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Patent US7416803 - Solid acid electrolytes for electrochemical devices - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsImproved solid acid electrolyte materials, methods of synthesizing such materials, and electrochemical devices incorporating such materials are provided. The stable electrolyte material comprises a solid acid capable undergoing rotational disorder of oxyanion groups and capable of extended operation...http://www.google.com/patents/US7416803?utm_source=gb-gplus-sharePatent US7416803 - Solid acid electrolytes for electrochemical devicesAdvanced Patent SearchPublication numberUS7416803 B2Publication typeGrantApplication numberUS 10/211,882Publication dateAug 26, 2008Filing dateAug 1, 2002Priority dateJan 22, 1999Fee statusPaidAlso published asUS8202663, US20030104258, US20090075149Publication number10211882, 211882, US 7416803 B2, US 7416803B2, US-B2-7416803, US7416803 B2, US7416803B2InventorsSossina M. Haile, Calum Chisholm, Ryan B. Merle, Dane A. Boysen, Sekharipuram R. NarayananOriginal AssigneeCalifornia Institute Of TechnologyExport CitationBiBTeX, EndNote, RefManPatent Citations (29), Non-Patent Citations (32), Referenced by (3), Classifications (70), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetSolid acid electrolytes for electrochemical devices
US 7416803 B2Abstract
Improved solid acid electrolyte materials, methods of synthesizing such materials, and electrochemical devices incorporating such materials are provided. The stable electrolyte material comprises a solid acid capable undergoing rotational disorder of oxyanion groups and capable of extended operation at elevated temperatures, that is, solid acids having hydrogen bonded anion groups; a superprotonic, trigonal, tetragonal, or cubic, disordered phase; and capable of being operating at temperatures of ˜100� C. and higher.
1. A fuel cell comprising an electrolyte membrane operative in the presence of water vapor, wherein said electrolyte membrane comprises
a solid acid having a crystal structure which becomes disordered with concomitant high conductivity upon achieving a superprotonic phase; and
said electrolyte membrane being capable of operation at temperatures of at least 100� C. in the presence of water vapor.
2. An electrolyte membrane, said membrane comprising:
a solid acid of the general form: (MxM′1−x)3H3x(YO4)2, where M is any alkali or transition metal or other functional group having a +1 charge, M′ is any alkaline earth or transition metal having a +2 charge, Y is selected from the group consisting of P, As, and mixture thereof, and X is less than or equal to 1; and
said electrolyte membrane being capable of operation at temperatures of at least 100� C.
3. An electrolyte membrane, said membrane comprising:
a solid acid of the general form: M′3H2x[(Y1−x, Ax)O4]2, where M′ is any alkaline earth or transition metal having a +2 charge, A is one of either Si or Ge, Y is selected from the group consisting of P, As, and mixture thereof, and X is less than or equal to 1; and
4. The electrolyte membrane as described in claim 2, wherein M is selected from the group consisting of: Li, Na, K, Rb, Cs, Fr, and NH4.
5. The electrolyte membrane as described in claim 2 or 3, wherein M′ is selected from the group consisting of: Be, Mg, Ca, Sr, Ba, Ra, and Pb.
6. The electrolyte membrane as described in claims 2 or 3, further comprising a structural binder material.
7. The electrolyte membrane as described in claim 6, wherein the structural binder material is a species selected from the group consisting of: graphite, polymers, ceramics, glasses, and metals.
8. The electrolyte membrane as described in claims 2 or 3, further comprising a separate conducting material.
9. The electrolyte membrane as described in claim 8, wherein the conducting material is selected from the group consisting of: conducting polymer, metals and an electronically conducting carbon material.
10. The electrolyte membrane as described in claims 2 or 3, wherein said solid acid includes at least one variable valence element.
11. The electrolyte membrane as described in claims 2 or 3 wherein said solid acid is water insoluble.
12. The electrolyte membrane as described in claims 2 or 3, wherein said solid acid is thermally stable at temperatures above 100� C.
13. The electrolyte membrane as described in claims 2 or 3, wherein said solid acid conducts protons.
14. The electrolyte membrane as described in claims 2 or 3, wherein said solid acid has a proton conductivity of about 10−5 Ω−1 cm−1 or higher at the temperature of utilization.
15. The electrolyte as described in claim 2 or 3, wherein said solid acid conducts both protons and electrons.
16. An electrochemical device incorporating the solid acid electrolyte membrane described in any of claim 2 or 3.
17. The electrochemical device as described in claim 16, wherein the device is selected from the group consisting of: fuel cells, batteries, hydrogen separation membranes, and membrane reactors.
18. An electrolyte membrane, said membrane comprising:
i) a solid acid of the general form: (MxM′1−x)3H3x(YO4)2, wherein M is an alkali or a transition metal or other functional group having a +1 charge, M′ is an alkaline earth or a transition metal having a +2 charge; Y is selected from the group consisting of P, As, and mixture thereof; and X is less than or equal to 1;
ii) a separate conducting material selected from the group consisting of a conducting polymer, a metal and an electronically conducting carbon material; and
iii) said electrolyte membrane being capable of operation at temperatures of at least 100� C.
19. An electrolyte membrane, said membrane comprising:
i) a solid acid of the general form: (MxM′1−x)3H3x(YO4)2, where M is any alkali or transition metal or other functional group having a +1 charge, M′ is any alkaline earth or transition metal having a +2 charge; Y is selected from the group consisting of P, As, and mixture thereof; and x is less than or equal to 1; wherein said solid acid includes at least one variable valence element; and
ii) said electrolyte membrane being capable of operation at temperatures of at least 100� C.
20. An electrolyte membrane, said membrane comprising:
ii) said electrolyte membrane being capable of operation at temperatures of at least 100� C. and conducting both protons and electrons.
21. An electrolyte membrane, said membrane comprising:
i) a solid acid of the general form: M′3H2x[(Y1−x, Ax)O4]2, wherein M′ is an alkaline earth or a transition metal having a +2 charge; A is Si or Ge; Y is selected from the group consisting of P, As, and mixture thereof; and x is less than or equal to 1;
22. An electrolyte membrane, said membrane comprising:
i) a solid acid of the general form: M′3H2x[(Y1−x, Ax)O4]2, wherein M′ is an alkaline earth or a transition metal having a +2 charge; A is Si or Ge; Y is selected from the group consisting of P, As, and mixture thereof; and x is less than or equal to 1; wherein said solid acid includes at least one variable valence element; and
23. An electrolyte membrane, said membrane comprising:
24. The fuel cell of claim 1, further comprising a structural binder material.
25. The fuel cell of claim 24, wherein the structural binder material is a species selected from the group consisting of: graphite, polymers, ceramics, glasses, and metals.
26. The fuel cell of claim 1, further comprising a separate conducting material.
27. The fuel cell of claim 26, wherein the conducting material is selected from the group consisting of: conducting polymer, metals and an electronically conducting carbon material.
28. The fuel cell as described in claim 1, wherein said solid acid is thermally stable at temperatures above 100� C.
29. The fuel cell as described in claim 1, wherein said solid acid conducts protons.
30. The fuel cell as described in claim 1, wherein said solid acid has a proton conductivity of about 10−5 Ω−1 cm−1 or higher at the temperature of utilization.
31. The fuel cell as described in claim 1, wherein said solid acid conducts both protons and electrons.
32. An electrochemical device comprising an electrolyte membrane operative in the presence of water vapor, wherein said electrolyte membrane comprises
a solid acid having a crystal structure which becomes disordered with concomitant high conductivity upon achieving a superprotonic phase;
said electrolyte membrane being capable of operation at temperatures of at least 100� C.; and
wherein the electrochemical device is selected from the group consisting of a fuel cell, a hydrogen separation membrane, membrane reactors and an electrolysis cell
said electrolyte membrane of said fuel cell, said hydrogen separation membrane and said membrane reactor being in contact with an atmosphere containing water vapor; and
said electrolyte membrane of said electrolysis cell being in contact with water.
This application is a continuation-in-part of U.S. application Ser. No. 09/439,377, filed Nov. 15, 1999, now U.S. Pat. No. 6,468,684, which claims priority to U.S. Provisional Application Nos. 60/116,741, filed Jan. 22, 1999; 60/146,946, filed Aug. 2, 1999; and 60/151,811, filed Aug. 30, 1999, the disclosures of which are fully incorporated herein by reference; and this application also claims priority to U.S. Provisional Application Nos. 60/309,807, filed Aug. 1, 2001; and 60/355,362, filed Feb. 6, 2002, the disclosures of which are also fully incorporated herein by reference.
The invention described herein was made in performance of work under contracts to the National Science Foundation [DMR-9902882] and the Office of Naval Research [N00014-01-1-0304 and N00014-02-1-0192], and is subject to the provisions of Public Law 96-517 (U.S.C. 202) in which the Contractor has elected to retain title.
The present invention relates to electrolytes for electrochemical devices, methods of synthesizing such materials, and electrochemical devices incorporating such materials; and more particularly to electrolytes made from novel solid acid materials.
Electrochemical devices depend on the flow of protons, or the flow of both protons and electrons, through a proton conducting material, such as a membrane. Accordingly, materials which conduct protons, or both protons and electrons, have applications as electrolytes or electrodes in a number of electrochemical devices including fuel cells, electrochemical or supercapacitors, sensors, hydrogen separation membranes and membrane reactors.
