NZ537841A

NZ537841A - Microcell electrochemical devices and assemblies with corrosion-resistant current collectors, and method of making the same

Info

Publication number: NZ537841A
Application number: NZ537841A
Authority: NZ
Inventors: Ray R Eshraghi
Original assignee: Microcell Corp
Priority date: 2002-07-02
Filing date: 2003-06-13
Publication date: 2006-09-29
Also published as: AU2003238243A2; EP1518292B1; US20040005498A1; WO2004006377A1; US6884539B2; DE60332533D1; EP1518292A4; AU2003238243A1; CA2490126C; CN1666375A; JP2005531911A; ATE467921T1; CA2490126A1; EP1518292A1; JP4783570B2; CN100423350C

Abstract

Microcell electrochemical devices and assemblies, and their methods for manufacture are disclosed. A fibrous microcell structure includes an inner electrode 102, a hollow fibrous membrane separator 104 in contact with the inner electrode, an electrolyte embedded in the hollow fibrous membrane separator, and an outer electrode 108. At least one of the inner and outer electrodes includes a metal clad composite having two or more metal layers 112, 114 bonded together by solid-phase bonding. A fuel cell made up of these fibrous microcell elements is also disclosed.

Description

<div class="application article clearfix" id="description"> 537 WO 2004/006377 PCT/US2003/019023 MICROCELL ELECTROCHEMICAL DEVICES AND ASSEMBLIES WITH CORROSION-RESISTANT CURRENT COLLECTORS, AND METHOD OF MAKING THE SAME DESCRIPTION Field of the Invention 10 This invention relates to microceil electrochemical devices and assemblies, and method of making the same. More specifically, this invention relates to microceil electrochemical devices and assemblies that comprise current collectors of high electrical conductivity, high corrosion resistance, and high mechanical endurance and resistance to peeling and wearing. 15 Background of the Related Art Electrochemical cells, such as batteries and fuel cells, have positive and negative electrodes that are separated in such manner as to avoid internal short-circuiting, while the electrodes are in contact with an electrolyte medium, which chemically reacts with the electrodes to generate flow of 20 electrons, thus providing electrical energy when the circuit is coupled with an external load. A recent innovation in the electrochemical energy field is the development of microcells - small-sized electrochemical cells for battery, fuel cell and other electrochemical device applications. The microceil technology is described in U.S. Patent Nos. 5,916,514; 5,928,808; 5,989,300; 6,004,691; 25 6,338,913; and 6,399,232, all to Ray R. Eshraghi. , The microceil structure described in these patents comprises hollow fiber structures with which electrochemical cell components are associated. WO 2004/006377 PCT/US2003/019023 The aforementioned Eshraghi patents describe an electrochemical cell structure in microfiber form, which contains a first current collector, a membrane separator, electrolyte medium, and a second current collector. Specifically, the Eshraghi patents disclose a hollow fibrous membrane separator, impregnated with electrolyte medium and having a first metal fiber (inner current collector) 5 disposed inside thereof and a second metal fiber (outer current collector) disposed on the outer surface of such hollow fibrous membrane separator, wherein the first and second metal fibers constitute positive and negative current collectors of the microceil. Multiple fibrous microcells as described hereinabove can then be serially and/or parallelly 10 connected together, and packed/bundled into a unitary microceil assembly, which is characterized by high current density and high voltage output. The positive and negative current collectors of the Eshraghi microcells, as described in the above-listed patents, are in contact with the reactive electrolyte medium. They therefore are subjected to a 15 harsh chemical environment. Since the current collectors of the microcells are formed of very thin metal fibers, they are especially susceptible to corrosion, which may result in electrical disconnection within individual microcells or between serially or parallelly connected microcells, eventually shortening the useful life and/or reducing the power density of the microceil assemblies. 20 Eshraghi U.S. Patent Nos. 6,338,913 and No. 6,399,232 suggest several corrosion management structures for enhancing the corrosion resistance of the current collectors in the microceil devices or structures. For example, current collectors can be manufactured from graphite materials; alternatively, current collectors can be formed of aluminum or copper coated with corrosion-resistant carbonaceous coatings. Although the graphite or carbon-coated current collectors have 25 significantly enhanced corrosion resistance in comparison with the conventional metal current collectors, they are not mechanically robust (i.e., the graphite current collectors are easily broken, 2 WO 2004/006377 PCT/US2003/019023 and the carbon coating are easily peeled off, exposing the underlying metal core to the corrosive electrolyte), which will result in eventual electrical disconnection within or between the microcells. There therefore is a continuing need in the art to identify and utilize improved materials for forming 5 current collectors of high corrosion-resistance, high electrical conductivity, and high mechanical integrity in such microceil structures, and it is accordingly an object of the present invention to provide a microceil structure or assembly comprising current collectors formed of corrosion-resistant materials for significantly prolonging the useful life and enhancing the reliability of such microceil structure or assembly. 