JP2004505417A - Microcell electrochemical devices and assemblies and methods of making and using the same - Google Patents

Abstract

The assembly of the microcell structure and 70 is efficiently utilized for electrochemical energy generation / conversion. The microcell structure of the present invention is applied to a fuel cell, a battery system, or the like, and is processed into a sheet shape (60, 62, 64, 66) that produces a high voltage and a high current density output, and is bundled as a lower structure. It can be easily made from individual fibrous microcell elements assembled into a larger bundled structure.

Description

[0001]
Field of the invention
The present invention relates to electrochemical devices and assemblies with microcells, methods of making such devices using various techniques, and methods of using such devices and assemblies.
[0002]
Technical description
In the technical field of energy supply and energy conversion equipment, especially in the development of fuel cells and batteries, develop equipment with sufficient power (high current and / or high voltage), high current density and high energy output per unit volume Attempts have been made to do so.
[0003]
Electrochemical cells, such as batteries and fuel cells, are relatively simple in structure, use an anode and a cathode that are separated to avoid internal short circuits, and arrange the electrodes so that they come into contact with the electrolyte solution. I have. When the electrode circuit is conjugated to an external load by a chemical reaction of the electrodes, the chemical energy of the reaction is converted to electrical energy and the flow of electrons produces power.
[0004]
In battery cells, a separator can be used between each electrode, in which multiple sheet-like elements are arranged in a continuously facing assembly or such sheets are wound together in a (helically) rotated configuration You can also.
[0005]
Fuel cells are currently of great interest as power sources for electric vehicles and in distributed power applications.
[0006]
In a fuel cell, fuel is introduced and brought into contact with the electrode (anode), and the oxidant contacts the other electrode (cathode), establishing the flow of cations and anions and coupling external loads to the cell. Then, a flow of electrons occurs. The output of the current is controlled by a number of factors, such as the catalyst immersed in the electrodes (eg, platinum in the case of a liquid hydrogen fuel cell), the kinetics of the specific fuel / oxidant electrochemical reaction.
[0007]
Currently, single cell voltages range from about 0.6 to 0.8 volts for many fuel cells. As current density increases, voltage and cell efficiency decrease correspondingly, so operating voltage varies with current. As the current density increases, much of the potential energy is converted to heat, which reduces the electrical energy of the cell.
[0008]
It is also possible to incorporate a reformer into a fuel cell and create an arrangement in which the reformer generates fuel such as hydrogen from a feedstock such as natural gas or methanol. Thereafter, the fuel products from the reformer are used in the fuel cell to produce electrical energy.
[0009]
In this technique, many types of fuel cells are described. To name this,
・ Polymer electrolyte fuel cell using fluorinated sulfonic acid polymer or similar polymer as electrolyte
An alkaline fuel cell that uses an electrolyte such as potassium hydroxide and is a substrate between electrodes containing a catalyst such as nickel, silver, metal oxide, spinel, or noble metal, and that maintains the KOH electrolyte.
・ A phosphoric acid fuel cell using concentrated phosphoric acid as the electrolyte that operates at high temperatures
A molten salt fuel cell using an alkaline carbonate or sodium / potassium electrolyte, operating at a temperature of about 600-700 ° C. in a lithium aluminate ceramic substrate, wherein the alkaline electrolyte forms a highly conductive molten salt;
Using a metal oxide such as yttria-stabilized zirconia as the electrolyte and operating at a high temperature, oxygen ion conduction is promoted between the cobalt-zirconia or nickel-zirconia anode and the strontium-doped lanthanum manganate cathode , Solid oxide fuel cell
and so on.
[0010]
Fuel cells are relatively efficient and have very low levels of exhaust gas / emission solids. Because of these features, fuel cells are currently of great interest as energy conversion devices. The efficiency of conventional fuel cell plants is typically in the range of 40-55%, depending on the lower heating value (LHV) of the fuel being used.
[0011]
In addition to low emissions to the environment, the fuel cell operates at a constant temperature, and the heat generated from the electrochemical reaction can be applied to waste heat power generation, improving overall efficiency. Because the efficiency of fuel cells is completely independent of size, fuel cell designs are scalable to a wide range of electrical power from watts to megawatts.
[0012]
A recent innovation in the field of electrochemical energy is the development of small electrochemical cells, or microcells, used in the application of electrochemical devices such as batteries and fuel cells. All microcell technologies are based on RayR. This is described in U.S. Patent Nos. 5,916,514, 5,928,808, 5,989,300, 6,004,691 to Eshraghi. The microcell structures described in these patents consist of hollow fiber structures connecting electrochemical cell components.
[0013]
The above-mentioned Eshraghi patent describes an electrochemical cell structure in which a single cell is composed of an electrode or its active material, a separator of a porous membrane, an electrolyte, a second electrolyte or a fiber containing the active material. are doing. The design of the cell is also described in the Eshraghi patent, in which adjacent monofilaments are utilized, one being an electrode or its active material, a monofilament containing the separator and electrolyte, and the second being a second electrolyte. It is a single fiber composed of Thus, adjacent fibers become the anode and cathode of the cell. In the present invention, Eshraghi's microcell technology has made further strides.
[0014]
Detailed description of the invention and its preferred embodiment
The disclosures of Eshraghi U.S. Patent Nos. 5,916,514, 5,928,808, 5,989,300, 6,004,691 are all hereby incorporated by reference. As used herein, the term microcell refers to a cell structure that electrochemically generates or converts energy, and includes a porous membrane separator having an electrolyte disposed within its porosity. The separator of the porous membrane is in contact with the conductive fibers, which are in contact with or coated with the electrocatalyst forming the anode and cathode of the electrochemical cell.
[0015]
In the description that follows, reference is made primarily to the readily available embodiments of the fuel cell of the present invention, but the description is directed to corresponding battery cells, and other forms of electrochemical cell devices consistent with the present invention. I am grateful that the same can be applied to.
[0016]
Naturally, battery cells differ from fuel cells in that when electrochemical activity is required, the active material (of the electrodes) is present in the battery and stored in the cell, rather than being provided outside the structure.
[0017]
Therefore, when microcells are used for battery cells, no lumen is required at the center of the fiber, which results in a correspondingly simplified fiber bundle of the modular assembly in battery cell applications. Thus, microcells in battery cell applications are structurally and operatively different from microcells used in fuel cells.
[0018]
In a special form, the microcell consists of the active material of the internal electrode, the microporous membrane separator in contact with the active element of the internal electrode, the electrolyte in the pores of the microporous membrane separator, and the external electrode active element The active part of the internal and external electrodes is composed of one or more electrodes, current collectors and electrocatalytic components.
[0019]
In another particular configuration, the microcell may include a fibrous internal electrode. This internal electrode is surrounded by a microporous membrane separator, in which an electrolyte is placed in the porosity, and an electrocatalyst is applied along with the conductive material on the pore side (forming the internal electrode) or the shell side (external Electrode forming) or coated with an electrocatalyst.
[0020]
In fuel cell applications, the hollow fibers of the microcells define the passage lumen through which gas or liquid supply components (such as fuel or oxidizer) pass. Many types of electrolytes can be used in microcell fuel cells, depending on the particular relevant application.
[0021]
In a preferred form, all components of the microcell are processed into a monofilament assembly. Microcells can be of any defined length, and typically have a diameter to length ratio much greater than one. In addition, it can be easily formed into a plurality of microcell assemblies, including a bundle-like configuration, which will be described in detail below. Such microcell assemblies, or collections of such assemblies, can be assembled to form a fuel cell module whose overall arrangement is similar to a shell and tube heat exchanger.
[0022]
When multiple microcell elements are fabricated to incorporate a bundle of multiple cell modules into a single overall configuration, the resulting single miniature configuration produces a high density of energy output and can be a fuel cell or In addition, the volume (and "footprint") of the electrochemical cell device processed from such a bundle can be minimized.
[0023]
In one embodiment, the microcell device of the present invention is fabricated using internal electrodes (or multiple current collector fibers) surrounded by a microporous membrane separator. In such an embodiment, the electrocatalyst of the inner electrode is coated or impregnated on the inner wall of the membrane separator (or coated on the inner current collector fibers).
[0024]
In one embodiment, the membrane separator wall is impregnated with an electrocatalyst of a catalyst solution. In another alternative embodiment, during the membrane spinning process, a thin catalyst paint is pumped through holes in the membrane separator.
[0025]
One technique for forming an assembly with a porous separator-electrode is to coat the current connector fibers with an electrocatalytic paint. In one embodiment, such coating is performed by extrusion. In another embodiment, the current connector fibers are coated with a plating solution. In yet another embodiment, the current connector fibers are coated by plasma deposition of a metal catalyst.
[0026]
When stacking fuel cells or forming modules, microcell fibers are bundled and attached to separate and seal the pore side and the shell side of the cells. In a large fuel cell structure, the microcell can also be wound around a perforated central axis, thereby providing a structure in which the rotating shaft can enclose gas on the shell side of the cell.
[0027]
For the elements of the microporous membrane separator used in the fuel cell embodiment and other electrochemical cell embodiments of the present invention, it is not possible to use an appropriate method of impregnating or mixing the electrolyte. , Always useful. An illustratively preferred technique for impregnating the electrolyte is solution impregnation.