One particularly important application for these materials is in fuel cells. Fuel cells are attractive alternatives to combustion engines for a wide variety of applications, because of their higher efficiency and the lower level of pollutants produced from their operation. There are three common types of fuel cells relevant to this patent: 1) a direct hydrogen/air fuel cell system, which stores hydrogen and then delivers it to the fuel cell as needed; 2) an indirect hydrogen/air fuel cell, in which hydrogen is generated on site from a hydrocarbon fuel, cleaned of carbon monoxide, and subsequently fed to the fuel cell; and 3) a direct methanol fuel cell (“DMFC”), which feeds a methanol/water solution directly to the fuel cell. An example of this later fuel cell was described, for example, in U.S. Pat. No. 5,559,638, the disclosure of which is incorporated herein by reference.
Regardless of the fuel cell design chosen, the operating efficiency of the device is limited by the efficiency of the electrolyte at transporting protons. Typically, perflourinated sulphonic acid polymers, polyhydrocarbon sulfonic polymers, and composites thereof are used as electrolyte membrane materials for fuel cell. However, these conventional materials utilize hydronium ions (H3O+) to facilitate proton conduction. Accordingly, these materials must be hydrated, and a loss of water immediately results in degradation of the conductivity of the electrolyte and therefore the efficiency of the fuel cell. Moreover, this degradation is irreversible, i.e., a simple reintroduction of water to the system does not restore the conductivity of the electrolyte.
As a result, fuel cells utilizing these materials require peripheral systems to ensure water recirculation and temperature control to keep the water from evaporating. Not only do these systems increase the complexity and cost of these fuel cells, but because the system cannot exceed a temperature of 100� C. the fuel cell catalysts and other systems cannot be operated a maximum efficiency. Higher temperatures would also reduce carbon monoxide poisoning of the fuel cell catalyst.
It has recently been shown that the solid acids such as CsHSO4 can be used as the electrolyte in fuel cells operated at temperatures of 140-160� C. Use of this material greatly simplifies fuel cell design relative to polymer electrolyte fuel cells because hydration of the electrolyte is not necessary and, because of the elevated temperature of operation, residual CO in the fuel stream can be better tolerated. The high conductivity of CsHSO4 and analogous materials results from a structural phase transition that occurs at 141� C. from an ordered structure, based on chains of SO4 groups linked by well-defined hydrogen bonds, to a disordered structure in which SO4 groups freely reorient and easily pass protons between one another. Thus, disorder in the crystal structure is a key prerequisite for high proton conductivity.
Ultimately, solid acid electrolytes may solve many of the problems facing state-of-the-art polymer based fuel cells. These problems include inability to operate at temperatures above 100� C. (which would increase the CO tolerance of the Pt catalyst), humidification requirements, and methanol permeation across the electrolyte. The technological objectives of this work are thus to simply fuel cell operation by use of alternative electrolytes. However, the lifetime of these sulfate and selenium based solid acids is insufficient for commercial applications. The poor lifetime of both CsHSO4 and CsHSeO4 under fuel cell operating conditions results from the reduction of sulfur and selenium by hydrogen in the presence of typical fuel cell catalysts, according to:
2CsHSO4+4H2 - - - >Cs2SO4+H2S+4H2O.
2CsHSeO4+4H2 - - - >Cs2SeO4+H2Se+4H2O.
Accordingly, a need exists for solid acid compounds with high proton conductivity that are stable under fuel cell conditions, and processing methodologies that lead to high performance membrane-electrode-assemblies (MEAs) based on these solid acid compounds.
Accordingly, the present invention is directed to a stable electrolyte material comprising a solid acid capable of forming hydrogen bonds and undergoing rotational disorder capable of extended operation at elevated temperatures, such as, for example, solid acids having a tetrahedral or octahedral hydrogen bonding anion group; a superprotonic trigonal disordered phase; and/or being capable of operating at temperatures of ˜100� C. Specifically, the current invention is directed to several classes of improved solid acid electrolyte materials, methods of synthesizing such materials, and electrochemical devices incorporating such materials.
In one embodiment, the invention is directed to an electrolyte comprising a solid acid having a superprotonic trigonal phase. In one such embodiment, the solid acid may be chosen from phosphate species of the general form: (MxM′1−x)3H3x(PO4)2, where M is any alkali or transition metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +; and M′ is any alkaline earth or transition metal having a +2 charge, such as Mg2+ . . . Ba2+, Pb2+. Alternatively, the solid acid may directed to a mixed phosphate compound having the general form: M3H2x[(P1−x, Six)O4]2 or M3H2x[(P1−x,Gex)O4]2 where M is any alkaline or transition metal having a +2 charge, such as Mg2+ . . . Ba2+, Pb2+.
In another embodiment, the invention is directed to an electrolyte comprising a solid acid having a tetrahedral anion chosen from the group PO4, PO3F and PO3H. In such an embodiment, the solid acid may be of the general form: MH1+x(PO3A)1−x(PO4)x and M3Hx[(PO3A)x(PO4)1−x]2, where M is any alkali metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +, and A is F or H. Thus, the solid acid species may be chosen from monofluorophosphate and phosphite species or from mixed monoflurophosphate/phosphate and mixed phosphite/phosphate species. Finally, the solid acid species may also be chosen from molecules having mixed chromate/phosphate tetrahedral anion species. Such molecules have the general form: MH1+x(CrO4)1−x(PO4)x and M3Hx[(CrO4)x(PO4)1−x]2, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +.
In still another embodiment, the invention is directed to an electrolyte comprising a solid acid having an octahedral anion. In such an embodiment, the solid acid may be chosen from fluorosilicates and germanates of the general form: MHSiF6 and MHGeF6, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +. The solid acid may also be chosen from mixed phosphosilicates and phosphogermanates of the general form: MHx(P1−xSix)F6 and MHx(P1−xGex)F6, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +. The solid acid may also be chosen from compounds with aluminum flouride octahedral anion groups AlF6.
In yet another embodiment, the invention is directed to a membrane comprising the solid acid electrolyte. In such an embodiment, the invention may further comprise a structural binder or matrix material to enhance the mechanical integrity and/or chemical stability of the membrane. In these embodiments the binder may comprise any suitable stabilizing material, such as, for example a polymer, a ceramic, or an oxide glass.
In still yet another embodiment, the invention is directed to an electronically conducting matrix material, such as a metal or a carbon based material.
In still yet another embodiment, the invention is directed to methods of synthesizing the solid acids according to the current invention.
In still yet another embodiment, the invention is directed to an electrochemical device incorporating the solid acid electrolyte. In such an embodiment the electrolyte may be incorporated into any electrochemical device requiring a flow of either protons or protons and electrons across a membrane to function, such as, for example, a fuel cell, a hydrogen separation membrane, or an electrolysis cell.
FIGS. 1 a to 1 e show graphical representations of the properties of an exemplary CsH(PO3H) solid acid according to the current invention;
FIG. 2 shows a graphical representation of the temperature decomposition properties of exemplary solid acid electrolytes under nitrogen according to the current invention;
FIG. 3 shows a graphical representation of the conductivity properties of exemplary solid acid electrolytes under air according to the present invention;
FIG. 4 shows a graphical representation of the conductivity properties of exemplary solid acid electrolytes according to the present invention;
FIG. 5 shows a graphical comparison of the decomposition properties of conventional (CsHSO4) and exemplary solid acid electrolytes under hydrogen according to the present invention;
FIG. 6 shows a graphical comparison of the decomposition properties of conventional (CsHSO4) and exemplary solid acid electrolytes under vapor phase methanol according to the present invention;
FIG. 7 shows a graphical representation of the temperature decomposition properties of exemplary solid acid electrolytes under nitrogen synthesized according to the current invention;
FIG. 8 shows a graphical representation of the conductivity properties of exemplary solid acid electrolytes synthesized according to the current invention;
FIG. 9 shows a graphical representation of the conductivity properties of exemplary solid acid electrolytes synthesized according to the current invention;
FIGS. 10 a and 10 b show a pictorial reproduction of exemplary membranes made of exemplary solid acid electrolytes according to the current invention;
FIG. 11 shows a schematic of an exemplary hydrogen/air fuel cell using an exemplary solid acid electrolyte membrane according to the current invention;
FIG. 12 shows a schematic of an exemplary direct methanol fuel cell using an exemplary solid acid supported by a binder according to the current invention;
FIG. 13 shows a schematic of another exemplary hydrogen separation membrane using an exemplary proton conducting solid acid according to the current invention;
FIG. 14 shows a schematic of an exemplary hydrogen separation membrane using an exemplary mixed electron and proton conducting solid acid according to the current invention; and
FIG. 15 shows a schematic of an exemplary embodiment of a membrane reactor using an exemplary solid acid according to the current invention.
The present invention is directed to a stable electrolyte material comprising a solid acid capable of forming hydrogen bonds and undergoing rotational disorder and capable of extended operation at elevated temperatures, such as, for example, solid acids having a tetrahedral or octahedral hydrogen bonding anion group; a superprotonic trigonal, tetragonal or cubic disordered phase; and/or being capable of operating at temperatures of 100� C. and higher. Such materials are referred to as “solid acid electrolytes” or “electrolytes” herein.