10 SUMMARY OF THE INVENTION The present invention in one aspect relates to a fibrous microceil structure comprising: an inner electrode, a hollow fibrous membrane separator in contact with the inner electrode, 15 an electrolyte embedded in the hollow fibrous membrane separator, and an outer electrode, wherein at least one of the inner and outer electrodes comprises a metal clad composite having two or more metal layers bonded together by solid-phase bonding. 20 Another aspect of the present invention relates to an electrochemical cell device, including a plurality of fibrous microceil structures as described hereinabove. Such electrochemical cell device can be either a fuel cell or a battery cell. Preferably, such electrochemical cell device is a fuel cell. Yet another aspect of the present invention relates to a fuel cell comprising microceil fibrous 25 elements, wherein each microceil fibrous element comprises an inner current collector, an inner catalyst layer, a hollow fibrous membrane separator in contact with the inner catalyst layer and the 3 WO 2004/006377 PCT/US2003/019023 inner current collector, an electrolyte embedded in the hollow fibrous membrane separator, an outer catalyst layer, and an outer current collector, wherein at least one of the inner and outer current collectors comprises a metal clad composite having two or more metal layers bonded together by solid-phase bonding. 5 Other aspects, features and advantages of the invention will be more fully apparent from the ensuing disclosure and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS 10 Figure 1 is a cross-sectional view of a microceil current collector formed of a two-layer metal clad composite, according to one embodiment of the present invention. Figure 2 is a cross-sectional view of a microceil current collector formed of a three-layer metal clad 15 composite, according to another embodiment of the present invention. Figure 3 is a schematic representation of formation of the three-layer metal clad current collector of Figure 2 from a metal billet. 20 Figure 4 is a cross-sectional view of a fibrous microceil structure, having both inner and outer current collectors formed of two-layer metal clad composites, according to one embodiment of the present invention. Figures 5A-C are cross-sectional views of microceil current collectors formed of metal clad 25 composites of various shapes. 4 WO 2004/006377 PCT/US2003/019023 DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The disclosures of Eshraghi U.S. Patent Nos. 5,916,514; 5,928,808; 5,989,300; 6,004,691; 6,338,913; and 6,399,232 hereby are incorporated herein by reference, in their respective entireties 5 and for all purposes. As used herein, the term "microceil" refers to an electrochemical cell energy generation or conversion structure, including a membrane separator having electrolyte embedded therein. The electrolyte material can be a solid ion-exchanging material evenly distributed within the membrane 10 separator, or solid ion-exchanging particles immobilized in micropores of the membrane separator; alternatively, the membrane separator itself may be formed of ion-exchanging material that functions as electrolyte medium. The membrane separator is in contact with electrically conductive fibers, which in turn are in contact with or are coated with electrocatalyst and form positive and negative electrodes for the electrochemical cell. 15 While the ensuing description herein is primarily directed to fuel cell embodiments of the instant invention, it will be appreciated that the description can be analogously applied to corresponding battery cells and to other forms of electrochemical cell devices, consistent with the invention. 20 A battery cell of course differs from a fuel cell in that the electrochemically active material in a battery is present and stored in the cell, as opposed to being externally furnished to the structure when electrochemical activity is desired, as in a fuel cell. Accordingly, when used in a battery cell, the microceil does not require a lumen at the center of the fiber, thereby correspondingly simplifying the bundling of fibers in modular assemblies for battery cell applications. Microcells 25 for battery cell applications thus have structural and operational differences from microcells used in fuel cells. 5 WO 2004/006377 PCT/US2003/019023 In a specific embodiment of the present invention, the microceil comprises an inner electrode, a membrane separator in contact with the inner electrode, electrolyte embedded in the membrane separator, and an outer electrode, wherein at least one of the inner and outer electrodes comprises a 5 metal clad composite having a metal core formed of a first metal or metal alloy, and a metal outer layer formed of a second metal or metal alloy, wherein the metal core and the metal outer layer are bonded to each other at their interfacial surfaces by solid-phase bonding. In conventional fuel cells, use of naked solid metal material is generally avoided, due to the high 10 corrosiveness of the electrochemical reactive materials and the electrolyte. Material for forming current collectors in such conventional fuel cells generally have been limited to graphite type materials. However, graphite materials have very poor mechanical