[0028]
The porous membrane separator element itself can be of various types and structures and can be shaped for use in certain types of fuel cells and other electrochemical cell applications. For example, in a polymer electrolyte fuel cell, a porous structure with asymmetric pathways is preferred, resulting in a continuous layer of ion exchange polymer adjacent to the electrocatalyst layer. In an acid or alkaline fuel cell, it is desirable to use a foamed porous membrane element. Thanks to the advanced methods of the present technology, the choice of membrane separator configuration and morphology can be readily determined without undue experimentation.
[0029]
Fuel cells produced from microcells in accordance with embodiments of the present invention are monopolar and do not require bipolar flow plates. Because the cells and current collectors are fibrous, the surface area of a large electrode can be reduced to a very small volume. The parallel connection of the individual bundled cells adds current, allows very high current density per unit volume, and allows the microcell assembly to operate at high voltage and high efficiency.
[0030]
In one embodiment, the internal electrodes of each microcell are connected, forming a first terminal in the microcell assembly, and the current flowing outside the shell of the fiber element, or the shell of such a bundle of microcells. The collector is the second end. When such an assembly is constructed and arranged for use in a fuel cell, the fuel and oxidant pass through the respective shell-side and hole-side electrodes of the respective bundle. In the individual microcell elements of this fuel cell, the microporous membrane is soaked with a suitable electrolyte to form a barrier or isolation element. Depending on the type of electrolyte, the microporous substrate and the electrolyte can be combined to form a new structure in the form of a solid substrate or a liquid-solid substrate.
[0031]
In an application example of a fuel cell using a microcell device including a single-fiber-shaped internal electrode element, the size of the internal electrode element is selected, and an appropriate sized lumen is formed on the hole side of the membrane separator including the electrode. I do. A plurality of fibers can be attached to the holes of the hollow fiber membrane separator to create an interstitial space forming a lumen within the hollow fibers. The formation of the lumen is important because when the fuel cell is operated, the lumen allows the fuel or oxidant (liquid or gas) to reach the internal electrodes.
[0032]
In a preferred form, the electrocatalyst and conductive material of the second electrode are coated or extruded or impregnated on the outside of the microporous membrane separator shell, the electrolyte is placed in the micropores of the membrane separator, and the microcell Form the structure.
[0033]
The microporous membrane separator can be formed from any suitable material structure. In one embodiment, a microporous membrane separator is fabricated from a material selected from the group of semipermeable ion exchange membranes and a porous membrane coated on the shell or pore side of a permselective or ion exchange polymer. I do.
[0034]
In this microcell structure, the internal electrode or current collector is firmly fixed in the hole in the separator, adjacent to the inner wall of the fiber, and the electrolyte or electrolyte / electrocatalyst layer is in contact at the interface. When the fibrous microcell structures are bundled closely together, the outer electrode or current collector can be in intimate contact with the electrolyte on the shell side or the electrolyte / electrocatalyst layer of the adjacent cell.
[0035]
Therefore, in fuel cell applications, the lumen of the microcell structure must be "open" enough to allow the gas supply (fuel or oxidant) to pass through the lumen during normal operation. For such a purpose, it is desirable that the fuel cell device includes a pump, a fan, a blower, a compressor, a discharge device, and the like. Since the flow rate required to operate the fuel cell requires only a relatively low pressure drop, the pumping required (to pass the gas supply through the hollow fiber lumen of the microcell) is of the type described above. It can be easily handled by a commercially available liquid driver device.
[0036]
Continuous connection of microcell structures and assemblies
To achieve high current density at the voltage level of a single microcell, multiple microcells are connected in parallel. Parallel connection of microcells for this purpose can be easily achieved by bundling the microcells in parallel with each other and connecting the ends of the current collector to each end of the obtained microcell assembly.
[0037]
However, achieving high voltages beyond the voltage generated from a single microcell requires continuous interconnection of the microcells. As will be described in further detail below, depending on the required microcell assembly geometry, a variety of methods can be used to achieve a continuous connection. For example, a rectangular or cylindrical configuration may be desirable.
[0038]
In accordance with the invention, a bundle of substructures of fibrous microcells in parallel is first assembled to obtain the desired current. The bundle of substructures is then connected in series to achieve the desired voltage.
[0039]
One preferred approach to forming a substructure bundle of microcell assemblies is to form a sheet-like arrangement of microcell elements, usually arranged in parallel. Here, the microcells are adjacent to each other and the current collectors extend from the ends of the normally adjacent and co-aligned flat sheet (ie, the ends of the current collectors are usually coplanar with each other). The current collector protruding from the microcell is usually coextensive with the depth of the assembly surface of the microcell sheet from which the current collector protrudes) . Next, the first layer of the microcell element is covered with a second layer constituting the outer current collector element, and the outer current collector extends from the side of the stacked sheets opposite to the side from which the inner current collector protrudes. To be arranged. Furthermore, the outer current collector extends outward, usually to the same length, so that they are mutually aligned at the ends of the outer current collector, and are usually mounted on a single vertical plane, relative to the flat horizontal surface of the sheet assembly .
[0040]
For the purpose of forming the above-mentioned sheet assembly, the fibrous microcell parts constituting the first layer can be fixed to each other, and such elements can be formed into a single net structure or sheet structure. In a similar manner, the outer current collector overlaps the fibrous microcell element, such as by an inner connecting mesh or braided structure, side-by-side adhesive tape, or other method of making a parallel-assembled current collector element. Can be mutually stabilized by a sheet structure or a network structure.
[0041]
Fortunately, any suitable method can be used to form a sheet-like layer for each of the microcell assemblies described herein. Such layers can be preformed, for example, by weaving the microcells or current collector fibers into a sheet, embedding them in a resinous substrate, or other suitable methods.
[0042]
Once the layers of the microcell element and the layers of the outer current collector component are brought into contact with each other in superposition, the composite structure is rotated into a cylindrical shape, joining the opposite ends of each other, forming the diversity of the microcell, A subassembly bundle can be formed.
[0043]
Such an assembly can be combined in any suitable manner, for example, when processing a hollow fiber filtration module, using methods conventionally used to attach hollow fiber membranes. As a result, the combined substructure bundle has an anode and a cathode at each end. One terminal is formed by an inner current collector element protruding from the microcell element of the first described layer, and the other terminal is formed by a current collector protruding from the opposite end of the substructure bundle. .
[0044]
Then, the positive electrode of the first substructure bundle is connected to the negative electrode of the next bundle, and this is repeated to continuously connect the bundles. The long strands of the connected bundle are then alternately rolled at each end and at the junction between the subsequent microcells, and re-bundled into a cylindrical shape. The substructure bundle assemblies that have been rolled up so as to be placed in an alternating side-by-side relationship are then joined at each end thereof to form a composite bundle having multiple substructure bundles.
[0045]
The continuous bundle includes fibrous microcells in both parallel and continuous connections that make up a single structure, which is then combined with a shell and tube heat exchange assembly, described in detail below. Place in a frame like
[0046]
As is apparent from the above discussion, in order to avoid a short circuit between the bundles of the substructure, it is necessary to cover each bundle with a porous but electrically insulating material. Therefore, each bundle can be covered in a fiberglass or porous packaging film, in which the bundle is inserted or wrapped in a packaging material.
[0047]
By alternately forming substructure bundles and packing each end alternately into a bundle, the positive end of the bundle can be closer to the negative electrode of another bundle. This alternative technique requires a continuous connection by first attaching the substructure bundle and then connecting the positive pole of the first bundle to the negative pole of the next adjacent bundle. Substructure bundles can also be connected simply by forming electrical connections for each microcell. Instead, at the connection points of the bundle (all microcell fibers are connected in parallel in a substructure bundle), a terminal plate with a mirror image of the surface and a continuous connection of terminals designed and constructed on that plate Can be used, and the plates are electrically connected at each connection point of the bundle, automatically forming a continuous connection.
[0048]
Yet another alternative for attaching substructure bundles is to fabricate a sealed tube sheet membrane at the end of each bundle. Thereafter, each bundle can be inserted into a frame to open each end with the same parameter (perimeter) size as the underlying structure bundle. By performing such processing, each bundle can be sealed at each end of the container by, for example, an O-ring or another sealing method, and there is no need to attach the bundle again. With such a configuration, each bundle of substructure can be removed from or placed in a container so that it can be easily and easily affected, thereby increasing the power generation capacity of the microcell device as a whole. , Can be lowered.
Alternatively, by alternately stacking the microcell layers and outer current collectors and repeating the arrangement, the bundle of substructures can also be machined into a rectangle, with the desired height and rectangular cross-sectional area. The layers comprising the microcell fiber element and the outer current collector can be sheet-like, as described above.
[0049]
When connecting the fibrous microcell elements and the layers as the substructure of the outer current collector in series, the current collector elements usually have the same length characteristics as the fibrous microcell elements and the respective fibrous microcell elements The microcell element and the current collector layer vertically offset each other. In such an arrangement, the outer current collector element is moved beyond the other end of the fibrous microcell layer and the outer current collector element is correspondingly shortened at the opposite end, so that the first layer (lower layer) Are longer than the end of the outer current collector layer.
[0050]
Thus, at each end of the layered assembly, there is a "shortened" line in the upper or lower layer, and it is this short end portion that forms a bonded structure at each end of the entire assembly.