The term solid acids used herein refers to compounds which have properties that are intermediate between those of a normal acid, such as, H2SO4, and a normal salt, such as, Cs2SO4. In general, the chemical formula of the solid acids of the type used according to the present invention can be written as a combination of the salt and the acid, such as, CsHSO4 (0.5 Cs2SO4*0.5H2SO4), which was previously described in U.S. patent application Ser. No. 09/439,377 now U.S. Pat. No. 6,468,684, filed Nov. 15, 1999, the disclosure of which is incorporated herein by reference. Solid acids generally comprise oxyanions, such as, for example, SO4, SO3, SeO4, SeO3, PO4, PO3F, PO3H AsO4, SiF6 or AlF6 etc., which are linked together via O—H . . . O hydrogen bonds. In addition, they contain cations for overall charge balance. The structure may contain more than one type of oxyanion XO4, XO3 XO3A or XF6 group, and may also contain more than one type of cation M species. Under certain conditions of temperature and pressure, generally between about 50 and 100� C., the crystal structure of these solid acids becomes disordered. Concomitant with this disordered state, known as the superprotonic phase, is an increase of the conductivity of the solid acid, often by several orders of magnitude, to between about 10−3 to 10−2 Ω−1 cm−1. Because of the structure of these solid acids, the proton transport mechanism does not rely on the motion of hydronium ions. As a result, solid acids do not need to be hydrated to function and can be operated at elevated temperatures to increase efficiency and reduce the potential for poisoning contamination of the catalyst medium in the electrochemical device.
Although several conventional superprotonic solid acid species are discussed above, these materials generally suffer from by hydrogen in the presence of typical fuel cell catalysts, such as, for example, the reduction of CsHSO4 to H2S according to:
A similar reduction reaction occurs for CsHSeO4.
In addition, many solid acids are water soluble, such as CsHSO4 and CsHSeO4, and thus do not have long lifetimes in the presence of liquid water
Accordingly, the current invention is directed to improved solid acid structures which do not suffer from reduction in the presence of catalytic materials such as Pt and other transition metal elements. Indeed, any solid acids having a tetrahedral or octahedral hydrogen bonding anion group; a superprotonic trigonal disorder phase; and/or being capable of operating at temperatures of ˜100� C. in the presence of typical fuel cell catalysts may be utilized as an electrolyte material in the current invention.
For example, Applicants have discovered that by replacing the Sulfur (or Se) of superprotonic solid acids with elements such as Si and Ge the reduction reaction can be avoided because analogous reduction compounds such as H4Si and H4Ge are extremely unstable. Thus, for example, superprotonic acids such as LaHSiO4, BaH2SiO4, and SrH2GeO4 etc. are preferably used in the devices and materials of the current invention.
In one exemplary embodiment, the invention is directed to a solid acid having a disordered trigonal phase and a tetrahedral anion. For example, it is well known that the compounds Pb3(PO4)2 and Rb3H(SeO4)2 are essentially isostructural at room temperature, with the exception of incorporated protons in the selenate compound. Upon heating, both undergo a transition to a disordered, trigonal phase. Because of the incorporation of protons into the selenate, this disorder is accompanied by an increase of protonic conductivity by several orders of magnitude.
Accordingly, in one exemplary embodiment of a solid acid electrolyte according to the invention having a trigonal disordered phase and a tetrahedral anion the solid acid electrolyte is chosen from the phosphate species of the general form: (M1−xM′x)3H3(PO4)2, where M is any alkaline earth or transition metal having a +2 charge, such as Mg2+ . . . Ba2+, Pb2+; and M′ is any alkali metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +. ncorporation of protons into the phosphate compounds, by substitution of an alkali metal or ammonium ion onto the alkaline earth site, gives rise to a superprotonic high conductivity trigonal disordered phase. An exemplary intermediate alkali-alkaline earth acid phosphate, as formulated here, is Na2CaH2(PO4)2.
In a second exemplary embodiment of trigonal solid acids having tetrahedral anions according to the invention, protons are introduced into the trigonal compounds such as Pb3(PO4)2 by substituting species such as Si4+ and Ge4+ for the P5+. The reduction in positive charge can then be balanced by incorporated protons. For example, in such an embodiment, suitable solid acids can be chosen from the group described by the form: M3H2x[(P1−x,Six)O4]2 and M3H2x[(P1−x,Gex)O4] where M is any alkali or transition metal having a +2 charge, such as Mg2+ . . . Ba2+, Pb2+.
In another embodiment directed to a solid acid electrolyte material having a tetrahedral anion, the tetrahedral anion group, PO3F, is utilized. It is well-known that PO3F, is isoelectronic with SO4, and also shares chemical properties. For example, the compound CsHPO3F is known in the literature, and has a room temperature structure which shares some similarities to the superprotonic tetragonal structure of CsHSO4. The proton content in monofluorophosphate solid acids can be increased by introducing phosphate anions according to the general chemical formula MH1+x(PO3F)1−x(PO4)x, which includes the simple compounds MHPO3F, in analogy to known MH1+x(SO4)1−x(PO4)x compounds. The PO3F anion can be utilized to replace SO4 not only in compounds of general stoichiometry MHSO4, but also in those with stoichiometry M3H(SO4)2. Accordingly, in yet another embodiment of a solid acid having a tetrahedral anion, the solid acid may be chosen from monofluorophosphate and mixed monofluorophosphate/phosphate species of the general form: M3H(PO3F)2 and M3H1+2x[(PO3F)1−x(PO4)x]2, where M is any alkali metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +.
Still another type of tetrahedral group that can be considered a viable substitute for SO4 (or SeO4) is PO3H. The chemical similarity between SO4 and PO3H, is somewhat less than that between SO4 and PO3F, because the P—H bond is quite distinct. Nevertheless, the room temperature structures are built on similar hydrogen bonded tetrahedral units. Several compounds in the MH(PO3H) family are known, including CsH2PO3, KH2PO3, LiH2PO3 and NH4H2PO3. In comparison to compounds such as CsH2PO4, it is noteworthy that the oxidation state is +3 rather than +5, and thus the phosphites are unlikely to be susceptible to reduction during fuel cell operation. Accordingly, in yet another alternative embodiment the tetrahedral solid acid species may be chosen from mixed phosphite and phosphite/phosphate species of the general form: MH(PO3H), M3H(PO3H)2, MH1+x(PO3H)1−x(PO4)x, and M3H1+2x[(PO3H)1−x(PO4)x]2 where M is any alkali metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +.
Moreover, the Applicants have discovered that solid acids in which the sulfate group is replaced with the phosphite will have similar structures, phase transitions and proton transport properties to CsHSO4, but advantageously will not show the degradation from the production of H2S. High temperature investigations of the compound CsH(PO3H) (or CsH2PO3, cesium hydrogen phosphite) revealed that this material undergoes a transition, with an onset of 137� C., to a phase of high proton conductivity. These results are summarized in FIGS. 1 a to 1 e, discussed below. The transition is accompanied by a large heat of transformation, ΔH=58�2 J/g (12.4�0.4 kJ/mole), and exhibits measurable hysteresis, occurring at 96� C. upon cooling, as shown in FIGS. 1 a to 1 c. High temperature X-ray powder diffraction showed that the high temperature phase is cubic, with ao=4.896(1) Å, and likely takes on a CsCl structure, with Cs atoms at the corners of a simple cubic unit cell, and PO3H groups at the center. The conductivity in the high temperature phase at 160� C. is 5.5�10−3 Ω−1 cm−1, and the activation energy for proton transport is 0.40�0.01 eV, as shown by comparison in FIGS. 1 d and 1 e. These values suggest that proton transport is facilitated by rapid PO3H group reorientations in the cubic phase of CsH(PO3H), as is known to occur in the high temperature, tetragonal phase of CsHSO4.
Still another type of solid acid electrolyte material having a tetrahedral anion is formed by K2CrO4 demonstrating the interchangeable nature of sulfates and chromates. Chromates have also been shown to exhibit the same tetrahedral disorder at elevated temperatures that sulfates do, and therefore, the tetrahedral solid acid species may also be chosen from the mixed chromate species of the general form: MH1+x(CrO4)1−x(PO4)x, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +. Mixed sulfate/phosphate compounds have been synthesized with superprotonic phase transitions temperatures lower than the compound end members. For example, in Cs2HSO4H2PO4 the superprotonic phase transition is at 90� C., as compared to CsHSO4 at 141� C. and CsH2PO4 at 230� C. The lowered phase transition temperature in the analogous chromate/phosphates compound helps prevent problematic dehydration of the phosphate above the superprotonic phase transition temperature, and by replacing sulfate with chromate, reduction of the sulfate to H2S in a fuel cell environment is avoided.
In another alternative embodiment, the invention is directed to solid acid electrolyte compounds that contain an octahedral polyanion. In this class, materials such as KPF6 form structures in which disorder is sustained at slightly elevated temperature. However, such materials contain no protons. By replacing the PF6 polyanion with SiF6 or GeF6, protons can be introduced for charge balance reasons. It is also noteworthy that unlike their sulfate and phosphate cousins, these salts and acids are insoluble in water. Accordingly, the solid acid may be chosen from fluorosilicates and germanates of the general form: MHSiF6 and MHGeF6, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4.
Alternatively, the known structural transition in compounds such as KPF6 to a disordered state can be taken advantage of for proton transport by partial (rather than complete) chemical substitution of the PF6 anion by SiF6 or GeF6. Because proton incorporation accompanies the substitution, high conductivity in the high-temperature disordered phase can be obtained. +. Accordingly, in this alternative embodiment of the solid acid, the solid acid electrolyte material may be chosen from mixed phosphosilicates and phosphogermanates of the general form: MHx(P1−xSix)F6 and MHx(P1−xGex)F6, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . . Cs+, NH4 +.
In still another embodiment, the solid acid may have an octahedral anion group according to: AlF6. Exemplary embodiments of such compounds would be MH2AlF6 and M2HAlF6, where M is any alkaline metal or other functional group having a +1 charge, such as, Li+ . . . Cs+, NH4 +; or M′HAlF6, where M′ is +2, where M′ is any alkali or transition metal having a +2 charge, such as Mg2+ . . . Ba2+, Pb2+. Other embodiments would also include mixtures of the above species with MHSiF6, MHGeF6 and MPF6 The preferred material for any specific electrochemical device depends on the application. For example, the preferred species may depend on the needs of a device, such as, high conductivity, low cost, thermal stability or chemical stability, etc.