strength and formability and are not suitable to form microfibrous current collectors in the microceil structures, wherein the outer diameter of such microfibrous current collectors is usually within the range of from about 100 jim 15 to about 10 mm. Eshraghi U.S. Patent Nos. 6,338,913 and No. 6,399,232 suggest coating aluminum or titanium current collectors with corrosion-resistant materials, such as carbonaceous material or amorphous metal. However, such coatings lack uniformity and leave pinholes at certain area susceptible to 20 corrosion. Moreover, such coatings are only loosely bonded to the underlying current collector element via Van der Waals forces, and thus have the tendency to peel and delaminate from the current collector element under the severe corrosive conditions and thermal cycles that characterize the fuel cell operation. 25 Despite the conventional wisdom that avoids use of naked solid metal materials in the fibrous microceil structures, the present invention employs a metal clad composite in forming the fibrous 6 WO 2004/006377 PCT/US2003/019023 current collectors of the electrodes in the microceil devices or structures described hereinabove, which shows good corrosion resistance and high mechanical strength and formability in comparison with the above-mentioned graphite or carbon-coated current collectors. The use of solid metal materials without any carbon coating or amorphous metal coating, in the metal clad composites of the present invention, thus embodies an approach that has been contraindicated by the conventional wisdom and approach of the prior art, but use of such metal clad composites achieve surprisingly satisfactory results that have not been contemplated by the conventional wisdom, with respect to corrosion resistance, electrical conductivity, mechanical strength, and reliability. Figure 1 shows a cross-sectional view of a current collector 10 useful in a microceil as described hereinabove. The microceil current collector 10 is a two-layer metal clad composite, comprising a metal core 12 and a metal outer layer 14. 15 The metal core 12 is formed of a first metal or metal alloy, preferably a metal or metal alloy that is characterized by a low electrical resistance (e.g., resistance less than 10 |xI2'cm, preferably less than 1 n£Vcm), high mechanical strength, good formability, and low manufacturing cost, such as copper, aluminum, brass, bronze, nickel, silver, etc. More preferably, the metal core 12 is formed of a metal selected from the group consisting of copper and aluminum, and alloys thereof, and most 20 preferably, the metal core 12 is formed of copper. 10 The metal outer layer 14 is formed of a second metal or metal alloy, preferably a metal or metal alloy that is characterized by high corrosion-resistance, high mechanical strength, and good formability, such as titanium, niobium, nickel, zirconium, gold, tantalum, platinum, palladium, 25 silver, etc. More preferably, the metal outer layer 14 is formed of a metal selected from the group 7 WO 2004/006377 PCT/US2003/019023 consisting of titanium, niobium, nickel, gold, platinum, and alloys thereof, and most preferably, such metal outer layer 14 is formed of titanium. The above lists of metals and metal alloys are only exemplary and are not intended to limit the 5 broad scope of the present invention. The metal core 12 and the metal outer layer 14 are bonded together at their interfacial surface by solid-phase bonding, which is the bonding of two different metals without the formation of any liquid phase material at their interfaces. 10 The solid-phase bonding of two different metals is achieved by a hot co-extrusion process, wherein the two metals are pressed together at an elevated temperature, to cause deformation of such metals in form of reduction in cross-sectional area of the metals. The elevated temperature is within a range of from just above the minimum re-crystallization temperature of the metal that has the lower 15 re-crystallization temperature to the highest temperature at which both metals may be deformed without any pulling apart or any formation of brittle compounds or liquid phase material at the interface of the metals being bonded. By applying pressure at such elevated temperature, it is possible to solid-phase bond layers of any two or more metals to form a multiple-layer metal clad composite. 20 The strength of the solid-phase bonding is a function of the elevated temperature and the amount of deformation that such metals undergo. Preferably, the elevated temperature is within a range of from about 400°C to about 900°C, and the amount of deformation that such metals undergo is expressed as a reduction in cross-sectional area ratios of such metals, e.g., in a range of from about 25 7:1 (i.e., the cross-sectional area reduces from 7 to 1 due to such deformation) to about 64:1 (i.e., the cross-sectional area reduces from 64 to 1 due to such deformation). 8 WO 2004/006377 PCT/US2003/019023 The solid-phase bonding formed according to the above-described method can be further strengthened by a subsequent sintering step. The thermal energy provided by such sintering step increases atomic mobility of the metals and effects growth of the bond areas at the bonding 5 interface between the metals. As a result, the solid-phase bonding between such metals is further strengthened. In another embodiment of the present invention, at least one of the inner and outer electrodes of the microcells comprises a metal clad composite having a metal core formed of a first metal or metal 10 alloy, an intermediate metal layer formed of a second metal or metal alloy, and a metal outer layer formed of a third metal or metal alloy, wherein the metal core, the intermediate metal layer, and the metal outer layer are bonded to one another at their respective interfacial surfaces by solid-phase bonding. 