[0051]
A porous insulating sheet material is placed on this substructure layer assembly, and a second substructure layer assembly is made on the porous insulator sheet. In the second substructure layer assembly, the lower layer is placed directly on a porous insulator sheet, superimposed on the outer current collector layer and offset each other, and the new substructure layer cathode is replaced by the first in the overall assembly. As the negative electrode of the lower structure layer, it is arranged so as to come on the same surface. This processing pattern is continued until the desired lower structure layer is at the desired height and the desired voltage can be achieved. For example, the ends of the anode and cathode current collectors at each end are connected to each other, together with a conductive rod or cord as described below.
[0052]
Alternatively, the laminar assembly can be processed by electrically connecting the fibrous sheet with the anode and cathode ends of the adjacent layers first before stacking the respective substructure layers. Thereafter, the last stacked lower structure layer is joined at both ends of the assembly, and the holes of the lower structure layer assembly are separated from the shell side and sealed. The combined bundle of fibers is then placed in a perforated tube which acts as a fuel inlet to the hollow fiber shell side of the assembly. For example, fibrous microcell elements and outer current collectors are alternated so that the fibers are layered by placing a straight or beaded epoxy or other binding compound at each end so that the layers overlap. Can be attached to Choosing a bonding material of appropriate viscosity so that the fibrous microcell elements are completely wetted and the resulting tubesheet is firmly fixed to the leak contents.
[0053]
Once bonded, the bundle or stack of microcell layers enters the container, and when fuel is injected at either end (shell or perforated), the shells and perforations of the microcell elements are sealed and separated. You. The resulting unit takes the form of a rectangular shell and a tubular heat exchanger, such a unit comprising one or more inlets for delivering fuel to the perforated side of the container and the fuel used from the perforated side of the container. It can be advantageously processed by having one or more outlets to remove ash.
[0054]
When the microcell elements are placed in stacked layers, such a stack is located on a tube that has holes at each end between the binders. Make the unperforated part of the tube longer than the other end of the container, for example, as described, provide a fuel inlet or outlet on the hole side of the microcell element, or make the tube longer than the container in a sealed state This creates a fuel inlet on the shell side of the microcell element. Stacks of layered microcells can be placed on either side of the perforated flues, creating symmetrical double stacks, as described in more detail below.
[0055]
In one aspect of the invention, a bundle of small substructures of a microcell assembly can be electrically connected in the same cell container, or a smaller fuel cell module can be electrically connected. , The overall battery voltage can be increased. As another embodiment of the present invention, one approach to achieving high voltage levels is to multiply the stack of fuel cells (each comprising a number of microcell devices) and supply gas in parallel, The stack itself is an assembly of continuously connected microcell bundles.
[0056]
In one embodiment, the conductive fibers are bundled with the microcell device such that the conductive fibers function as a current collector on the fiber shell side. The shell-side current collector, or alternatively the outer electrode coated with a suitable electrocatalyst, is connected to a common plate to build the first terminal of the bundle assembly. Similarly, an internal electrode that is longer than the microcell fiber holes is connected to the plate to form a second terminal in the assembly.
[0057]
In such a fuel cell assembly, the fuel or oxidant passes through the electrodes on the pore side or shell side of the fiber, respectively, and the membrane separator containing the electrolyte prevents the fuel or oxidant from migrating to the other electrode.
[0058]
In the present invention, the fiber structures of the microcells are usefully attached and the substructure bundles are connected in series or in parallel to form a substructure bundle that forms a larger, final bundle structure. As discussed above, some bundles of structures and substructures can be connected in parallel with other substructure bundles by connecting them in parallel with the parallel connection assembly of microcell elements. The reverse arrangement, in which the elements form a bundle of substructures, which are connected in parallel with one another, is also useful in some applications).
[0059]
In one preferred embodiment, the microcell fibrous structure is processed as a substructure bundle, and the bundle is collected together with the other bundles and rejoined to form a fuel cell module. Advantageous bonding substrates used to secure the structure of such microcell fibrous structures or bundles of substructures include any suitable bonding materials, such as epoxy, urethane, silicon, EPDM rubber, etc. It may be a substrate or a material substrate of a capsule.
[0060]
The substructure bundle can be made from a tube sheet sealed at each end with O-rings, similar to the process used in the assembly of the final module, and the substructure bundle is made of perforated metal or polymer. To the sheet. As a result, the fuel cell container has two surfaces, and one surface has at each end thereof a hole cut out to the outer diameter of the tube sheet of the bundle of the lower structure.
[0061]
This arrangement allows the power to be increased or decreased by adding or removing substructure bundles to or from the entire module (for example, in stationary transport batteries, or in electric transport vehicles that provide adjustable vehicle power, for power transport applications). Power in the field). When the substructure bundle is removed from the module, the holes in the surface can be sealed with an empty sheet the same size as the holes. This feature also allows individual bundles to be repaired by removing the defective substructure bundle and replacing it with a new bundle. The substructure bundle itself may be a coupling unit that forms a smaller substructure bundle.
[0062]
FIGS. 1-4 are perspective views of the structure of the fibrous element, showing the assembly of the microcell assembly.
[0063]
As shown in FIG. 1, a fibrous microcell sheet 10 is made up of a plurality of fibrous microcell elements 12 placed side by side in a parallel arrangement. Each fibrous microcell element 12, as shown, has been strengthened by a plurality of stitched seams 16 or has been strengthened using an attached method such as tape, adhesive, etc. The element sheet of the microcell is formed.
[0064]
The sheets 10 shown are side by side with one another to the first end 18 of the element 12. That is, the ends are generally coextensive with respect to the axis of one another, and the ends 18 are in a common vertical plane extending across the sheet surface from which the inner current collector 14 protrudes.
[0065]
In a similar manner, the opposite ends 20 of the fibrous microcell elements 12 are aligned side-by-side with one another, the ends of which are typically on the opposite side of the fibrous microcell elements 12 to a vertically extending surface. , Side by side.
[0066]
In this manner, the fibers are laid flat, adjacent to each other, and gathered in a network-like structure to form a sheet of fibers.
[0067]
The plurality of outer current collectors 24 are also similarly stiffened in a side-by-side arrangement by stitched seams 26, or alternatively are stiffened using a connection method such as tape, adhesive lace, etc. As shown, a sheet 22 is formed. In such a sheet 22, the current collectors 24 comprising the respective ends 28 and 30 are aligned with one another, with each end of the fibrous current collector lying in a plane extending laterally vertically at each end of the mesh. Will be.
[0068]
Next, the sheet 10 of the fibrous microcell element 12 and the sheet 22 of the fibrous current collector element 24 were overlapped such that the current collector sheet 22 was on the sheet 10 of the fibrous microcell element, as shown in FIG. A coupling structure 32 is made.
[0069]
Such a coupling structure 32 causes the respective sheets 10 and 22 to vertically offset each other, such that the inner current collector element 14 of the sheet 10 is longer than the outer current collector of the sheet 22 as shown, and Correspondingly, on the opposite side of the coupling structure, the outer current collector of sheet 22 is longer than the end of inner current collector 14 of sheet 10. Thus, each outer current collector of the overlaid sheet 22 contacts a corresponding fibrous microcell element of the underlying sheet 10.
[0070]
In FIG. 4, the coupling structure 32 of FIG. 3 is the lowermost layer of the assembly formed thereon with the second layer 36 as the lower layer. The second layer 36 includes fibrous microcell elements 38 arranged side by side to form a corresponding sheet, and the second layer includes an outer current collector with seams 40 stitched as shown. A fixed sheet 48 is put on the fixed sheet.
[0071]
In this second layer, the fibrous microcell elements 38 are aligned with each other at their respective ends 42 and 44, and the sheet of outer current collector 48 is oriented in the longitudinal direction of the sheets of fibrous microcell elements 38. I have put it. In such an arrangement, the outer current collector 48 is longer than the end 42 of the fibrous microcell element 38, and the inner current collector 46 of the fibrous microcell element 38 is longer than the end of the outer current collector 48.
[0072]
At the same time, the current collectors projecting vertically from the first and second layers respectively at each end of the assembly are coextensive with respect to one another with respect to the axis. A porous insulating layer or fiberglass sheet 50 made of a polymer is placed between layers 32 and 36 as shown in FIG.
[0073]
FIG. 5 is a perspective view of the connector 52 connecting the current collector or electrode elements of the microcell fiber assembly. The connector 52 has two springs 54 and 56, which are at an angle of 90 ° to each other, so that the springs can be pressed together. When a plurality of current collectors or electrode elements are placed between the springs of the connector and the springs are pressed together, the current collectors or electrode elements are in firm electrical contact.
[0074]
FIG. 6 shows the microcell assembly of FIG. 4, in which the current collector element on the right side of the figure is fixed to the connector 52 and the two current collector elements are in electrical contact with each other.
[0075]
In FIG. 7, a perspective view of the microcell assembly 70 is shown in an exploded view, and the microcell sheet layers 60, 62, 64, and 66 connected in series are shown. The lower sheet layer 60 consists of inner current collector elements connected by connectors 72, the sheet of outer current collector overlying such a layer being fastened by connectors 74, in turn.
[0076]
The next layer up in this assembly consists of an inner current collector connected by a connector 78, which is connected to a connector 74 by an internal connection 76. Similarly, the outer current collector is coupled to connector 80.