Although the conductivity of the above-recited solid acids is described as purely protonic, these solid acid electrolytes can be made to conduct both electrons and protons depending on the choice of the M cation and the X element in the anion XO4, XO3 or XF6 portion of the above chemical formulae. For example, by using a given amount of a variable valence element, such as, Pb or In for M, or a transition metal element, such as, for example, Cr or Mn for X, the solid acid can be made to conduct electrons as well as protons.
The invention is also directed to methods of forming the superprotonic solid acid electrolyte materials described above. The synthesis of the stable, high-conductivity solid acid compounds derives from the Applicants' recognition that degradation of conventional solid acid materials, such as CsHSO4 occurs via the reduction of sulfur under hydrogen to yield H2S. This reduction reaction is normally slow, even at fuel cell operation temperatures of ˜100� C., however, it is highly accelerated in the presence of typical fuel cell catalysts.
However, Applicants have discovered that such reduction reactions can be eliminated by replacing the S (or Se) of conventional superprotonic solid acids with elements such as Si and Ge, as H4Si and H4Ge are extremely unstable and unlikely to form. Thus, target analogies to CsHSO4 and CsH2PO4 are, for example, LaHSiO4 and BaH2SiO4, etc.
An additional benefit of such compounds, in cases where alkaline earth or rare earth metals are incorporated rather than alkali metals, is that the resultant compound is water insoluble. In cases where alkali metals are utilized, new stoichiometries such as Cs2H2SiO4 can be probed.
However, in general, acid silicates and germanates are more difficult to synthesis than the analogous sulfates and phosphates both because of the insolubility of the former group of compounds in water, and because of their tendency to form polymerized structures (with Si—O—Si or Ge—O—Ge linkages) rather than crystallizing with isolated XO4 groups.
Accordingly, in a first exemplary embodiment, one method of synthesizing such solid acid electrolyte materials begins with the synthesis of known acid silicates and germanates. Most such compounds contain small alkali or alkaline earth ions. In order to prepare crystalline compounds incorporating large cations (which are necessary for high proton conductivity) the same synthesis procedures are followed with the exception that one or more of the reactant materials is changed, for example, replacing NaOH with CsOH to yield a cesium acid silicate or germanate.
In a second exemplary approach to large cation silicates and germanates an ion exchange reaction is carried out on known compounds. That is, Na can be replaced in a known acid silicate with Cs by soaking the original material in molten CsOH.
In a third exemplary approach compounds containing Li rather than H are formed, and then an ion exchange reaction is carried out in an acid media. For example, the compound LaLiSiO4 is known, the lithium can be replaced with protons using an acid that will not dissolve the base material.
Several exemplary chemically stable superprotonic solid acids have been synthesized according to the above methods including: NaCaHSiO4, BaH2SiO4, SrH2GeO4 and Na2H2SiO4�xH2O. Synthesis methods employed for each are as follows:
CsH(PO3H): The compound CsH(PO3H) was synthesized from aqueous solutions of cesium carbonate and phosphorous acid in which the Cs:PO3H mole ratio was fixed at 1:1. Just enough water was added to ensure complete dissolution, and then the solution gently heated to induce H2O evaporation and precipitation of the product. The resultant material was separated from the mother liquor by filtering and rinsed with acetone.
NaCaHSiO4: combine NaOH, Ca(OH)2 and SiO2 (in a 3:2:2 molar ratio) with a few drops of water and place in a thermal bomb at 280� C. for 48 hours. (B. G. Cooksley and H. F. W. Tayer, Acta. Cryst. B30 (1974) 864-867.)
BaH2SiO4: dissolve NaOH and Na2SiO3 in hot deionized water and then add aqueous BaCl2 (mole ratio of Ba:Si=1.2:1) to induce precipitation of the desired product. (G. Kruger and W. Wieker, Z. Anorg. Allg. Chem. 340 (1965) 227-293.)
SrH2GeO4: combine Sr(OH)2 and GeO2 (in a 1:1 molar ratio) and place in a thermal bomb at 280� C. for several days; or, mix Sr(OH)2 and GeO2 (in a 1:1 molar ratio) in hot water to induce formation of the desired product. (H. Nowotny and G. Szekely, Monat. Chem. Ver. Teile Wissenshft. 161 (1952) 568-582.)
Na2H2SiO4.5H2O: dissolve NaOH and Na2SiO3 in hot deionized water (mole ratio of Na:Si=4.65:1) and slowly evaporate excess water to induce crystal growth of the desired product. (P. B. Jamieson and L. S. Dent Glasser, Acta Cryst. 20 (1966) 373-376.)
Diffraction patterns of the resultant materials were then used to confirm that the desired products were obtained, although it should be understood that in some cases minor amounts of impurity phases will be present. The thermal behavior of the two exemplary dihydrogen silicates according to the invention, BaH2SiO4 and Na2H2SiO4.5H2O has been investigated, and these compounds have been shown to be stable to ˜320� C. (decomposition) and 70� C. (melting), respectively. (G. Kruger and W. Wieker, Z. Anorg. Allg. Chem. 340 (1965) 227-293; J. Flesche, B. Ketterer and R. L. Schmid, Thermochim. Acta 77 (1984) 109-121). The remaining two compounds, NaCaHSiO4 and SrH2GeO4 were characterized by the Applicants by thermal methods (thermogravimetry and calorimetry) and all four compounds were examined by impedance spectroscopy to evaluate their suitability as fuel cell electrolytes. In the case of the sodium calcium acid silicate, H/D ion exchange and subsequent conductivity measurements were additionally performed to establish the nature of the charge-carrying species.
The results in FIG. 2, show thermal gravimetric curves of NaCaHSiO4 and SrH2GeO4, and show that the silicate compound undergoes a gradual weight loss from room temperature to 460� C. of ˜1%, then a rapid decomposition, giving rise to an additional 3.5% weight loss by 560� C., with a maximum in the weight loss rate at 505� C. The overall weight change corresponds to 0.42 moles H2O (per mole NaCaHSiO), which is close to the expected value of 0.5 moles. In contrast, SrH2GeO4 undergoes a rapid weight loss centered at 315� C., which begins at 295� C. and is essentially complete by 335� C. The total weight change of 9.6% corresponds to 1.2 moles of H2O (per mole SrH2GeO4). That this value is greater than the expected value of 8.0% (1 mole H2O/SrH2GeO4) suggests that the initial weight loss over the temperature range 70-295� C. of 1.6 wt % corresponds to the loss of surface water. These results show that the NaCaHSiO4 and SrH2GeO4 compounds exhibit relatively good thermal stability to ˜400� C. and 280� C., respectively.
Calorimetric measurements (results not shown) indicated that none of these compounds undergoes a structural phase transition. That is, no sharp transitions to a superprotonic phase were observed. Rather broad thermal events corresponding to dehydration as established from the gravimetric measurements, were obtained.
The conductivities of the compounds in Examples 1 to 3 are shown in FIG. 3. As shown, the sodium silicate could only be measured over a limited temperature range, but exhibits the highest conductivity of the four compounds at close to ambient temperatures, 1.3�10−6 Ω−1 cm−1 at 50� C.
In the case of the NaCaHSiO4 compound, the possibility that charge transport occurs, at least in part, by the motion of sodium ions cannot be a priori ruled out. A comparison of the conductivities of the as-synthesized material and the deuterated analog exposed to hot D2O for several hours) shows the deuterated material to be a much poorer conductor, as shown in FIG. 4, signifying that protons/deuterons are indeed the mobile species. Indeed, the one order of magnitude difference in the two conductivities, which is greater than what can be easily explained changes in either jump frequency or zero point energies, rules out the possibility of measurable alkali ion contributions to the conductivity. In addition, examination of the material post-deuteration by X-ray powder diffraction confirmed that structural changes had not taken place.
More significant than the conductivity is the stability of these silicates and germanates. As shown in FIG. 5, the thermal gravimetric behavior of NaCaHSiO4, SrH2GeO4, and CsHSO4 under flowing hydrogen gas and in the presence of a Pt catalyst material are compared. It is immediately evident that while the sulfate undergoes a dramatic weight loss under these conditions, both the silicate and germanate are quite stable. Similar results under methanol vapor (in the presence of Pt—Ru catalyst) were obtained, with NaCaHSiO4 exhibiting good stability and CsHSO4 exhibiting immediate weight loss, as shown in FIG. 6.
The greatest success of the direct synthesis route has been in the preparation of new single alkali silicates, in particular those containing cesium. The reaction of CsOH with SiO2 (4:1 molar ratio) at 900� C. yielded a highly crystalline product, but one which likely did not contain acid protons. Reaction of these two starting materials (2:1 molar ratio) in a thermal bomb at 280� C. also yielded a highly crystalline product. This second product, however, has a markedly different diffraction pattern than the first, and the synthesis conditions suggest that the material contains acid protons. The thermal gravimetric curves of these two materials, cesium silicate #1 and cesium silicate #2, are shown in FIG. 7.
The first material is thermally stable to 800� C. (with the exception of a small weight loss due to the desorption of surface water adsorbed post-synthesis), which is consistent with the absence of acid protons. The second material is thermally stable to only ˜400� C., consistent with the presence of acid protons.