15 Figure 2 shows a cross-sectional view of a microceil current collector 20 as described hereinabove. The microceil current collector 20 is a three-layer metal clad composite, comprising a metal core 22, an intermediate metal layer 24, and a metal outer layer 26. The metal core 22 is formed of a first metal or metal alloy, preferably a metal or metal alloy that is 20 characterized by low electrical resistance (i.e., resistance less than 10 |jflcm, preferably less than 1 Hfl cm), high mechanical strength, good formability, and low manufacturing cost, such as copper, aluminum, brass, bronze, nickel, silver, etc. More preferably, the metal core 22 is formed of a metal selected from the group consisting of copper and aluminum, and alloys thereof, and most preferably, the metal core 12 is formed of copper. 25 9 WO 2004/006377 PCT/US2003/019023 The intermediate metal layer 24 and the metal outer layer 26 are formed of a second metal and a third metal or metal alloy, respectively. The second and the third metals or metal alloys preferably are characterized by high corrosion-resistance, high mechanical strength, and good formability, such as titanium, niobium, nickel, zirconium, gold, tantalum, platinum, palladium, silver, etc. More 5 preferably, the second metal or metal alloy for forming the intermediate metal layer 24 is selected from the group consisting of titanium, niobium, nickel, and alloys thereof, and the third metal or metal alloy for forming the metal outer layer 26 is selected from the group consisting of niobium, platinum, tantalum, gold, zirconium, and alloys thereof. Most preferably, the intermediate metal layer 24 is formed of titanium or titanium alloy, and the metal outer layer 25 is formed of niobium 10 or niobium alloy. As mentioned hereinabove, the specific metals and metal alloys identified herein are only exemplary and are not intended to limit the broad scope of the present invention. 15 The following is a list of preferred two- and three-layer metal clad composites useful for forming the microceil current collectors of the present invention: Metal Composite No. Metal Core Intermediate Layer Outer Layer 1 Copper X Titanium 2 Copper X Nickel 3 Copper Titanium Platinum 4 Copper Titanium Gold 5 Copper Titanium Tantalum 6 Copper Titanium Niobium 7 Copper Titanium Zirconium 10 WO 2004/006377 PCT/US2003/019023 8 Copper Niobium Platinum 9 Copper Nickel Platinum 10 Copper Nickel Gold According to a preferred embodiment of the present invention, the three-layer microceil current collector 20 of Figure 2 is formed by the following steps (as shown in Figure 3): 5 (1) providing a base metal rod 32 comprising the metal or metal alloy for forming the metal core 22 of Figure 2, such as copper or aluminum; (2) providing a first metal tube 34 comprising the metal or metal alloy for forming the intermediate metal layer 24 of Figure 2, such as titanium, niobium, or nickel, wherein 10 the first metal tube 34 has an inner diameter that is larger than the diameter of the base metal rod 32, so that the first metal tube 34 can fit around the base metal rod 32; (3) providing a second metal tube 36 comprising the metal or metal alloy for forming the metal outer layer 26 of Figure 2, such as niobium, tantalum, platinum, or gold, wherein the second metal tube 36 has an inner diameter that is larger than the outer diameter of 15 the first metal tube 34, so that the second metal tube 36 can fit around the first metal tube 34; (4) hot co-extruding the base metal rod 32, the first metal tube 34, and the second metal tube 36 together to form a metal billet 40 that comprises three layers of metals bonded together by solid-phase bonding; and 20 (5) drawing the metal billet 40 into thin metal wire 50 via a series of cold drawing and annealing steps, wherein the thin metal wire 50 is characterized by fibrous conformation and small diameter, and wherein the thin metal wire 50 comprises three 11 WO 2004/006377 PCT/US2003/019023 different metal layers (cannot be seen in Figure 3) corresponding to the metal core 22, the intermediate metal layer 24, and the metal outer layer 26 in Figure 2. The thin metal wire 50 can be cut into appropriate lengths and used to form the inner and/or outer 5 current collectors of the microceil structure or microceil assembly as described hereinabove. The microceil current collectors of the present application may have an outer diameter within a range of from about 100 urn to about 10 mm, more preferably from about 100 nm to about 1000 Urn, and most preferably from about 200 (xm to about 500 (im. 10 If the microceil current collector of the present application comprises a two-layer metal clad composite as described hereinabove, the metal core may have an outer diameter within a range of from about 10 nm to about 10 mm, more preferably from about 100 pm to about 1000 nm, and most preferably from about 150 nm to about 500 p.m. 15 If the microceil current collector of the present application comprises a three-layer metal clad composite as described hereinabove, the intermediate metal layer may have an outer diameter within a range