[0077]
The connector 80 is connected by an internal connection 82 to a connector 84 of the next higher layer in the assembly. A connector 84 connects the current collector inside the next higher layer, and at the opposite end of this layer, a connector 86 is connected via an internal connection 88 to a connector 90 on the top layer of the assembly. The current collector is connected.
[0078]
Connector 90 connects the current collector inside the top layer of the assembly, and at the opposite end of the top layer of the assembly, the outer current collector is connected by connector 92.
[0079]
Each layer of the assembly is separated from adjacent layers by a corresponding porous insulating sheet 94, 96, 98, respectively.
[0080]
With the above arrangement, each component layer of the assembly of FIG. 7 is joined to the next adjacent layer in a continuous manner from top to bottom, as is evident from the respective connectors being shown inverted in the figure. are doing.
[0081]
FIG. 8 is a schematic diagram of an assembly 100 in a layered arrangement of successively connected microcell layers, wherein layers 102 and 104 are separated by a porous insulating sheet 110 and layers 104 and 106 are porous insulating layers. Sheets 112 and 106 and 108 are separated by a porous insulating sheet 114.
[0082]
FIG. 9 is a three-dimensional perspective view of an array 130 in which microcell layers are continuously connected. The bottom layer is shown, which is a sheet of fibrous microcell elements 122. From 122, an inner current collector element 124 projects to the left of the layer and an outer current collector element 126 overlies to form a microcell layer. As shown in the schematic, the bottom layer is shown to be electrically separated from the next overlying layer by a porous insulating layer 128. Other layers have the same configuration. The top layer 130 is composed of three fibrous microcell elements arranged side by side, as shown, and the sheets of other fibrous microcell elements of this assembly are correspondingly configured. . In this way, a structure of a bundle of microcells is formed.
[0083]
FIG. 10 shows an arrangement 136 in which bundles 138 of the substructure of the microcell are connected. Here, a bundle of component substructures is continuously coupled to opposing current collector elements 140 and 142, respectively, and adjacent bundles are separated from electrical contact by a porous insulating sheet 147. And the possibility of a short circuit is gone. As shown, the bundles 138 of the substructure are joined at each end by binders 144 and 146.
[0084]
FIG. 11 is a perspective view of a tube 150 with doubly stacked bundles of microcell layers with perforations 154 in the upper surface 152 and optionally the lower surface (not shown in FIG. 11). Two fixing walls 156, 158 are on both sides to fix the fiber sheet in place. Stack the fibers on the perforated tube until the desired voltage is obtained. As shown, a liquid inlet / outlet tube 160 is connected to the inner plenum chamber tube 150.
[0085]
The reclined fiber sheet can be bonded with epoxy. Alternatively, the fiber sheet can be bundled and attached to the container to complete the process. The fibers bind at each end such that the open ends remain open. The perforated tube serves as an inlet for the fiber on the shell side.
[0086]
FIG. 12 shows a cross-sectional elevation view of the microcell fiber bundle 162 embedded in the container 150. This fiber bundle is composed of fibrous microcell element layers 164 and 166, with an outer current collector element sheet 168 therebetween, and a porous sheet between the adjacent current collector and fibrous microcell element sheet. The sheet 170 made of an insulating material is separated. This bundle is attached by a bonding material 163.
[0087]
FIG. 13 is a side view of the container of FIG. 12, showing the fixed wall 156 and the liquid inlet / outlet tube 160 of the container and the connection of the terminals on each side 180 and 182 of the bundle.
[0088]
FIG. 14 shows an arrangement 186 in which fibrous microcell sheets are joined in two substructure bundles 188 and 190 on the opposite side of the conduit 196 that receives the feed gas from the inlet 198. The feed pipe has holes on the upper surface and the lower surface, and the bundles of the lower structures constituting the bundle are fastened with the binding material 192 at the upper bundle and fastened with the binding material 194 at the lower bundle.
[0089]
FIG. 15 is a side view of a two-tier arrangement 200 in which the microcell elements are configured to stack on each side of a perforated tube. A gas supply tube 198 is shown in the figure. The arrangement shown in this figure includes connector / terminal components 202, 204, 206 that couple corresponding current collector elements.
[0090]
FIG. 16 is a perspective view of a fibrous microcell element assembly 210 attached to one side of a perforated tubing, including a gas inlet 224 and a stationary wall 216. A bundle of bound rectangular microfibers is arranged, and the ends are bound by binders 218 and 220.
[0091]
FIG. 17 shows a container 230 in which fibers are placed on both sides of a perforated pipe 238. The container has a central portion 232 having an outlet 242 for discharging gas from the shell side of the microcell assembly, an end portion 234 having an outlet 248 for discharging gas used on the hole side, and gas on the hole side. It comprises a distal end 236 with an inlet 246 for introduction into the container. A perforated conduit is arranged to feed gas to the central portion 232 of the vessel, creating a flow on its shell side.
[0092]
FIG. 18 is an elevational view of a system 250 that includes a bundle of microcells 280 joined at each end by bonds 266 and 268. These binders keep the inner surface of the container 252 tightly sealed by the O-rings 270 and 272.
[0093]
The container 252 has a flange 256 connecting the end 258 and the center of the container. There is an inner volume 252 in the center of the container, with an end volume 278 separated by a binder 268 and an end volume 282 by a binder 266. The fuel inlet 276 leads to a terminal volume 278 and the terminal volume 282 leads to an outlet 284 for the used gas.
[0094]
The used gas outlet 264 is connected to the internal volume 262. The feed pipe 260 extends to the center of the microcell bundle 280 having the internal volume 262, and has a vertical hole. The supply gas is introduced to the shell side of the microcell bundle 280 having the internal volume. The used gas is discharged to the outlet 264. The fuel introduced from the inlet 276 into the terminal volume 278 flows through the pore side of the microcell element of the bundle 280, flows from the bundle to the terminal volume 282, and is discharged from the outlet 284 of the container 252.
[0095]
The current collector couples to a terminal 292 of the terminal volume 282, the terminal structure extending out of the container 252. At the opposite end volume 278, the other inner and outer current collectors couple to terminal 290, which extends outside the container.
[0096]
FIG. 19 shows a perforated tubing 300 with an open end 302. A hole 308 is opened along the length of the central portion 306.
[0097]
FIG. 20 shows fibrous microcells and shell side current collector sheets 312, 314 that can be rotated or wrapped around the perforated tube 300 of FIG. FIG. 21 shows a state in which the sheet is being rotated, and FIG. 22 shows a state in which the sheet has been rotated.
[0098]
The sheet is placed on the other sheet, and the end of the fibrous microcell sheet 312 is longer at one end than the current collector sheet 314 on the shell side, and the current collector sheet 314 on the shell side is longer at the other end. Thereafter, the sheets 312, 314 are tightly wrapped around the perforated tube 300 and fastened with binders 322 and 324.
[0099]
FIG. 23 shows fibrous microcells, sheets 332 and 334 of the current collector on the shell side, and an insulating sheet 330 (such as fiberglass or a porous plastic material). FIG. 24 is a perspective view of a sheet assembly 338, 340, 342, 344, 346 including two sheets of fibrous microcells and two current collectors on the shell side.
[0100]
FIG. 25 is a side view of the microcell assembly 338, 340, 342, 344, 346 using the filled fiber layer. An insulating sheet is placed between the two fiber layers forming the cell. As shown in FIG. 25, if the sheet on one side of the insulator is longer than the end of the insulator, the fiber layer can be connected to another fiber layer continuously.
[0101]
FIG. 26 is a cross-sectional view of a bundle 350 of microcells. This is an assembly in which a cathode 352 is scattered on an anode 354 and bundled.
[0102]
FIG. 27 is a side view in the case where the bundles 360 of the lower structure of the microcell are continuously connected, and the bundles 362, 366, 370, 374 of the lower structure are internally connected by connectors 364, 368, and 372, respectively. . The connector is preferably flexible, since the substructure bundle chains are folded like an accordion so that they can be folded back into the previous bundle or forward into the next bundle. Those that bend in the direction are most preferred.
[0103]
FIG. 28 is a perspective view of a connector 376 used to connect the bundle of the substructure of the microcell as a component in a continuous manner. The connector 376 comprises a pair of spaced-apart springs 378, 380, each of which can be pressed together by tools such as pliers, compressing the protruding current collector of the bundle of substructures. Hold firmly. This spring is conductive and interconnected by a bendable yoke element 382 itself. The yoke element can be made of wire, metal filament, or the like, and serves to electrically interconnect the bundle of substructures to which respective springs 378 and 380 are connected.
[0104]
FIG. 29 shows an assembly 390 having a plurality of bundles, in which a feed tube 394 corresponding to each bundle 391 is inserted, a tube sheet 393 is attached, and an O-ring sealing agent 392 is used to prevent leakage therethrough. It is a cross-sectional elevation view at the time of sealing.
[0105]
FIG. 30 is a cross-sectional elevation view of the multi-bundle assembly of FIG. 29. In this, the respective bundles are connected successively, and are numbered corresponding to FIG. By connecting the wires 398 in a continuous arrangement, each adjacent bundle is interconnected by interconnected terminal elements 396 and 400.
[0106]
FIG. 31 is a cross-sectional view of a fuel cell module containing a plurality of substructure bundles, numbered corresponding to FIG. 29, and having the empty closed element 402 and 404 causes the tube sheet 393 surrounding the module to be closed.