Although the conductivities of these materials, as shown in FIG. 8, are not as high as the acid sulfates, the increased stability of the materials and the relatively high conductivity shows great potential as an electrolyte material.
Likewise, synthesis of new acid silicates by ion exchange of the alkali species in NaCaHSiO4 yielded results which are summarized in Table 1, below, along with the appropriate reaction conditions.
Ion Exchange Experiments
Crucible/Bomb
Δσ*
4 M CsOH
IonEx-1
IonEx-2
IonEx-3
RbC2H3O2 270
IonEx-4
KC2H3O2 340
IonEx-5
KC2H3O2 305
IonEx-6
KH2PO4 290
IonEx-7
IonEx-8
IonEx-9
*change in conductivity
As shown in FIG. 9, whereas in some cases the ion exchange process produced little effect on the NaCaHSiO4, in others it resulted in the crystallization of completely new phases. In general, the change in conductivity induced by the ion exchange was less than an order of magnitude. However, it should be noted that exposure of NaCaHSiO4 to molten potassium acetate (IonEx-5) results in an increase in conductivity of two orders of magnitude, without inducing significant changes to the crystal structure.
The final route for the preparation of new alkali acid silicates and germanates, that involving proton exchange from Li containing compounds, is described with reference to the compounds Li4SiO4 and LaLiSiO4, which have been successfully synthesized, both by solid state reaction following the procedures outlined by Pfeiffer (J. Nucl. Mat. 257 (1998) 309-317) and Sato et al. (Solid State Ionics 83 (1996) 249-256), respectively. The synthesis of these and other compounds indicate that direct synthesis of acid silicates requires more extreme hydrothermal conditions, i.e., higher pressures and temperatures. However, the ion exchange methods (which have led to an increase in the conductivity of NaCaHSiO4 by two orders of magnitude) show excellent results.
Although the above discussion has focussed on the solid acid electrolyte materials in their raw form, it should be understood that for integration into electrochemical devices the solid acid electrolyte materials of the current invention are preferably formed into membranes (MEAs). Accordingly, this invention is also directed to methods of fabricating membranes from the solid acid electrolyte materials described herein.
Fabrication of thin, high density solid acid membranes generally entails the simultaneous application of high temperatures and pressures (uniaxial). Applicants have found that application of pressures of ˜700 psi and temperatures of ˜190� C. yield transparent membranes of CsHSO4, as shown in FIGS. 10 a and 10 b. Specifically, FIG. 10 a shows the image of hot pressed CsHSO4 with a sample thickness of 320 μm mounted in copper plate under reflected light, and FIG. 10 b shows the material with light shining from behind emphasizing translucency.
Although the above discussion has focussed on processing pure solid acid electrolyte materials, because of the mechanical difficulties described above, in one embodiment of the invention the solid acid electrolyte materials are processed as a composite in which the solid acid is embedded in a supporting matrix. In such a composite, the solid acid is in its superportonic state, exhibits high conductivity, and provides the desired electrochemical properties, whereas the support matrix provides mechanical support, and it may also serve to protect the solid acid from water in the environment. In such an embodiment any suitable matrix material may be utilized which would provide sufficient mechanical and/or chemical support, such as, for example, a polymer, a ceramic, or an oxide glass.
Accordingly, in one embodiment composite membrane of solid acids according to the invention and a simple structural polymer, such as polyvinylidene fluoride may be prepared by simple melt-processing, where the two components are lightly ground together and then hot-pressed at 180� C. and 10 kpsi for 15 minutes. The greatest difficulty often encountered with this method is in removing the electrolyte from the hot press without introducing cracks, and the method has a limitation that the thinnest membranes that can be fabricated by the method of hot-pressing is ˜200 μm. For non-polymeric matrix materials, the mixture of the two components is then hot pressed, preferably at a temperature which causes the solid acid to melt and flow, to yield a dense composite membrane.
In another example, the invention is directed to a method of forming thinner electrolytes in a stabilizing matrix. In one such embodiment, the membrane may be formed by providing a thermoset polymer in a monomer or prepolymer form and then polymerizing the polymer in situ with the solid acid. In this method, the two materials are again ground together and the polymerization/crosslinking catalyst agent is added. Any suitable prepolymer may be used, such as, for example, polyester resins. In one exemplary embodiment a solid acid was ground and mixed with the prepolymer. The polymerization catalyst was introduced and the mixture then poured onto a plate and pressed into a thin film. The film thus produced was then cured at 100� C. for approximately 2 hours.
In still another exemplary embodiment, the membrane may be formed by suspension casting. In this embodiment, the solid acid and matrix material are dissolved and/or dispersed in an appropriate solvent system, such as a water/ethanol solution. The membrane is then formed by casting the suspension and allowing the solvents to evaporate. In addition to polymers, membranes containing non-polymeric matrix materials, such as ceramic or oxide glass, can be formed by this method.
According to the above discussion, the solid acid is mixed with a supporting structure that is electrochemically unreactive, to form a composite material. Because, the solid acids of the current invention, without judicious selection of the M and X species, are inherently poor conductors of electrons, these materials alone may only be utilized to provide proton transport. However, in one embodiment of the invention the matrix material has conducting properties such that the composite membrane provides both electron and proton transport.
In a first embodiment, electronic conductivity is introduced into the solid acid by preparing a composite, via any of the above methods, comprised of the solid acid and a second substance which has a high electronic conductivity. This second substance may any suitable electronically conducting material, such as, for example, a conducting polymer, such as polyaniline; or a typical metal, such as copper; or graphite. In cases where the electronically conducting material is a metal, it may be further advantageous to provide a flexible and inert material, such as a polymer, into the composite to serve as a binder.
In a second embodiment, electronic conductivity is introduced into the solid acid by direct chemical substitution with variable valence ions as described earlier. For example, a portion of the phosphorous, silicon or germanium might be replaced with ions that exhibit variable valence states, such as manganese. Similarly, a portion of the alkali or alkaline earth metals might be replaced with large variable valence ions such as thallium, indium, lead and tin. The solid acid so modified may be used in an electrochemical device directly or may be combined with a supporting matrix material as a composite as discussed above.
Although the above discussion has focussed on the solid acid electrolyte materials of the current invention, and methods of forming such materials, the present invention is also directed to electrochemical devices incorporating such materials and membranes. Embodiments of some exemplary devices are shown in FIGS. 11 to 15.
FIGS. 11 and 12 show exemplary embodiments of a hydrogen/air fuel cell and a methanol fuel cell 10, in which the proton conducting membrane 12 is a solid acid electrolyte, alone or in composite form, of the type described herein sandwiched between two graphite layers 14. Because the membrane 12 need not be humidified to operate, the fuel cell system can be quite simple. For example, as shown, no humidification system, normally required for conventional fuel cell utilizing conventional electrolyte materials such as Nafion, is required. In addition, less rigid temperature monitoring and control may be used in the fuel cell. Because the solid acid based membrane need not be humidified, the fuel cell may be operated at elevated temperatures, and such high temperatures can enhance the kinetics of the electrochemical reactions and allow the fuel cell to withstand higher concentrations of CO in the fuel. In contrast, conventional humidified fuel cells cannot be operated above the boiling point of water (100� C.).
Although use of the solid acid electrolyte materials in fuel cells is an important application, such materials may also be incorporated into various membrane reactors. For example, the Pt-based catalyst 16 in the hydrogen/air fuel cell shown in FIG. 11 is very sensitive to CO poisoning, particularly at temperatures close to ambient. Therefore, in an indirect hydrogen/air fuel cell, the hydrogen produced by the reformer is often cleaned of CO impurities before it enters the fuel cell. Accordingly, in one embodiment, shown schematically in FIG. 13, the material is shown incorporated into a hydrogen separation membrane for the removal of CO and other gases from hydrogen.
In this embodiment, the hydrogen separation membrane 20 is made of a proton conducting electrolyte 22 of the type described herein, and is connected to a current source 24. Hydrogen gas 26, mixed with other undesirable gases 27, is introduced onto one side (inlet) 28 of the membrane and clean hydrogen gas 26 a is extracted from the other side of the membrane. In this embodiment, application of current causes the hydrogen gas to dissociate into H+ and e−. Because the membrane conducts only protons, these protons are the only species which can migrate through the membrane. The electrons migrate through the current source to the outlet side 29 of the membrane, where the H+ combines with electrons from the current source to form hydrogen gas. Such membranes are substantially impervious to other gases and fluids. This overall hydrogen separation process is driven by the electric current applied from the current source 24.
Another type of hydrogen separation membrane is shown in FIG. 14. In this embodiment, the hydrogen separation membrane 30 is made of a mixed proton and electron conducting membrane 36. Such a membrane might be made by including, for example, a given amount of a variable valence element, such as, Cr or Mn for X, to the solid acid, as described above. Alternatively, the membrane may be made as a composite in which the matrix substance may be an electronically conducting material, such as a conducting polymer, such as polyaniline, or a typical metal, such as aluminum or copper, or graphite.
Again, hydrogen gas 32, mixed with other undesirable gases 34 is introduced onto one side of the membrane 36, and clean hydrogen gas 37 is extracted from the other side of the membrane. During operation, on the inlet 38 side of the membrane 36 hydrogen gas is dissociated in H+ and e−. Because the membrane 36 is both proton conducting and electron conducting, both of these species migrate through the membrane. Again, however, the membrane is substantially impermeable to other gases and fluids 34. Hence, CO and other undesirable gases or fluids cannot so migrate. Meanwhile, the H+ and e− recombine to form hydrogen gas. The overall process is driven by the hydrogen chemical potential gradient, which is high on the inlet side of the membrane and low on the outlet side 39 of the membrane.