of from about 100 urn to about 10 mm, more preferably from about 100 nm to about 1000 jim, and most preferably from about 200 |im to about 500 nm, while the metal core may have 20 an outer diameter within a range of from about 10 |itn to about 10 mm, more preferably from about 100 Jim to about 1000 nm, and most preferably from about 150 ^m to about 500 f.im. However, the microceil current collectors of the present application are not limited to the two-layer or three-layer metal clad composite described hereinabove. A person ordinarily skilled in the art 25 can readily design metal clad composites having additional layers of metal or non-metal conductive materials, such as conductive polymers, carbonaceous materials, or conductive ceramics, etc., for 12 WO 2004/006377 PCT/US2003/019023 the purpose of further enhancing the corrosion resistance and mechanical strength of such metal clad composite for forming microceil current collectors useful for practicing the present application. 5 Moreover, the metal core of the metal clad composites is not limited to the solid form as described hereinabove. In a preferred embodiment of the present invention, such metal core may be a hollow, tubular metal element, through which heat-exchanging fluid (such as air or heat-exchanging liquids) can be passed. In such manner, the current collectors comprising such hollow, tubular metal core concurrently function as heat-exchanging tubes, for conducting heat generated by the 10 electrochemical reaction out of the microceil system. The conformation and shape of the metal clad composites are not limited to the illustrative examples that have been described hereinabove and shown in Figures 1-4. For example, such metal clad composites may have cross-sectional areas of various regular or irregular shapes, such as 15 circular, semi-circular, oval, crescent, cross, triangle, square, rectangular, parallelogram, trapezium, polyhedron, star-like, etc. The surface of such metal clad composite may be smooth, rough, spiked, grooved, etc. Figures 5A-C show various metal clad composites of different cross-sectional shapes. Figure 5A 20 shows a metal clad composite 310 of semi-circular shape, comprising a metal core 312 and a metal outer layer 314. Figure 5B shows a metal clad composite 320 of oval shape, comprising a metal core 322 and a metal outer layer 324. Figure 5C shows a metal clad composite 330 of star-like shape, comprising a metal core 332 and a star-like metal outer layer 334. 25 13 WO 2004/006377 PCT/US2003/019023 The microceil current collectors formed by the process described hereinabove comprise multiple layers of metals, while the metal core formed of copper or aluminum provides high electrical conductivity, the titanium, niobium, platinum, or gold intermediate/outer layer(s) provide high corrosion resistance against the harsh chemical environment to which such microceil current 5 collectors are constantly exposed, and the solid phase bonding between the metal core and the intermediate/outer layer(s) ensures mechanical integrity and reliability of such layered structure, with minimum risk of such intermediate/outer layer(s) being peeled off the metal core. Each metal layer in such fibrous microceil current collectors is very thin (e.g., from about 1 jim to about 200 |am). However, each metal layer is substantially continuous and uniform through out the whole 10 bonding surface, leaving few or no pinholes susceptible to corrosion. By using such microceil current collectors, the useful life of the overall microceil structure or microceil assembly including same is significantly prolonged. 15 Figure 4 shows a fibrous fuel cell 100 comprising an inner current collector 102, an inner catalyst layer 110, a hollow fiber membrane separator 104 comprising an electrolyte (not shown) in contact with the inner catalyst layer 110 and the inner current collector 102, an outer catalyst layer 106, and an outer current collector 108, according to a preferred embodiment of the present invention. The electrolyte may be solid ion-exchanging particles impregnated in the hollow fiber membrane 20 separator 104, or the hollow fiber membrane separator 104 may be formed entirely of ion-exchanging material that function as the electrolyte. Both the inner and outer current collectors 102 and 108 are formed of two-layer metal clad composites, comprising a metal core 112 of copper and a metal outer layer 114 of titanium. 25 14 WO 2004/006377 PCT/US2003/019023 The microfibrous current collectors formed of metal clad composites as disclosed herein are characterized by significantly enhanced corrosion resistance, low electrical resistance, longer useful life, excellent mechanical strength and ductility, and greater reliability in comparison with the microfibrous current collectors or current collectors disclosed in Eshraghi U.S. Patent Nos. 5 5,916,514; 5,928,808; 5,989,300; 6,004,691; 6,338,913; and 6,399,232. While the invention has been described herein with reference to specific embodiments, features and aspects, it will be recognized that the invention is not thus limited, but rather extends in utility to other modifications, variations, applications, and embodiments, and accordingly all such other 10 modifications, variations, applications, and embodiments are to be regarded as being within the spirit and scope of the invention. 15 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> WO 2004/006377 PCT/US2003/019023 THE CLAIMS WHAT IS CLAIMED IS: 5

