US2007009778A1PendingUtilityA1

Proton conducting membrane using a solid acid

Assignee: CALIFORNIA INST OF TECHNPriority: Jan 22, 1999Filed: Sep 6, 2006Published: Jan 11, 2007
Est. expiryJan 22, 2019(expired)· nominal 20-yr term from priority
C25B 13/05H01G 11/52B01D 53/228B01D 69/1411B01D 67/00411B01D 71/02Y02E60/10H01B 1/122H01M 6/181Y02E60/50H01M 8/0631C25B 13/04C01B 2203/0405B01D 2325/26B01D 2257/108B01D 67/0055Y02P70/50Y02E60/13B01D 71/00B01J 19/2475B01D 67/0044H01M 10/0562C01B 2203/0475C01B 2203/047H01M 8/1246B01D 53/32H01M 8/0662H01M 2300/0068H01M 8/1016H01M 8/0289H01M 6/18C01B 3/501
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Claims

Abstract

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.

Claims

exact text as granted — not AI-modified
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.

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