Finally, in FIG. 15, schematic diagrams of membrane reactors incorporating the electrolyte materials of the current invention are shown. In FIG. 15, a membrane reactor in which a mixed proton and electron conducting membrane of the type described above is utilized. The general reaction carried out in this reactor follows the following form:
A+B→C+H2.
Use of a mixed proton and electron conducting membrane in this reactor can enhance the reaction, giving yields that exceed thermodynamic equilibrium values. On the inlet side of the membrane reactor 40, the reactants 41 form products C 42 and H2 44. Under equilibrium conditions, the hydrogen concentration builds up and the forward reaction is slowed. With the use of the mixed hydrogen and electron conducting membrane 46, the hydrogen 44 is immediately extracted from the reaction region 48 via transport through the membrane and the forward reaction is enhanced.
Examples of such reaction in which yield could be enhanced by using such a membrane reactor include:
1) The steam reformation of methane to produce syngas according to:
CH4+H2O→CO+3H2 2) The steam reformation of CO to produce CO2 and H2:
CO+H2O→CO2+H2 3) The decomposition of hydrogen sulfide:
4) The dehydrogenation of propane to polypropylene; and 5) the dehydrogenation of alkane and aromatic compounds to various products.
Although one exemplary embodiment of a membrane reactor is discussed above in relation to FIG. 15, the membrane of the current invention may be used in other reactions which utilize either a proton or a mixed proton and electron conducting membrane, such as, for example, in selective hydrogenation reactions.
Although specific embodiments are disclosed herein, it is expected that persons skilled in the art can and will design solid acid electrolytes and electrochemical devices utilizing such materials that are within the scope of the following description either literally or under the Doctrine of Equivalents.
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S. M. et al., "Superprotonic Conductivity in Cs3(HSO4)(H2PO4),"1995, Solid State Ionics, vol. 77, pp. 128-134.17Jamieson, et al., "Sodium Silicate Hydrates. I. Crystallographic Data," Acta Crystallographica, Mar. 10, 1996, pp. 373-376, vol. 20, Part 3, International Union of Crystallography, Great Britian.18Lavrova, et al., "Disordering of Pentacesium Trihydrogen Tetrasulfate in Cs<SUB>5</SUB>H<SUB>3</SUB>(SO<SUB>4</SUB>)<SUB>4</SUB>-SiO<SUB>2 </SUB>Composite Proto Electrolytes," Inorganic Materials, 2002, vol. 38, No. 11, pp. 1172-1177.19Lewis, "Hawley's Condensed Chemical Dictionary," Thirteenth Edition, p. 910, John Wiley & Sons, Inc. (1997)20Meunier, et al., "Pulsed Laser Deposition of Superionic Ceramic Thin Films: Deposition and Applications in Electrochemistry," Applied Surface Science, 1998, pp. 466-470, vol. 127-129, Elsevier Science B.V.21Mhiri, "Hydrogen Bonding in Cs<SUB>1-x</SUB>M<SUB>x</SUB>HSO<SUB>4 </SUB>Protonic Conductors," Solid State Ionics, May. 1993, pp. 187-191, vol. 61, No. 1-3, Elsevier Science B.V.22M�nster, et al., "Periodical for Inorganic and General Chemistry," Notebook 5-6, Nov. 1965, pp. 225-360, vol. 340, Johann Ambrosius Barth Publishing, Leipzig.23Ohi, K. et al., "Ferroelectric Phase Transition in Rb2So4-(NH4)2SO4 and Cs2SO4-(NH4)2SO4 Mixed Crystals," Feb. 1978, Journal of the Physical Society of Japan, 44(2), pp. 529-536.24Pfeiffer, et al., "Synthesis of Lithium Silicates," Journal of Nuclear Materials, 1998, pp. 309-317, vol. 257, Elsevier Science B.V.25Politova, et al., "Ethylene Hydrogenation in Electrochemical Cell with Solid Proton-Conducting Electrolyte," Reaction Kinetics & Catalysis Letters, 1990, pp. 321-326, vol. 41, No. 2, Elsevier Science B.V.26Ponomareva, et al., "Composite protonic electrolytes in the system (NH<SUB>4</SUB>)<SUB>3</SUB>H(SO<SUB>4</SUB>)<SUB>2</SUB>-SiO<SUB>2</SUB>," Solid State Ionics, 2001, 145, pp. 205-210.27Ponomareva, et al., "Composite protonic solid electrolytes in CsHSO<SUB>4</SUB>-SiO<SUB>2 </SUB>system," State Ionics, 1996, 90, pp. 161-166.28Ponomareva, et al., "Effect of SiO<SUB>2 </SUB>morphology and pores size on the proton nanocomposite electrolytes properties," Solid State Ionics, 1999, 119, pp. 295-299.29Ponomareva, et al., "The influence of heterogeneous dopant porous structure on the properties of protonic solid electrolyte in the CsHSO<SUB>4</SUB>-SiO<SUB>2 </SUB>system," Solid State Ionics, 1999, 118, pp. 317-323.30Ponomareva, et al., "The investigation of disordered phases in nanocomposite proton electrolytes based on MeHSO<SUB>4 </SUB>(Me=Rb, Cs,K)," Solid State Ionics, 2001, 145, pp. 197-204.31Volkov, V. L., et al., "Cesium Ammonium Dihadrogen Arsenate Hydrates," Apr. 1997, Inorganic Materials (Translations of Neogranicheskie Materialy) 33(4), 496-499.32Zaidi, S. M. J. et al., "Solid Polymer Composite Electrolytes for PEMFC," 1998, Proc. Intersoc. Energy Convers. Eng. Conf., vol. 33.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS7807121 *Nov 14, 2004Oct 5, 2010Sud-Chemie AgLithium metal phosphates, method for producing the same and use thereof as electrode materialUS7998618Oct 4, 2010Aug 16, 2011Sud-Chemi AgLithium metal phosphates, method for producing the same and use thereof as electrode materialUS8329071Dec 8, 2009Dec 11, 2012Hestia Tec, LlcMulticomponent nanoparticle materials and process and apparatus therefor* Cited by examinerClassifications U.S. Classification429/491, 423/312, 204/295, 423/306, 423/305, 95/55, 423/308International ClassificationH01G9/00, H01M8/06, C25B13/04, H01M6/18, C01B25/32, B01D71/02, B01D71/00, B01D69/14, B01D53/32, H01M8/02, C01B3/50, B01J19/24, H01M8/10, C01B25/30, H01G9/155Cooperative ClassificationH01B1/122, H01M6/181, H01M8/0631, Y02E60/521, B01D69/141, B01D2325/26, C01B2203/0405, H01M8/1016, H01G9/155, H01M8/0662, B01D71/00, H01M6/18, B01D71/02, C25B13/04, H01M10/0562, C01B3/501, B01J19/2475, B01D67/0055, B01D67/0044, C01B2203/047, B01D2257/108, Y02E60/13, H01M8/0291, H01M2300/0068, B01D67/0041, Y02E60/525, B01D53/228, B01D53/32, H01M8/1246European ClassificationB01D67/00M11, H01M8/06B2B2, H01M8/12E2, B01D67/00M10, H01B1/12F, B01D67/00M18B, B01D53/22M, B01D71/02, B01J19/24P, C25B13/04, H01M6/18B, B01D71/00, B01D53/32, H01M8/10E, H01G9/155, H01M8/06C, H01M8/02E2, C01B3/50B, B01D69/14BLegal EventsDateCodeEventDescriptionFeb 5, 2003ASAssignmentOwner name: CALIFORNIA INSTITUTE OF TECHNOLOGY, CALIFORNIAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HAILE, SOSSINA M.;CHISOLM, CALUM;MERLE, RYAN B.;AND OTHERS;REEL/FRAME:013730/0884;SIGNING DATES FROM 20021216 TO 20030115Aug 4, 2008ASAssignmentOwner name: TRIPLEPOINT CAPITAL LLC, CALIFORNIAFree format text: SECURITY AGREEMENT;ASSIGNOR:SUPERPROTONIC, INC.;REEL/FRAME:021328/0833Effective date: 20080211Jan 25, 2012FPAYFee paymentYear of fee payment: 4RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services


text:
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text: SISTER Memorial Christmas Ornament Gift - "A Feather From a Guardian Angel" Sympathy In Memory - Personalized w/ Name - Custom Keepsake

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Steve Krug needs a Drupal expert - FAST - Boston PHP (Boston, MA)
Steve Krug needs a Drupal expert - FAST
Wednesday, November 10, 2010 6:08 PM
Hi All,Steve Krug is presenting at our next meetup on November 17th. He emailed our leadership team this afternoon about an urgent need for a Drupal expert to help out with a worthy cause. Please respond to Steve directly at his email address below.Here is what Steve needs in his own words: "I have a friend who's been pulling together a redesigned web site for a terrific local non-profit. A series of volunteers have redone the existing site in Drupal 7, and it's almost done. But now at the last minute the most recent Drupal person working on it suddenly left the country(!) My friend has figured out a fair amount about Drupal on her own, but right now she needs urgent help answering a few questions. I'm hoping I can find a generous Drupal-website savvy person who might be willing to spend half an hour on the phone looking at a few things and answering questions. And oh, yes, the tricky part: Soon. Like tomorrow. Any help would be greatly appreciated. Just send me email at [address removed]. Thanks!"

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text:
Strike On Move
Latest News for: strike on m.o.v.e
Urgent: Israel says starting strikes on Iranian targets in Syria
21 (Xinhua) -- Israel has started striking ......
