18 . A membrane as in claim 3 , wherein said solid acid is Cs 2 (HSeO 4 ) (H 2 PO 4 ).
19 . A membrane as in claim 3 , wherein said solid acid is (NH 4 ) 3 H(SO 4 ) 2 .
20 . A membrane as in claim 3 , wherein said solid acid is (NH 4 ) 2 (HSO 4 ) (H 2 PO 4 ).
21 . A membrane as in claim 3 , wherein said solid acid is Rb 3 H (SO 4 ) 2 .
22 . A membrane as in claim 3 , wherein said solid acid is Rb 3 H (SeO 4 ) 2 .
23 . A membrane as in claim 3 , wherein said solid acid is Cs 1.5 Li 1.5 H(SO 4 ) 2 .
24 . A membrane as in claim 3 , wherein said solid acid is Cs 2 Na (HSO 4 ) 3 .
25 . A membrane as in claim 3 , wherein said solid acid is TlH 3 (SeO 3 ) 2 .
26 . A membrane as in claim 3 , wherein said solid acid is CsH 2 AsO 4 .
27 . A membrane as in claim 3 , wherein said solid acid is (NH 4 ) 2 (HSO 4 ) (H 2 AsO 4 ).
28 . A membrane as in claim 3 , wherein said solid acid is CaNaHSiO 4 .
29 . A membrane as in claim 3 , further comprising an electrochemical device, using said membrane for proton transport.
30 . A membrane as in claim 1 wherein said solid acid material is formed of a material that is not water soluble.
31 . A proton conducting membrane, formed of an solid acid material in a superprotonic phase, said solid acid material being of the general formula M a H b (XO t ) c , where t is 3 or 4, the M material is at least one material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl or NH 4 + , and the X material is at least one material from the group consisting of Si, P, S, As, Se, or Te.
32 . A membrane as in claim 31 wherein said solid acid is non-water soluble.
33 . A method of conducting protons across a barrier, comprising:
forming a membrane from a solid acid material; and
using said solid acid material to conduct protons.
34 . A method as in claim 33 , wherein said solid acid is of a type that is capable of a superprotonic transition between a first temperature and a second temperature; and
operating said membrane as a proton conducting membrane at a temperature between said first and second temperatures.
35 . A method as in claim 33 wherein said solid acid material is of the general form M a H b (XO t ) c .
36 . A method as in claim 35 wherein M is Cs.
37 . A method as in claim 35 wherein M is NH 4 + .
38 . A method as in claim 35 wherein X includes silicon.
39 . A method as in claim 33 wherein said protons are conducted in a fuel cell.
40 . A method as in claim 33 wherein said protons are conducted in a hydrogen separator.
41 . A method as in claim 33 wherein said protons are conducted in an electrolysis cell.
42 . A method as in claim 33 wherein said protons are conducted in a battery.
43 . A proton conducting membrane, comprising:
an solid acid material; and
a structural binder for said solid acid material, forming a membrane with said solid acid material.
44 . A membrane as in claim 43 wherein said structural binder is a polymer.
45 . A membrane as in claim 44 wherein said solid acid material is a type capable of a superprotonic transition at a specified temperature.
46 . A membrane as in claim 43 wherein said solid acid material is a non-water soluble solid acid material.
47 . A membrane as in claim 44 wherein said polymer is a melt processable polymer.
49 . A membrane as in claim 44 wherein said polymer is an in-situ polymerized polymer.
50 . A membrane as in claim 43 wherein said structural binder is a ceramic.
51 . A membrane as in claim 43 wherein said structural binder is a glass.
52 . A membrane as in claim 43 wherein said structural binder is electronically insulating.
53 . A membrane as in claim 43 wherein said structural binder is electrically conducting.
54 . A membrane as in claim 53 wherein said conducting material is a conducting polymer.
55 . A membrane as in claim 53 wherein said conducting material is a metal.
56 . A membrane as in claim 55 wherein said metal is mixed with a polymer.
57 . A membrane as in claim 53 wherein said conductor is formed by direct chemical substitution with variable valence ions.