1. A fibrous microceil structure comprising: an inner electrode, 10 a hollow fibrous membrane separator in contact with the inner electrode, an electrolyte embedded in the hollow fibrous membrane separator, and an outer electrode, wherein at least one of the inner and outer electrodes comprises a metal clad composite 15 having two or more metal layers bonded together by solid-phase bonding.

2. The fibrous microceil structure according to claim 1, wherein said metal clad composite includes a metal core and a metal outer layer. 20

3. The fibrous microceil structure according to claim 2, wherein said metal core comprises a first metal or metal alloy selected from the group consisting of copper, aluminum, brass, bronze, nickel, silver, and mixtures or alloys thereof.

4. The fibrous microceil structure according to claim 2, wherein said metal core comprises 25 copper or copper alloy.

5. The fibrous microceil structure according to claim 2, wherein said metal core comprises aluminum or aluminum alloy. 30

6. The fibrous microceil structure according to claim 2, wherein said metal outer layer comprises a second metal or metal alloy selected from the group consisting of titanium, niobium, nickel, zirconium, gold, tantalum, platinum, palladium, silver, and mixtures and alloys thereof. 16 WO 2004/006377 PCT/US2003/019023

7. The fibrous microceil structure according to claim 2, wherein said metal outer layer comprises a second metal or metal alloy selected from the group consisting of titanium, niobium, nickel, gold, platinum, and mixtures and alloys thereof. 5

8. The fibrous microceil structure according to claim 2, wherein said metal outer layer comprises titanium or titanium alloy.

9. The fibrous microceil structure according to claim 2, wherein said metal core comprises 10 copper or copper alloy, and wherein said metal outer layer comprises nickel or nickel alloy.

10. The fibrous microceil structure according to claim 2, wherein said metal core comprises copper or copper alloy, and wherein said metal outer layer comprises titanium or titanium alloy. 15

11. The fibrous microceil structure according to claim 1, wherein said metal clad composite includes a metal core, an intermediate metal layer, and a metal outer layer.

12. The fibrous microceil structure according to claim 11, wherein said metal core comprises a 20 first metal or metal alloy selected from the group consisting of copper, aluminum, brass, bronze, nickel, silver, and mixtures or alloys thereof.

13. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy. 25

14. The fibrous microceil structure according to claim 11, wherein said metal core comprises aluminum or aluminum alloy.

15. The fibrous microceil structure according to claim 11, wherein said intermediate metal 30 layer comprises a second metal or metal alloy selected from the group consisting of titanium, niobium, nickel, zirconium, gold, tantalum, platinum, palladium, silver, and mixtures and alloys thereof. 17 WO 2004/006377 PCT/US2003/019023

16. The fibrous microceil structure according to claim 11, wherein said intermediate metal layer comprises a second metal or metal alloy selected from the group consisting of titanium, niobium, nickel, and mixtures and alloys thereof. 5

17. The fibrous microceil structure according to claim 11, wherein said intermediate metal layer comprises titanium or titanium alloy.