[0107]
FIG. 32 is a side view of a fuel cell module 410 having a plurality of substructure bundles 460, 462, and 464 made of microcells, and a branch pipe 450. The module includes a container 422 surrounding a central inner volume 424 separated by the container wall of the module and tube sheets 472 and 474. For the tube sheet 472, the undercarriage bundle is firmly secured at the O-ring element 438 and for 474, the undercarriage bundle is securely secured at the O-ring element 434. Fixed.
[0108]
The container end element is surrounded by end volumes 426 and 428, respectively. The end volume 426 has a manifold to which a conduit 450 is connected for flowing gas, and a bundle 460, 462 of three substructures by manifold lines 452 connected to branched lines 454, 456, 458. , 464, respectively. The branched lines 454, 456, 458 are connected to respective substructure bundles.
[0109]
The bundles of the lower structure are continuously connected to each other one after another by a connection line 440 interconnecting the bundles 460 and 462 of the lower structure and a connection line 442 interconnecting the bundles 462 and 464 of the lower structure. As shown, such continuous outer substructure bundles are joined by terminals 444 and 446, respectively.
[0110]
The right end portion of the container is connected to the main central element of the container by a flange 430 and is connected to each other in a mechanically clasp-like manner to secure the component elements of the container in a leaktight manner. be able to.
[0111]
In this container, one of the fuel and oxidant streams is introduced into the terminal volume 426 at the fuel inlet 466 and flows to the substructure bundle at the hole side.
[0112]
The outlet 468 is connected to the container 422 by the left element in the figure, and discharges the used supply gas from the terminal volume of the container.
[0113]
The used gas outlet 470 is located in the main central part of the container and discharges the used gas from the shell side of the bundle of the substructure in the inner volume 424 of the container.
[0114]
FIG. 33 shows a cross-sectional side view of the interior volume 506 of a container 515 containing a module 480 containing a bundle 494, 496, 489, 498 of the microcell substructure, passing through a conduit 514. FIG. In this arrangement, with tube sheets 500 and 502, the bundle of substructures is attached to a correspondingly sized receiving opening, and the tube sheets are secured tightly by an O-ring sealant 492 to prevent leakage of the container. I have. In this method, the interior volume of the container is divided into a central volume 506 and end volumes 526 and 528.
[0115]
The container is fitted with a supply gas inlet 510 and used gas outlets 508 and 512. Gas used on the shell side of the undercarriage bundle exits the vessel at outlet 508, and feed gas entering inlet 510 flows through the hole side of the undercarriage bundle and exits to terminal volume 528. . From the terminal volume 528, the gas used on the hole side is discharged from the container at the outlet 512.
[0116]
The bundle of substructures in the interior volume of the container 515 are connected to one another in succession by a continuous connector line 516, 518, 520, and the bundle of outer substructures arranged in series is terminals 522 and 524. Be combined.
[0117]
The container 515 can be opened at the flange 443 to remove the right-hand end, after which the respective substructure bundle can be evaluated and repaired or replaced.
[0118]
Therefore, the microcell according to the present invention can easily connect adjacent components (fibrous microcell sheet layers, bundles of the substructure) one after another, and can conduct electricity from a porous insulator. They can be isolated from each other by sheets or sheathing boards made of impermeable material or in such a way as to ensure that there is no electrical interference between adjacent microcell components. Thanks to the advanced methods of the present technology, the bundle of multiple substructures shown in FIGS. 32 and 33 is only an example, and in certain applications of the present invention, the demand for energy generation in particular embodiments may be reduced. The bundle of a number of substructures can be varied in various ways depending on the structural and operational parameters of other systems.
[0119]
In the manufacture of high voltage electrochemical cells utilizing the microcell components of the present invention, bundle or sheet assemblies of microcells are manufactured. For example, if a design current of 200 amps is required, a number of fibrous microcells are connected in parallel to generate the required current. The resulting microcell structure can be bundled into a cylinder or used to form an assembly with multiple layers. In the case of a bundle, the anodic and cathodic fibrous elements need to be electrically insulated, but must still be in intimate contact with each other. To achieve this high voltage, the sheets or bundles are connected in series, that is, the anode of one cell is connected to the cathode of the next adjacent cell. When cells, bundles, or sheets that are continuously connected to each other are embedded and sealed in the same container, an electrochemical cell module that generates a desired high voltage is obtained.
[0120]
Terminal management
When the microcell elements are bundled or otherwise assembled into a compact structure to form a modular electrochemical cell assembly, the resulting electrochemical energy generation / energy conversion device generates a large amount of heat during operation. I do.
Various methods are available for removing heat from the microse assembly in accordance with the present invention.
[0121]
In one aspect of the invention, the heat transfer tubes are distributed into microcell bundles, substructure bundles, or other collective microcell assemblies. In a preferred embodiment, such tubes are arranged in parallel with the fibrous microcell elements of the microcell assembly.
[0122]
In another embodiment, the heat transfer tubes are placed between the bundles of the substructure of the assembly, and the heat transfer tubes are at least opposite from one end of the tube sheet surface (where the end of the substructure bundle or part of the outside is attached). So that it extends to Thanks to the advanced method of this technology, the number, size and material of the heat transfer tubes depends on the amount of heat that needs to be recovered, the operating temperature of the fuel cell, the type of heat exchange liquid used, the pumping requirements of the liquid or the flow rate. Can be easily determined.
[0123]
In order to control the heat exchange liquid separation from the fuel flowing to the pore side of the microcell fiber of the fuel cell module, the length of the heat transfer tube must be longer than the tube sheet that seals the pore side of the microcell hollow fiber on the shell side. In addition, the length of the heat transfer tube can be selected. Next, the stretched heat transfer tube is attached again, and a barrier is formed between the hole of the heat transfer tube and the hole of the microcell hollow fiber.
[0124]
The final assembly of the fuel cell module with the heat transfer tubes is configured with an inlet for introducing the heat exchange liquid at one end of the first container, and two coupling sites (ie, microcell elements coupled with the coupled heat transfer tubes). It is preferable to include a second container with an inlet for introducing fuel on the hole side of the microcell between the two, and the structure of the container is a corresponding structure on the opposite side, and is used with a heat exchange liquid. It is desirable to have a respective outlet for discharging waste fuel.
[0125]
For a microcell electrochemical cell module in accordance with the present invention, an alternative thermal management design is to use a hollow, non-porous, non-porous, shell-side, or both, current collector for the microcell structure. Use porous, conductive and heat transfer tubes. Since the current collector terminates on the opposite side of each tubesheet, the heat exchange current collector tubes will be mounted as described above, and only one end will isolate the heat exchange liquid container from the hole side / supply. At the opposite end, the heat transfer tubes terminate in tube sheets.
[0126]
In this arrangement, the heat exchange liquid and the fuel flowing into the holes can be mixed at the outlet. In this system design, the heat exchange liquid does not enter the pores of the microcell and does not come into contact with the catalyst or electrolyte. For example, the fuel and heat exchange liquid flowing in the holes can be supplied to the module in the same direction, and the heat exchange liquid and the fuel flowing in the holes can be prevented from mixing except at the fuel inlet of the microcell.
[0127]
Next, the heat exchange liquid can be collected in another unit, or the heat exchange liquid can be collected and recycled using the plenum of the container. For example, when the fuel is gas or hydrogen gas, separation of the heat exchange liquid and the heat can be easily achieved.
[0128]
In special embodiments where the heat exchange liquid and the fuel flowing to the holes are the same (eg, air), the heat exchange liquid and the fuel can be mixed and need not be separated.
[0129]
In a further embodiment, heat is removed from the microcell module by conducting heat from a current collector on the shell or hole side of the microcell element. In this approach, the end of the current collector is extended and the heat exchange liquid located in the heat exchange channel located inside the container at the plenum inside the container containing the microcell module, or at the fuel inlet or outlet coming into or out of the fiber holes. Soak in In the latter case, the inlet and outlet of the heat exchange passage are tightly separated from the internal volume of the microcell module so as not to leak.
[0130]
Referring to the figure, FIG. 34 is a cross-sectional view of a microcell assembly 530 with heat transfer fibers and tubes 538 scattered (distributed) as shown.
[0131]
In the microcell assembly shown, each microcell bundle is attached to a correspondingly sized hole in tube sheet 536 and the microcell bundle is tightly sealed with an O-ring sealant to prevent leakage at such holes. ing. As another method, the end heat transfer tubes 538 of the microcell bundle 532 are attached, and the tube sheet 536 is formed.
[0132]
FIG. 35 is a cross-sectional elevation view of the fuel cell module showing the air / fuel path and the heat transfer path.
[0133]
The fuel cell module 540 includes a container 541 to which a microcell assembly 550 is attached by bonding materials 552 and 554. The binder is meshed with the O-ring sealant 556 and 558 to seal around the inner wall of the container. In this way, an interior volume 560 is created in the container secured by the binders 552 and 554. A gas outlet 586 is attached to the main center of the vessel and connects the gas flow to the shell side of the microcell element of the assembly 550.
[0134]
The fuel cell module of FIG. 35 is fitted so as to be tightly sealed with the inner wall of the container 541 and the O-ring sealing agent 578, and the tube sheet 562 and the inner wall of the container and the O-ring sealing agent 580, respectively. Tube sheet 578.
[0135]
In such an arrangement, an intermediate volume 576 is between the tie 552 and the tubesheet 578, at the end of the container, on the left side of the figure where the terminal volume is shown.