58 . A membrane as in claim 43 wherein said structural binder includes silicon.
59 . A membrane as in claim 43 wherein said structural binder is a polyester binder.
60 . A membrane as in claim 43 wherein said structural binder is electrochemically unreactive.
61 . A membrane as in claim 43 wherein said solid acid is of the of the general formula M a H b (XO t ) c , where:
the M material is a material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Te or NH 4 + , and
the X material is from the group consisting of Si, P, S, As, Se, or Te.
62 . A membrane as in claim 61 wherein M is Cs.
63 . A membrane as in claim 61 wherein X is Si.
64 . A membrane as in claim 61 where M is NH 4 + .
65 . A membrane as in claim 61 wherein said solid acid material is a solid acid material.
66 . A membrane as in claim 61 wherein said solid acid material is water insoluble.
67 . A membrane as in claim 53 wherein said solid acid material is processed to include variable valence elements.
68 . A fuel cell as in claim 67 , wherein said solid-acid material is water insoluble.
69 . A fuel cell as in claim 67 , wherein said solid acid material is of the general formula M a H b (XO t ) c , where:
the M group is a material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl or NH 4 + , and
the X material is from the group consisting of Si, P, S, As, Se, or Te.
70 . A method of operating an electrochemical device comprising:
providing a fuel to a proton conducting membrane; and
carrying out an electrochemical reaction at said proton conducting membrane, without humidifying said membrane.
71 . A method as in claim 70 , wherein said carrying out comprises operating at a temperature of 100° degrees C. or higher.
72 . A method as in claim 70 , wherein said proton conducting membrane includes an solid acid material.
73 . A method as in claim 70 , wherein said proton conducting membrane includes an solid acid material in a superprotonic phase.
74 . A method as in claim 72 , wherein said proton conducting membrane includes a binder.
75 . A method as in claim 74 , wherein said solid acid material is of the general formula M a H b (XO 4 ) c , where:
the M group is a material from the group consisting of Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Tl or NH 4 + , and
the X material is from the group consisting of Si, P, S, As, Se, or Te.
76 . A proton and electron conducting membrane, formed of an solid acid material.
77 . A membrane as in claim 76 wherein said solid acid material is of a type that is capable of a superprotonic transition at a specified temperature.
78 . A membrane as in claim 76 wherein said solid acid material is of the general formula M a H b (XO t ) c .
79 . A membrane as in claim 76 wherein said solid acid material is a solid acid material.
80 . A membrane as in claim 78 where X includes silicon.
81 . A membrane as in claim 76 , further comprising a binder for the solid acid material.
82 . A membrane as in claim 76 wherein said binder includes a conducting material.
83 . A membrane as in claim 82 wherein said conducting material includes a conductive polymer.
84 . A membrane as in claim 82 wherein said conducting material includes a metal material.
85 . A membrane as in claim 76 wherein said solid acid material has free valence electrons.
86 . A method of separating H 2 from other materials, comprising:
chemically reacting a H 2 at a surface of a proton and electron conducting membrane which is formed of materials including a solid acid material, to decompose said H into H+ and e−; and
using said membrane formed of an solid acid material to allow said H+ and e− to pass while blocking other materials including CO from passing.
87 . A proton conducting membrane comprising;
a Cs based solid acid material; and
a melt processable polymer binder for said solid acid material, forming a membrane with said solid acid material.
88 . A membrane as in claim 87 wherein said Cs based solid acid is one of CS 3 (HSO 4 ) 2 (H 1.5 (S 0.5 P 0.5 )O 4 ), Cs 3 (HSO 4 ) 2 (H 2 PO 4 ), Cs 5 (HSO 4 ) 3 (H 2 PO 4 ) 2 or Cs 2 (HSO 4 )(H 2 PO 4 )CsHSO 4 , CsHSeO 4 or Cs 5 H 3 (SO 4 ) 4 .xH 2 O.
89 . A membrane as in claim 87 wherein said melt processable polymer is polyvinylidine fluoride.
90 . A membrane as in claim 87 wherein said membrane is formed by hot pressing.