18. The fibrous microceil structure according to claim 11, wherein said metal outer layer comprises a third metal or metal alloy selected from the group consisting of titanium, 10 niobium, nickel, zirconium, gold, tantalum, platinum, palladium, silver, and mixtures and alloys thereof.

19. The fibrous microceil structure according to claim 11, wherein said metal outer layer comprises a third metal or metal alloy selected from the group consisting of platinum, gold, 15 niobium, tantalum, zirconium, and mixtures and alloys thereof.

20. The fibrous microceil structure according to claim 11, wherein said metal outer layer comprises niobium or niobium alloy. 20

21. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy, wherein said intermediate metal layer comprises titanium or titanium alloy, and wherein said metal outer layer comprises niobium or niobium alloy.

22. The fibrous microceil structure according to claim 11, wherein said metal core comprises 25 copper or copper alloy, wherein said intermediate metal layer comprises titanium or titanium alloy, and wherein said metal outer layer comprises platinum or platinum alloy.

23. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy, wherein said intermediate metal layer comprises titanium or 30 titanium alloy, and wherein said metal outer layer comprises gold or gold alloy.

24. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy, wherein said intermediate metal layer comprises titanium or titanium alloy, and wherein said metal outer layer comprises tantalum or tantalum alloy. 18 WO 2004/006377 PCT/US2003/019023

25. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy, wherein said intermediate metal layer comprises titanium or titanium alloy, and wherein said metal outer layer comprises zirconium or zirconium alloy. 5

26. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy, wherein said intermediate metal layer comprises niobium or niobium alloy, and wherein said metal outer layer comprises platinum or platinum alloy. 10

27. The fibrous microceil structure according to claim 11, wherein said metal core comprises copper or copper alloy, wherein said intermediate metal layer comprises nickel or nickel alloy, and wherein said metal outer layer comprises platinum or platinum alloy.

28. The fibrous microceil structure according to claim 11, wherein said metal core comprises 15 copper or copper alloy, wherein said intermediate metal layer comprises nickel or nickel alloy, and wherein said metal outer layer comprises gold or gold alloy.

29. The fibrous microceil structure according to claim 1, wherein said metal clad composite has an outer diameter within a range of from about 100 jim to about 10 mm. 20

30. The fibrous microceil structure according to claim 1, wherein said metal clad composite has an outer diameter within a range of from about 100 |j.m to about 1000 p.m.

31. The fibrous microceil structure according to claim 1, wherein said metal clad composite 25 has an outer diameter within a range of from about 250 p.m to about 500 urn.

32. The fibrous microceil structure according to claim 1, wherein said metal clad composite comprises more than three metal layers bonded together by solid-phase bonding. 30

33. The fibrous microceil structure according to claim 1, wherein said metal clad composite has a cross-sectional shape selected from the group consisting of circular, semi-circular, oval, crescent, cross, triangle, square, rectangular, parallelogram, trapezium, polyhedron, and star-like. 19 WO 2004/006377 PCT/US2003/019023

34. The fibrous microceil structure according to claim 1, wherein said metal clad composite has a cross-sectional shape selected from the group consisting of circular, semi-circular, oval, and star-like. 5

35. The fibrous microceil structure according to claim 2, wherein the metal core is a hollow, tubular metal element, through which heat-exchanging fluid flows, for conducting heat out of said fibrous microceil structure.

36. The fibrous microceil structure according to claim 11, wherein the metal core is a hollow, 10 tubular metal element, through which heat-exchanging fluid flows, for conducting heat out of said fibrous microceil structure.

37. An electrochemical cell device, including a plurality of fibrous microceil structures as in claim 1. 15

38. An electrochemical cell device according to claim 37, constituting a fuel cell.

39. An electrochemical cell device according to claim 37, constituting a battery cell. 20

40. A fuel cell comprising microceil fibrous elements, wherein each microceil fibrous element comprises: an inner current collector, an inner catalyst layer, a hollow fibrous membrane separator in contact with the inner catalyst layer and 25 the inner current collector, an electrolyte embedded in the hollow fibrous membrane separator, an outer catalyst layer, and an outer current collector, wherein at least one of the inner and outer current collectors comprises a metal clad 30 composite having two or more metal layers bonded together by solid-phase bonding. END OF CLAIMS 20 </div>