[0136]
Correspondingly, an intermediate volume 568 is formed between the bonding material 554 and the tube sheet 562, and in FIG. 35 the terminal volume is also shown in the right end portion of the container.
[0137]
The coolant inlet 582 is at the right end of the fuel cell module container, and the coolant inlet 590 is at the left end element of the container.
[0138]
A fuel inlet 584 connects to the intermediate volume 568 of the module, and a used fuel outlet 588 connects to the intermediate volume 576 at the opposite end of the module.
[0139]
Distributed in the cross-section of the microcell assembly 550 (across the vertical axis) are a plurality of hollow fiber heat transfer paths 604, which extend the full length of the microcell assembly and intermediate volume, and include tube sheets 562 and Extending beyond 578 to terminal volumes 566 and 565, respectively.
[0140]
A central conduit 592 enters the container from the right and extends to the center of the microcell assembly 550. Within the microcell assembly, there is a perforation in the feed line, which provides fuel to the shell side of the fibrous microcell element of the microcell assembly.
[0141]
The current collectors of the intermediate volumes 568 and 576 fit into terminals 600 and 602, respectively, which extend out of the container 541.
[0142]
Container 541 is connected to flange 570 and is secured by a suitable mechanical clasp. Here, the right center volume and the terminal volume of the container are removable and are connected to the interior of the fuel cell module.
[0143]
In operation, coolant flows to terminal volume 566 (from an external source not shown in FIG. 35), flows through open-ended heat transfer tubes 604, flows axially through the tubes to the opposite terminal volume 565. From which coolant is discharged through outlet 590. Also, the coolant may be recirculated to the inlet 582 for heat recovery, for example, as a continuous loop. At the same time, feeds (oxidant and fuel) are introduced into the shell side and the hole side of the microcell element of the microcell assembly 550, respectively, and power is generated by an electrochemical reaction, which causes an external load via terminals 600 and 602, respectively. It is transmitted to. For such purposes, the terminals are coupled to appropriate circuitry and external load components.
[0144]
FIG. 36 is a cross-sectional view of a microcell bundle 610 incorporating hollow fibers 614 interspersed with fibrous microcell elements 612. In such a bundle, the hollow fiber functions as an external electrode, and also allows heat exchange. Thus, during operation of the microcell assembly, in addition to passing through the bore of the lumen, for example, through a flow of heat transfer material, such as air, to remove heat generated by accidental electrochemical reactions from the bundle, Hollow fibers can be coated, impregnated and extruded with an electrocatalytic material, or otherwise configured as an electrode element and used functionally.
[0145]
FIG. 37 is a side view from a cross section of a fuel cell module using a hollow fiber heat transfer element.
[0146]
The fuel cell module 620 of FIG. 37 is constituted by a container 625, and is flanged with a flange structure 624. This separates the right part of the container and separates it from the main central part, leading to the internal structure of the module. The container 625 includes a bundle of microcells 626 joined by binders 628 and 630, the inner wall surface of the container 625 is tightly sealed so as not to leak with O-ring sealants 632 and 634, and the inner wall and the respective It defines an internal volume 636 in the container, separated by binders 628 and 630.
[0147]
In the axial direction of the bonding material 630 is a tube sheet 640, which defines an internal volume 660, and seals the inner wall of the container with an O-ring element 642.
[0148]
The heat transfer tubes that make up the current collector terminate in a tube sheet 628, which connects to the terminal volume 662 of the container 622.
[0149]
Outside the tubesheet 640 in the container is a terminal volume 658. The central conduit 641 is longer than the end wall 622 of the container and extends to the center of the microcell assembly 626. Such a central conduit is perforated in the microcell assembly and supplies fuel to the shell side of the assembly.
[0150]
The right part of the container is removable by a flange 624 and connects to the interior of the module. [0151]
Intermediate volume 660 has an inlet 646 for introducing fuel and flowing fuel to volume 662 via assembly 626. The volume 662 has an outlet 648 for discharging spent fuel. The intermediate volume 636 of the container has an outlet 538 for discharging spent fuel on the shell side.
[0152]
The end volume 658 of the module has an inlet 644 for introducing cooling water and flowing the cooling water to hollow fiber elements extending into this volume. Cooling water flowing axially through the hollow fiber element flows to the opposite end volume 662.
[0153]
The hollow fiber heat transfer path of this embodiment is formed by hollow fiber electrodes, and as shown, such electrodes are conjugated to the corresponding terminals 652 and 656, respectively, at the terminal volume.
[0154]
FIG. 38 is a cross-sectional elevation view of a fuel cell module that performs heat exchange from a current collector by heat conduction. The module 700 includes a container 702 containing a microcell assembly 704, to which a bonding material 706 sealed with an O-ring sealing material 710 and a bonding material 708 sealed with an O-ring sealing material 712 are attached. I have. As a result, the range of the internal volume 720 is defined, and the internal volume 720 is connected to the outlet 740 for discharging the used fuel.
[0155]
A central conduit 714 extends into the center of the microcell assembly 704 and is vertically drilled in the microcell assembly to supply fuel to the shell side of the assembly.
[0156]
The terminal volume 724 of the container 702 has an inlet 742 for introducing fuel and flowing fuel through a hole in the microcell assembly 704 to the terminal volume 722, from which the outlet 732 is used. Drain fuel.
[0157]
In this module, a heat exchanger 746 is included in the terminal volume 724 and contacts the current collector element of the microcell assembly to effect heat exchange. Heat exchange liquid (from a source not shown in FIG. 38) is introduced into a heat exchanger or inlet 748 and circulated and discharged from outlet 750.
[0158]
In a similar manner, the opposite end volume 722 has an inlet 728 for receiving and flowing the heat exchanger 780 and the heat exchange fluid, and an outlet 730 for discharging the heat exchange fluid from the second heat exchanger 780. included.
[0159]
Each terminal current collector is in conductive connection with terminals 738 and 736. The left portion of the container 702 is flanged with a flange 726 to allow easy opening of the container and access to the interior of the container.
[0160]
FIG. 39 is a circuit diagram of a fuel cell system as one embodiment of the present invention. The fuel cell system 780 includes a microcell module 782, which includes a coolant inlet 810, a coolant outlet 792, a fuel inlet 794, an oxidizer inlet 799, and a used fuel outlet 786. And a container 784 connected to the outlet 804 of the used oxidant. The fuel inlet 786 is connected to an exhaust line connected to the back pressure adjusting valve 788. In a similar manner, the outlet 804 of the used oxidant is coupled to an outlet line 806 that connects to a back pressure regulating valve 808. The respective back pressure regulating valves 788 and 808 can be adjusted to control the rate and extent of the electrochemical reaction involving the fuel and oxidants.
[0161]
The system includes a fuel supply tank 798 coupled to a fuel supply line 796 leading to a fuel injection pipe 794. Similarly, an oxidizer supply line 800 is coupled to the oxidizer tank 802 and is conjugated to an oxidizer inlet 799.
[0162]
In this system, a coolant circulation arrangement is provided, including a recirculation line 816 coupled to a coolant outlet 792, where a pump 818 and a heat exchanger 820 are located. The heat exchanger 820 removes heat from the warmed coolant and recycles this fluid to the surge tank 814 and returns it from the supply line 812 to the coolant inlet 810.
[0163]
As a result, when the system shown in FIG. 39 is operated, the coolant flows through the hollow fiber heat transfer tube of the container, continuously recirculates to the surge tank, and the surge tank causes the coolant to stagnate at a high rate. Perform electrochemical oxidation.
[0164]
Double membrane microcell structure and assembly
In particular applications of the invention, microcell structures are usually utilized in a double membrane configuration.
[0165]
In one embodiment, a microcell structure of this type is easily formed by hollow fiber internal separators, with the inner current collector and the internal electrode electrocatalyst attached to the shell side. Such hollow fiber inner separators are surrounded by hollow fiber outer separators. The pores of the outer hollow fiber membrane are eroded by the electrolyte, and the outer hollow fiber membrane shell side is coated with the electrocatalyst of the outer electrode to form a double membrane microcell structure.
[0166]
The dual membrane microcell structure is advantageous because the hollow fiber internal separator can be used as a membrane to selectively permeate fuel (such as hydrogen or oxygen), if desired. This can be achieved, for example, by coating the inner wall of the inner separator or the outer shell with a permselective material that preferentially allows the desired gas to penetrate the electrodes. Thus, this dual membrane design is advantageous in reducing or eliminating the contact of the electrocatalyst or electrolyte with potentially harmful impurities in the fuel. Materials that can be used for the permselective membrane include cellulose ether, polyimide, polysulfone, and palladium.
[0167]
In another microcell structure including a bilayer separator, the inner wall of the inner separator is CO-H₂It may be immersed in, or coated with, a reforming catalyst that performs O conversion at a low temperature. In such a design, the shell side of the internal separator is coated with a material that allows the choice of anode or cathode fuel.
[0168]
In another dual membrane design, the anode or cathode is coated with a material that can select hydrogen or oxygen. In such a case, it is necessary to make the permselective material for protection conductive on the shell side of the outer hollow fiber membrane so that the current collector of the external electrode and the electrocatalyst on the shell side can make electrical contact. A permselective material such as palladium may be used for such a purpose. Alternatively, if desired, a conductive permselective material can be used for either one of the cathode or anode components.