91 . A proton conducting membrane, comprising:
a NH 4 based solid acid material; and
a structural binder for said solid acid material, forming a membrane with said solid acid material.
92 . A membrane as in claim 91 wherein said structural binder is a melt processable polymer.
93 . A membrane as in claim 91 wherein said solid acid is one of CsH 2 PO 4 , Cs 5 (HSO 4 ) 3 (H 2 PO 4 ) 2 , Cs 2 (HSO 4 )(H 2 PO 4 ), Cs 3 (HSO 4 ) 2 (H 2 PO 4 ) 2 , Cs 3 (HSO 4 ) 2 (H 1.5 (S 0.5 P 0.5 )O 4 ), Cs 5 H 3 (SO 4 ) 4 .xH 2 O, TlHSO 4 , CsHSeO 4 , CS 2 (HSeO 4 )(H 2 PO 4 ), Cs 3 H(SeO 4 ) 2 (NH 4 ) 3 H(SO 4 ) 2 , (NH 4 ) 2 (HSO 4 )(H 2 PO 4 ), Rb 3 H (SO 4 ) 2 , Rb 3 H(SeO 4 ) 2 , Cs 1.5 Li 1.5 H(SO 4 ) 2 , Cs 2 Na(HSO 4 ) 3 , TlH 3 (SeO 3 ) 2 , CsH 2 AsO 4 (NH 4 ) 2 (HSO 4 )(H 2 AsO 4 ), T e O 4 , or CaNaHSiO 4 .
94 . A proton conducting membrane, comprising:
a solid acid silicate of the general form M A H B SiO 4 used in a proton conducting membrane.
95 . A membrane as in claim 94 further comprising a structural binder for said solid acid material.
96 . A membrane as in claim 94 wherein said solid acid is one of CaNaHSiO 4 , Cs 3 HSiO 4 or (NH 4 ) 3 HSiO 4 .
97 . A proton conducting membrane, comprising:
a Cs or NH 4 based solid acid; and
a ceramic or glass binder, forming a structural binder for said solid acid.
98 . A device as in claim 97 wherein said binder is porous.
99 . A method of using an electrochemical device, comprising:
forming a solid acid material into a proton conducting membrane; and
using said solid acid membrane to conduct protons.
100 . A method as in claim 99 further comprising heating said solid solid acid material to a temperature at which it undergoes a superprotonic transition, prior to said using.
101 . A method as in claim 99 wherein said solid solid acid compound is a sulfate or sulfate phosphate type solid acid.
102 . A method as in claim 99 wherein said solid solid acid compound is a selenate or selenate phosphate solid acid.
103 . A method as in claim 99 wherein said solid solid acid is a silicate.
104 . A method as in claim 99 wherein said forming comprises adding a binder to said material.
105 . A method as in claim 104 wherein said binder is a polymer.
106 . A method as in claim 104 wherein said binder is a ceramic/oxide glass.
107 . A material as in claim 104 wherein said binder is a conducting metal or semiconductor.
108 . A method of operating an electrochemical device, comprising:
forming a membrane using a solid acid material of the general form M a H b (XO t ) c ; and
using said solid solid acid material to conduct protons in the electrochemical device.
109 . A membrane as in claim 31 , wherein said solid acid is a solid solid acid material.
110 . A proton conducting membrane, formed of a solid acid material in a superprotonic phase.
111 . A method of operating an electrochemical device comprising:
providing a fuel to a proton conducting membrane which includes a carbon monoxide material therein, and
carrying out an electrochemical reaction at said proton conducting membrane, without removing said carbon monoxide material.
112 . A method of forming a membrane-electrode assembly, comprising:
forming a composite film including a polymer and an solid acid of the general form M a H b (XO t ) c ;
forming said composite film onto a backing;
forming electrodes on said backing; and
hot pressing said material to form an assembly.
113 . A method as in claim 112 , wherein an solid acid to polymer volume ratio is 50/50.
114 . A method as in claim 112 , wherein said backing is graphite paper.
115 . A method as in claim 33 , wherein said protons are conducted in a supercapacitor.