Israel carries out strikes on Iranian targets in Syria after a reported exchange of fire. ... ....
1st LD: Israel launches strikes on Iranian targets in Syria
21 (Xinhua) -- Israel's military said early Monday that it has launched strikes on Iranian targets inside Syria and warned the Syrian ......
21 (Xinhua) -- Israel's military said early Monday that it has launched strikes on Iranian targets inside Syria and warned the ......
Israel confirms air strikes on Iranian forces in Syria
JERUSALEM — In an extraordinary statement, the Israeli military confirmed early Monday that it attacked Iranian military targets in Syria, hours after carrying out a rare daylight air raid near the Damascus International Airport ... “We have started striking Iranian Quds targets in Syrian territory,” the military statement said ... ....
Saudi-led forces launch air strikes on Yemen's capital
A newly-released video shows the second Israeli attack on Syria in two days. According to the Israeli military, the strikes were carried out to prevent "Iranian entrenchment" in Syria ... ....
Israel declares strikes on Iranian targets in Syria
Israel struck in Syria early on Monday as part of its increasingly open assault on Iran's presence there, in a second consecutive night of military action. ... ....
In a rare public admission, Israel confirmed early Monday that it carried out airstrikes on Iranian military targets inside Syria. "We have started striking Iranian Quds targets in Syrian territory....
Description of airstrikes marks rare departure from Israel's years-long policy of ambiguity regarding activities in neighboring war-torn Syria ... ....
Israel's military said it was carrying out strikes on Iranian targets in Syria early Monday after it intercepted a rocket fired from Syrian territory hours earlier ... air defences went into action after Israel earlier in the day launched air strikes on the south of the country....
The overnight missile strikes killed 11 people, including as many as four Syrian soldiers, foreign media reported, and damaged the international airport in Damascus ... In the past it had rarely acknowledged individual strikes ... He said the military was on an “elevated level of readiness’ after the attack....

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text:
BBC - About Radio 1Xtra
On air. On the ground. BBC Radio 1Xtra is home to the likes of Trevor Nelson, Dotty, MistaJam, DJ Target and David Rodigan.
BBC Sounds app - Find out how to get the BBC Sounds app on your mobile or tablet.
Digital TV - there's several options. Freeview channel 701; Freesat channel 701; Sky TV (UK) channel 0137; Virgin Media channel 907
Online - For all support listening online, please use BBC Sounds help.
You can email us at 1Xtra.Enquiries@bbc.co.uk.
We receive a lot of emails, texts and tweets each day and do our best to read them all, but we can’t promise to reply to them all individually.
You can also join us on Facebook or follow us on Twitter: @1Xtra
Texting us: You can text us on 88111. Texts will not be included in your inclusive text bundles, and the exact cost of each message depends on your service provider - it is typically between 10 and 15 pence per message. MMS (Picture) messages may cost more - you should check with your service provider for exact details. Please make sure you take care when entering our number as some subscription services have similar numbers to ours.
Post: You can send stuff to us at BBC 1Xtra, London, W1A 1AA
Listening Online: If you are having a problem listening to 1Xtra online, please visit the Sounds help page.
How do I send you my music to listen to?
The best way to do this is through BBC Music Introducing. You need to...
The music uploader is only for artists in the UK.
There's lots more good advice on the BBC Introducing website.
How do I get a job/work experience placement/DJ position at 1Xtra?
You can search and apply for BBC job and work experience opportunities here.
How do I request a track or shout out?
You can try texting or tweeting the show on-air, but we do get thousands of shout out requests each day and can usually only mention a handful of people. Please don’t be upset if the DJ doesn’t mention you.

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text: _.Kj.prototype.Ae=function(){var a=new gj;this.H=a;var b=_.Rh.Cb();b.kb=!0;this.R();b.Pa=a;_.mfa(b);a.Za=b;b=_.Of("Im6cmf").Na()+"/jserror";$ha(b);b=_.Zd(_.Of("cfb2h").Na());kj.buildLabel=b;if(Jj)for(var b=Jj.H,c=0;c<_.Ij.length;c++)b.push(_.Ij[c]);var b=window,d,c=new Ifa,e=b||window,f=e.document.documentElement,g=new Wfa(f);a:{for(var l=0;lJéssica Lima - Google+Press question mark to see available shortcut keysHomeCollectionsJoin Google+Send FeedbackHelpRegionPrivacy Policy - Terms of Service - Maps Terms©2017 GoogleSearchSign inAboutSearchSign inJéssica Lima1 follower1 followerAboutJéssica's postsLooks like you've reached the endLooks like you've reached the endUnable to load more. RetryWait while more posts are being loaded

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GUNS N ROSES Sweet Child O Mine Welcome To The Jungle 45 rpm 7 NEW record | eBay Please enable JavaScript Our new search experience requires JavaScript to be enabled. Please enable JavaScript on your browser, then try again.
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text:
Amazon Video TV Shows Movies Shorts Help Getting Started Settings Your Video Library Your Watchlist Ender's Game
TOP 1000 REVIEWERVINE VOICE on November 9, 2013Format: DVD
Does the book no justice, but worth the watch.
Published 10 hours ago by B. Shaw
4.0 out of 5 starsTime to read the book again
The book is better but it still works
Published 3 days ago by Robert J. Levay
3.0 out of 5 starsSomeone make this into a TV show!
Definitely read the book first. Pretty thrilling to see the battle room, but the movie moves at such a fast pace that if you don't have any knowledge of the characters, you'll miss...
Published 3 days ago by Katie Parsons
It was a very good adaptation of the book. I am looking forward to see what they do with the rest of the series.
3.0 out of 5 starsStarship Troopers in reverse?
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Published 10 days ago by Livia Vaughn

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text:
Android: How to restore webview when switching among activities? - Stack Overflow
Android: How to restore webview when switching among activities?
I have a webview in activity A and I'm navigating to activity B, so when I switch back to activity A I want to restore the webview, i.e., to reload its most recent URL and can go backward to view the history.
My problem is I reset the webview to null when activityA.onPause() gets called to avoid memory leak, but then I have problem restoring it when activityA.onResume() gets called since my design will have to create a new webview instance. That way even if I can restore the latest url I can't restore the history.
android webview restore share|improve this question asked Feb 7 '13 at 3:17
dirty one, you have to save your data on your onPause() method maybe in preferences, and retrieve the data from preference on your onResume() method and set your data to your webview. Another way to solve this problem is to use activityForResult.
Thanks! That's how I do now, I was hoping to have a neater approach.:-)
– Green Ho
Feb 7 '13 at 7:58
Not the answer you're looking for?	Browse other questions tagged android webview restore or ask your own question.	asked
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text:
"Lay Science" puppet show by Eric Lindley + Katie Shook -- OPENING NIGHT 2/4/11 Tickets, Fri, Feb 4, 2011 at 7:30 PM | Eventbrite
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value: This website is an American event management and ticketing website. The service allows users to browse, create, and promote local events.


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Faur�: Impromptus, Nocturnes, Romances, Barcarolles - CD W9VG The Cheap Fast | eBay
Details about Faur�: Impromptus, Nocturnes, Romances, Barcarolles - CD W9VG The Cheap Fast
Faur�: Impromptus, Nocturnes, Romances, Barcarolles - CD W9VG The Cheap Fast
19 Sep, 2017 22:07:44 AEST
282633656609
Last updated on 19 Sep, 2017 19:48:23 AEST View all revisions
Record Label: Conifer EAN: 5014505000019
UPC: 5014505000019
Artist: Kathryn Piano Stott, Kathryn Stott
Genre: Barcarolle, Classical, Impromptu, Nocturne, Romance, Song Without Words
Contributing Artists: Kathryn Piano Stott, Kathryn Stott


text:
Grand Tour (cycling) - Wikipedia
In road bicycle racing, a Grand Tour is one of the three major European professional cycling stage races: Tour de France, Giro d'Italia and Vuelta a España. Collectively they are termed the Grand Tours, and all three races are similar in format being multi-week races with daily stages. They have a special status in the UCI regulations: more points for the UCI World Tour are distributed in Grand Tours than in other races,[1] and they are the only stage races allowed to last longer than 14 days.[2]
The Giro d'Italia is generally run in May, the Tour de France in July, and the Vuelta a España in late August and September. The Vuelta was originally held in the spring, usually late April, with a few editions held in June in the 1940s. In 1995, however, the race moved to September to avoid direct competition with the Giro d'Italia, held in May.
The Tour de France is the oldest and most prestigious in terms of points accrued to racers of all three,[1], and is the most widely attended sporting event in the world,[3] while the Giro d'Italia is generally seen as the second-most important.[4][5][6] The Tour, the Giro and the Road World Cycling Championship make up the Triple Crown of Cycling.
2 UCI rules
3 Latest edition details
4 Grand Tour winners
5.1 Most Grand Tour wins per rider
5.2 Wins by country
5.3 Winners of all three Grand Tours
5.4 Winners of three or more consecutive Grand Tours
5.5 Winners of two Grand Tours in a season
5.6 Most mountains classification wins
5.7 Most points classification wins
5.8 Most young rider classification wins
5.9 Most Grand Tour stage wins
5.10 Grand Tour finishers
In their current form, the Grand Tours are held over three consecutive weeks and typically include two rest days near the end of the first and second week. The stages are a mix of long massed start races (sometimes including mountain and hill climbs and descents; others are flat stages favoring those with a sprint finish), as well as individual and team time trials and non-competitive exhibition and rest days. Unlike most one-day races, stages in the Grand Tours are generally under 200 kilometers in length.