[0169]
Yet another design utilizing double membrane processing utilizes a conductive hollow fiber internal separator. Such conductive hollow fiber separators can be made of sintered metal, carbon, or graphite. In some embodiments of such a dual membrane design, depending on the conductivity of the inner hollow fiber, an inner current collector is not required.
[0170]
The inner and outer hollow fiber membranes can be any suitable commercially available membranes, for example, polypropylene, polysulfone, polyacrylamide, and the like. In one embodiment, the membrane is selectively permeable, such as allowing the feed gas (fuel, oxidant) to selectively pass without passing through other gases and components (such as fuel impurities) that may be present. Process to have. By a specific example method, a protective hydrogen permeable barrier layer is deposited by depositing a solution, coating with an electrolyte, etc. to form a palladium film on the membrane surface that allows hydrogen to pass but nitrogen or oxygen is closed. Can be done. See, for example, Gryaznov et al. , "Selectivity in Catalysis by Hydrogen-Porous Membranes", Discussions of the Faraday Society No. 72 (1982), pp. 147-64. 73-78, Gryaznov, "Hydrogen Permeable Palladium Membrane Catalysts", Platinum Metals Review, 1986 30 (2), pp. 146-64. 68-72, and Armor, "Catalysis with Permselective Inorganic Membrane", Applied Catalysis, 49 (1989), pp. 90-80. Please refer to 1-25.
[0171]
FIG. 40 is a cross-sectional view of a micro-cell 900 having a double-membrane design using a conductive permselective membrane for the anode or the cathode of the micro-cell. Microcell 900 comprises an outer electrocatalyst layer 912, a microporous membrane / electrolyte 910, an electrocatalyst 908, an inner hydrogen or oxygen selective membrane 906, a current collector or electrode element 902 in an inner hole 904. I have.
[0172]
FIG. 41 is a cross-sectional view of a microcell 914 having a double isolation design using a permselective membrane for protecting the anode or the cathode of the microcell. The microcell 914 includes an outer electrocatalyst layer 930, a microporous membrane / electrolyte 928, an electrocatalyst 926, a current collector or electrode element 922, a porous inner separator 920, an inner hydrogen or oxygen selective membrane 918, It is constituted by an inner hole 916.
[0173]
FIG. 42 is a cross-sectional view of a microcell 932 in a dual isolation design using a permselective membrane covering the anode and cathode elements of the microcell. The microcell 932 includes an outer hydrogen or oxygen selective conductive membrane 948, an electrocatalyst layer 946, a microporous membrane / electrolyte 944, an electrocatalyst 942, a current collector or electrode element 940, and a porous inner separator 938. , An inner hydrogen or oxygen selective film 936, and an inner hole 934.
[0174]
FIG. 43 is a cross-sectional view of a microcell 950 with a dual isolation design using a permselective membrane covering both the anode and cathode of the microcell and a conductive internal separator. Microcell 950 includes an outer hydrogen or oxygen selective conductive membrane 966, an electrocatalyst layer 964, a microporous membrane / electrolyte 962, an electrocatalyst 960, a conductive, porous current collector or electrode element 958, an inner Of hydrogen or oxygen selective membrane 956 and inner hole 952.
[0175]
FIG. 44 is a cross-sectional view of a microcell 970 having a double isolation design using a permselective membrane covering both the anode and the cathode of the microcell and a reforming catalyst on the inner wall of the internal separator. Microcell 970 comprises an outer electrocatalyst layer 986, a microporous membrane / electrolyte 984, an electrocatalyst 982, a current collector or electrode element 980, an internal hydrogen or oxygen selective membrane 978, a porous internal separator 976, It comprises a CO-water conversion / reforming catalyst 97 and an inner hole 972.
[0176]
Manufacture of microcell structures and assemblies containing them
For commercial mass production, it is desirable to be able to produce a microcell device containing most of its components in a single extrusion step at a high rate. An important aspect of this mass processing process is to surround the internal electrodes with microporous membrane separators.
[0177]
For this purpose, a conductive fiber chain can be passed through the center of the tube at the tip of the extrusion (spinneret). The material that forms the skeleton of the microporous membrane separator, called the "dope," is continuously extruded around the tube at the tip of the hole, forming conductive fiber chains. An internal flocculant, such as a gas such as nitrogen or a liquid such as water, passes through the bore tube along the internal electrode fibers or fibrous current collector.
[0178]
In the operation described above, the size of the microcell fibers is determined by the size of the extrusion opening. Such openings may be of various sizes, for example from a scale of less than 100 microns, and the membrane may be correspondingly thin, a few microns thick.
[0179]
When the ink paste is used in the microcell processing method, the electrocatalyst paste is simultaneously extruded from the holes. The extruded fibers are immersed in an external flocculant such as a quench bath or water. When the extruded fibers undergo an agglomeration / quenching operation, a microstructured membrane structure is immediately formed around the internal electrode when the water-soluble compound at the pore reaches the aggregating / deactivating agent.
[0180]
By selecting parameters such as membrane dope formation, the type of flocculant used, and the temperature of the spinning operation, and controlling them accordingly, the pore structure, porosity, and pore size of the membrane separator can be accurately determined. Can control. Specific conditions can be easily determined by such a process with simple experimentation without undue effort, thanks to the advanced methods of the present technology.
[0181]
A variety of materials are useful and unlimited for forming microporous membrane separators, such as polysulfone, polyacrylamide, other high temperature polymers, glass, and ceramic materials.
[0182]
By the spinning process described above, the microcell can be continuously processed at a high rate.
[0183]
In the case of a polymer electrolyte fuel cell or an electrocatalyst for an external electrode, for example, after forming a microporous membrane separator-encapsulated internal electrode structure, the encapsulated structure is ion-exchanged on the outside (shell side) with an ion exchange polymer. Coat or impregnate. A similar extrusion process can advantageously provide such an outer coating.
[0184]
FIG. 45 is a schematic process diagram of a solution impregnation system 988 for immersing the membrane fibers 992 with Nafion or an electrocatalyst. The membrane fibers 992 exit the fiber spool 990 and, by the action of the rollers 994, pass through a solution bath 996 where the fibers are impregnated. The impregnated fibers then pass over guide rolls 998, through rows of heating elements 999, and finally to take-up winder 1000.
[0185]
A further application of the electrochemical cell of the invention is for the production of chemical substances. The present invention can be advantageously applied to chemical synthesis using a microcell processed according to the present invention. This microcell has a high current density per unit volume required for a chemical reaction, a distance of an electrode film (thickness). ) Minimizes internal resistance, and provides high efficiency due to low mass transfer resistance.
[0186]
Further, hydrogen and oxygen can be generated in a place where other forms of electric power can be used by using the microcell processed according to the present invention. In such an application field, hydrogen (or other fuel gas) generated in the cell can be stored and used for power generation.
[0187]
For example, after a polymer porous film is formed around a current collector in a microcell fiber structure, this structure is directly applied to an electrolyte solution of a water-soluble polymer such as a Nafion solution (a 5% solid solution or an alcohol solution). And the polymer electrolyte can be immersed in the pores of the porous polymer membrane. Depending on the time during which the porous polymer membrane is immersed in the composition of the electrolyte impregnating agent during the process, and the number of times of contacting the repetitive structure with this composition (ie, once or twice) The amount of impregnated polymer electrolyte can be variously selected.
[0188]
In the same process line where the electrolyte was soaked, or alternatively in a subsequent processing operation, in one process embodiment, the microcell fibers are dried and H₂[PtCl₆] To the platinum as an electrocatalyst material. Thereafter, sodium borohydride (NaBH)₄) To reduce the platinum composition to elemental metallic platinum.
[0189]
Using this continuous technique in accordance with one embodiment of the present invention, only the shell exterior of the membrane is impregnated with platinum. After attaching the fiber to the container by pumping the platinum plating solution out of the hole in the fiber, the inner wall of the membrane is impregnated.
[0190]
In another embodiment, both the shell side and the pore side of the fiber are impregnated after the fiber is installed.
[0191]
After impregnating the pores of the membrane with Nafion's electrolyte solution for ion exchange, according to another aspect of the invention, the electrocatalyst is coated with airfoil platinum loaded with activated carbon of a suitable particle size. Activated carbon particles loaded with platinum are usually in the range of 5-10% by weight. In principle, the composition of the paste is prepared as an emulsion of activated carbon particles on which platinum is applied, Nafion ionomer as binder and polytetrafluoroethylene which is Teflon®. The shell side of the fiber is then coated with a paste or alternatively extruded.
[0192]
The paste can be coated on the inside of the fiber wall in various ways. In one approach, the paste is extruded simultaneously while rotating the porous membrane separator element around the current collector. The second approach involves extruding the paste around the current collector before inserting the current collector into the membrane fibers. As a third approach, once the cell assembly has been formed and mounted, a thin paste can be pumped into the pores of the porous membrane separator.
[0193]
In another embodiment, the electrolyte is placed inside a porous membrane separator element and the catalyst is applied by electrodeposition from a solution containing platinum ions, an electroplating solution process, or an electroless plating solution process.
[0194]
Corrosion control of microcell assembly
In the field of application of conventional fuel cell technology, the materials used as current collectors are usually limited to the type of graphite. Current collectors made of aluminum or titanium can be coated with a corrosion-resistant coating such as gold, but under excessive corrosive conditions and thermal cycling that are characteristic of fuel cell operation, such coatings can It tends to peel off or delaminate from the current collector element.