The prizes include the individual general classification, the team classification, the King of the Mountains, the points classification, and often the best young rider classification, in addition to other less known classifications. The most contested ones are the individual general classification (general classification in the Tour de France, general classification in the Giro d'Italia, and general classification in the Vuelta a España) ; king of the mountains classification (mountains classification in the Tour de France, mountains classification in the Giro d'Italia, and mountains classification in the Vuelta a España); and points classification (points classification in the Tour de France, points classification in the Giro d'Italia, and points classification in the Vuelta a España). Only three riders have won all three in the same race: Eddy Merckx in the 1968 Giro d'Italia and 1969 Tour de France, Tony Rominger in the 1993 Vuelta a España and Laurent Jalabert in the 1995 Vuelta a España.[7]
Over the years, 32 riders have completed all three Grand Tours in one year. Of these, Adam Hansen is the only one to do so five times. Marino Lejarreta has done it four times, Bernardo Ruiz three times, Eduardo Chozas and Carlos Sastre twice each, and 27 more riders have achieved the feat once.
UCI rules[edit]
Latest edition details[edit]
Giro d'Italia (2018)
Dates: 4–27 May 2018
Dates: 1–23 July 2017
Vuelta a España (2017)
Dates: 19 August-10 September 2017
Grand Tour winners[edit]
1912 Team Atala (ITA) (Carlo Galetti (3/3),
Giovanni Micheletto & Eberardo Pavesi) Odile Defraye (BEL)
1915 Not contested due to World War I
1937 Gino Bartali (ITA) (2/5) Roger Lapébie (FRA) Not contested due to the Spanish Civil War
1940 Fausto Coppi (ITA) (1/7) Not contested due to World War II
1941 Not contested due to World War II Julián Berrendero (ESP) (1/2)
1943 Not contested due to World War II
1957 Gastone Nencini (ITA) (1/2) Jacques Anquetil (FRA) (1/8) Jesús Loroño (ESP)
1960 Jacques Anquetil (FRA) (2/8) Gastone Nencini (ITA) (2/2) Frans De Mulder (BEL)
1963 Franco Balmamion (ITA) (2/2) Jacques Anquetil (FRA) (6/8) Jacques Anquetil (FRA) (5/8)
1988 Andrew Hampsten (USA) Pedro Delgado (ESP) (2/3) Sean Kelly (IRL)
2006 Ivan Basso (ITA) (1/2) Floyd Landis (USA)
Óscar Pereiro (ESP) Alexander Vinokourov (KAZ)
2010 Ivan Basso (ITA) (2/2) Alberto Contador (ESP)
Andy Schleck (LUX) Vincenzo Nibali (ITA) (1/4)
2011 Alberto Contador (ESP)
Michele Scarponi (ITA) Cadel Evans (AUS) Juan José Cobo (ESP)
2013 Vincenzo Nibali (ITA) (2/4) Chris Froome (GBR) (1/6) Chris Horner (USA)
2015 Alberto Contador (ESP) (7/7) Chris Froome (GBR) (2/6) Fabio Aru (ITA)
2016 Vincenzo Nibali (ITA) (4/4) Chris Froome (GBR) (3/6) Nairo Quintana (COL) (2/2)
2017 Tom Dumoulin (NED) Chris Froome (GBR) (4/6) Chris Froome (GBR) (5/6)
2018 Chris Froome (GBR) (6/6)
Most Grand Tour wins per rider[edit]
4 Coppi, FaustoFausto Coppi (ITA) 7 2 (1949, 1952) 5 (1940, 1947, 1949, 1952, 1953) 0
Contador, AlbertoAlberto Contador (ESP) 7 2 (2007, 2009, 2010) 2 (2008, 2011, 2015) 3 (2008, 2012, 2014)
7 Froome, ChrisChris Froome (GBR) 6 4 (2013, 2015, 2016, 2017) 1 (2018) 1 (2017)
8 Binda, AlfredoAlfredo Binda (ITA) 5 0 5 (1925, 1927, 1928, 1929, 1933) 0
Bartali, GinoGino Bartali (ITA) 5 2 (1938, 1948) 3 (1936, 1937, 1946) 0
11 Rominger, TonyTony Rominger (SUI) 4 0 1 (1995) 3 (1992, 1993, 1994)
Heras, RobertoRoberto Heras (ESP) 4 0 0 4 (2000, 2003, 2004, 2005)
Grand Tour general classification wins by country
Winners of all three Grand Tours[edit]
Seven cyclists have won all three of the Grand Tours during their career:[10]
Chris Froome (GBR): 4 Tours (2013, 2015, 2016, 2017), 1 Giro (2018), 1 Vuelta (2017).
Winners of three or more consecutive Grand Tours[edit]
Chris Froome (GBR): 3 Grand Tours - Tour (2017), Vuelta (2017), Giro (2018).
No cyclist has ever won all three Grand Tour events in the same season.
Winners of two Grand Tours in a season[edit]
Ten riders have achieved a double by winning two grand tours in the same calendar year.
Seven cyclists have won the Tour and the Giro in the same calendar year:[10]
The Tour/Vuelta double has been achieved by three cyclists:[10]
Chris Froome (GBR): 2017
Of the above ten, Pantani, Roche and Battaglin's doubles were their only Grand Tour victories in their careers. Only two cyclists have placed in the top ten at all three Grand Tours in the same calendar year: Raphaël Géminiani in 1955 and Gastone Nencini in 1957.
Most mountains classification wins[edit]
Main articles: King of the Mountains and List of Grand Tour mountains classification winners
1 Gino Bartali (ITA) 9 2 (1938, 1948) 7 (1935, 1936, 1937, 1939, 1940, 1946, 1947) 0
Federico Bahamontes (ESP) 9 6 (1954, 1958, 1959, 1962, 1963, 1964) 1 (1956) 2 (1957, 1958)
Most points classification wins[edit]
Main articles: Points classification and List of Grand Tour points classification winners
Most young rider classification wins[edit]
2 Jan Ullrich (GER) 3 3 (1996, 1997, 1998) 0
Nairo Quintana (COL) 3 2 (2013, 2015) 1 (2014)
Most Grand Tour stage wins[edit]
Three cyclists have won stages in all three of the Grand Tours in the same season: Miguel Poblet (ESP) in 1956, Pierino Baffi (ITA) in 1958 and Alessandro Petacchi (ITA) in 2003.[11]
Cyclists whose names are in bold are still active.[12] This list is complete up to and including the 2017 Vuelta a España.
Tour[13]
8 Delio Rodríguez Spain 0 0 38 38
Francesco Moser Italy 2 23 2 27
16 Guido Bontempi Italy 6 16 4 26
19 Franco Bitossi Italy 4 21 0 25
André Greipel Germany 11 7 4 22
Grand Tour finishers[edit]
Only 34 riders have finished all three Grand Tours in one season. Adam Hansen has done this six times, Marino Lejarreta four times and Bernardo Ruiz achieved it in three different years, while Eduardo Chozas and Carlos Sastre have completed the accomplishment twice.[14][15]
The rider with most participations on Grand Tours is Matteo Tosatto with 34 (12 Tours, 13 Giros and 9 Vueltas). The rider who has finished most Grand Tours is also Matteo Tosatto, with 28 (12 Tours, 11 Giros and 5 Vueltas). Adam Hansen has finished the most consecutive Grand Tours: 20 tours from 2011 Vuelta a España till 2018 Giro d'Italia. The best average finish was the first time three Grand Tours were finished in one season, when Raphaël Géminiani finished 4th, 6th and 3rd in the Giro, Tour and Vuelta, respectively.
Final GC position
Luis Javier Lukin 1988 32 82 60
José Luis Uribezubia (fr) 1971 29 50 27
^ a b c "UCI Cycling regulations—Part 2: Road Races" (PDF). January 1, 2017. p. 64. Retrieved 2017-07-06.
^ a b "UCI Cycling regulations". p. 41. Archived from the original on 2011-06-23. Retrieved 2012-07-20.
^ http://uk.businessinsider.com/tour-de-france-2016-numbers-2016-6?r=US&IR=T
^ An American in Italy cyclingnews.com, May 5, 2009
^ Million dollar, baby! cyclingnews.com, January 12, 2007
^ Vuelta a España A-Z cyclingnews.com, September 7, 2008
^ "Tony Rominger". Cycling Hall of Fame.com. 1961-03-27. Retrieved 2012-07-20.
^ Riche, Antoine (19 March 2005). "Doubler deux Grands Tours revient à la mode" (in French). CyclisMag. Archived from the original on 20 November 2010. Retrieved 11 November 2010.
^ "Tour de France shorts: Armstrong is back, an Alpine Etape du Tour". Cyclingnews.com.
^ a b c d "Historical Results – The Grand Tours". Retrieved 2012-07-20.
^ "Petacchi equals Poblet and Baffi". cyclingnews.com. September 9, 2003.
^ "Giro d'Italia 2009" (pdf). Infostrada sports. 2009. p. 208. Retrieved 29 June 2011.
^ "Le Tour en chiffres : Les vainqueurs d'étapes" (PDF). ASO. Retrieved 2010-07-26.
^ L'impresa di Adam Hansen: completati Giro, Tour e Vuelta in un anno, Spazio Ciclismo, 9. sept. 2012
^ "Tour Xtra: Tour Records". cvccbike.com.
(clasificación por equipos)
Retrieved from "https://en.wikipedia.org/w/index.php?title=Grand_Tour_(cycling)&oldid=845706099"
Road bicycle racing terminology
This page was last edited on 13 June 2018, at 15:56 (UTC).

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