[0195]
By using the microcell element, a material of the current collector other than the graphite material can be used as a component. The metal fibers used in the microcell structure of the electrochemical cell module can achieve durable corrosion resistance by being coated by various techniques. Useful coating techniques for such purposes include, but are not limited to, electrochemical deposition, electroless coating, dip coating, extrusion, etc. using a corrosion resistant metal composition or a polymeric material such as polyanaline.
[0196]
A preferred approach for metallic materials for coatings used in current collectors includes using amorphous metal compositions deposited by plasma coating techniques. In general, the corrosion resistance is better when the composition of the coating agent is amorphous. In addition, various amorphous metal compositions result in very large surface areas. An example of such a metal composition having a large surface area is a nickel-hydrogen electrocatalyst material. The use of such a high surface area metal composition essentially leads to an increase in the surface area of the fibrous microcells, and such an amorphous metal coating is effective for hydrogen storage in fuel cells. Can have significant structural and operational advantages.
[0197]
Another approach to improving the corrosion resistance of metal fiber materials is to coat the metal fibers with a polymerization precursor or other organic coating and carbonize the coating. The carbonization of the polymer that forms the graphite material on the metal fibers results in a coating that is corrosion resistant but has higher conductivity than carbon or graphite alone.
[0198]
If pinholes are present in the coating process, they can corrode or break the connection from one part of the microcell to another, which reduces the useful power density of the cell. Another approach is to use a manufacturing method that places the carbon fibers together on the pore or shell side of the microcell so that the carbon fibers are in intimate contact with the current collector of the microcell. Avoid. In such an arrangement, if the current collector erodes during operation of the electrochemical cell, the carbon or graphite fibers maintain the flow of current therethrough, resulting in considerable corrosion. If the current collector element breaks or deteriorates, the electricity will not be interrupted.
[0199]
It is advantageous to coat the metal fibers with a compound, such as a polymer material, in order to increase the service life of the metal current collector fibers under conditions in which the fuel cell has corroded, after which the coated fiber polymer material is heated. Becomes susceptible to decomposition. Utilizing a conventionally used technique of forming carbon fiber itself, the fiber-coated material is pyrolyzed and converted to carbon.
[0200]
The formation of a continuous layer of metallic current collector fibers (regardless of size) results in the formation of radially and longitudinally conducting fibers, while the surface protects the underlying metal from corrosion and is therefore corrosion resistant.
[0201]
FIG. 46 is an elevational view of a conductor element 1002 that includes a metal fiber 1004 having an outer surface coated with a polymeric compound 1006. The fibers are coated by any suitable method, such as, for example, thermal spraying, dip coating, roller coating.
[0202]
FIG. 47 shows the corresponding fiber 1002 after pyrolysis of FIG. Its outer surface is composed of a pyrolytic carbon coating 1008.
[0203]
Regarding the preparation of the current collectors and electrodes, in one embodiment of the present invention, the conductive metal fibers of the microcell are comprised of copper, aluminum, or titanium fibers and have a diameter of about 100 microns to about 10,000 microns. Range and coated with a corrosion-resistant metal of appropriate thickness, such as gold or platinum.
[0204]
Alternatively, carbon / graphite fibers having a good conductivity in the range of about 100 microns to about 10,000 microns in diameter can be utilized and cured with a metal catalyst such as platinum. Such hardening of platinum can be attributed to H₂[PtCl₆] To a plating solution containing sodium borohydride (NaBH₄) To reduce the platinum compound to the elemental metal platinum.
[0205]
With respect to current collectors, pinholes and coating defects accelerate corrosion of metal current collectors. To avoid cutting off the microcells' voltages and currents that could result in fibrous cells being cut or inoperable as a result of such corrosion (resulting in loss of conductor continuity). It is advantageous to place the fibrous carbon current collector beside the coated metal fibers. FIG. 48 shows a fibrous carbon current collector 1014 placed beside the coated metal fiber 1012. As shown in FIG. 48, the carbon fibers 1014 will be in intimate contact with the coated fibers 1012.
[0206]
FIG. 49 shows a fiber assembly obtained by cutting the coated metal fiber 1012 of FIG. If the continuity of the coated metal fiber is cut at one point due to corrosion, the carbon fiber 1014 in contact with the two parts of the corroded metal fiber 1012 maintains continuity and the depth of the carbon fiber / metal fiber arrangement Along, current can be passed from one to the other.
[0207]
Microcell assembly moisture management
In the electrochemical reaction of the microcell, where water is a by-product of the reaction, the fuel can be humidified to prevent the membrane from drying out, and the microcell assembly can be filled with excess water or excess water. It is desirable to include a water management system for removal.
[0208]
Generally, if the microcell structure has a large surface area and low mass transfer resistance, removing water from the microcell module is less of a problem than conventional planar fuel cell structures.
[0209]
Various alternatives may be utilized to further enhance the water management capabilities of the microcell fuel cell module. For example, if a heat transfer tube is used in a fuel cell assembly, and the assembly is made of a material such as a hollow fiber membrane coated with Nafion or another ion exchange polymer that can selectively permeate water, and When the heat exchange liquid is water, a heat transfer tube can be used to supply water to the fuel cell or remove heat from the fuel cell.
[0210]
One approach to removing heat from the fuel cell is to have a porous planar hollow fiber membrane to distribute the microcell bundle. In this structural arrangement, during operation of the fuel cell, water penetrates the walls of the membrane by wicking and is passed down through the holes of the hollow fiber and removed from the active surface. The resulting water can then be collected in a plenum in the container containing the module and drained from the system.
[0211]
The present invention considers various approaches to removing water from the fuel cell. In fuel cells made of fibrous cells or microcells, hollow fiber membranes treated with hydrophilic compounds can be intermittently packed between fibrous cells containing electrodes or current collectors to remove the generated water. . Since these hollow fiber membranes are in close contact with the shell side of the cell and the pore side is open, the water generated by the fuel cell is absorbed by the wick phenomenon and passes down the pores of the hollow fiber membrane to form the electrode. Is removed from the cell containing As a result, the cells can be prevented from overflowing with water.
[0212]
When the module is mounted vertically, water can also be collected by gravity at the bottom of the cell and drained from it.
[0213]
FIG. 50 shows a cross section of a bundle 1020 of hollow fibers and microcell tubes. Among them, flat hollow fiber elements 1026 are interspersed with microcell fiber elements 1022 and shell-side electrodes 1024. Utilizing such hollow fiber elements, water is passed from the assembly. FIG. 51 is a cross-sectional elevation view of a microcell fuel cell module 1030, such as a container 1032 that includes a vertically arranged microcell assembly 1036, as shown. The container 1032 has a flange 1034 that allows the top end of the container to be removed to access the internal components of the microcell assembly and other modules.
[0214]
The microcell assembly 1036 is attached at the upper end with a binder 1040 and is tightly sealed with an O-ring sealant 1042 to prevent leakage with the inner wall of the container. Similarly, the microcell assembly 1036 is attached at its lower end with a binder 1044 and is tightly sealed with an O-ring sealant 1046 to prevent leakage with the inner wall of the container.
[0215]
A central conduit 1080 is fitted into the microcell assembly 1036, which is perforated with the internal volume of the microcell assembly. In addition, a fuel inlet 1060 supplies fuel from the upper end volume 1048 to the pore side of the microcell element of the assembly. Fuel discharged at the lower end of the hollow fiber element enters the lower end volume 1050 and is discharged from the container at outlet 1072 or 1070.
[0216]
The outlet 1078 is in the inner volume 1038 of the container and discharges the used fuel in the inner volume (shell side).
[0217]
The lower end of the container 1032 is constituted by a plenum chamber 1076, which receives water (condensate) flowing to the lower portion of the container by gravity and discharges overflowing water from the outlet 1072 or 1070.
[0218]
As shown, at each end of the microcell assembly, a current collector element is coupled to a respective terminal 1082 and 1084.
[0219]
Accordingly, the hollow fiber tubular elements utilized in the microcell assembly allow the excess water to penetrate the passages in such hollow fiber holes and drain it into the plenum chamber, thereby removing the water from the electrochemical fuel cell module. , Can easily remove excess water.
[0220]
In addition, water can be transported from the microcell assembly using any suitable method, including flowing water from the microcell bundle to a collection tube or location, using surface tension or capillary effect elements and structures. including. As an example, on March 3, 1981, Leslie C. et al. Kun and Elias G .; The reinforced structure of the film compression apparatus described in U.S. Pat. No. 4,253,519 issued to Ragi effectively utilizes the overlay structure for microcell fibers or bundles of similar construction, and bundles of substructures. The liquid is collected by flowing, and is discharged from the fuel cell module.
[0221]
In each of the foregoing approaches, the electrolyte / catalyst-impregnated coated fibers can optionally be coated with an emulsion of Teflon® polytetrafluoroethylene to impart hydrophobicity to the membrane / electrode assembly. With such flexible measures, water introduced or formed in the cell is repelled from the catalyst surface, improving the effectiveness of the catalyst site for fuel or oxidizing agents (such as hydrogen and oxygen).
[0222]
Although the present invention has been described herein with reference to a particular embodiment, features, and aspects, the present invention is not limited to this, but is extended to, and adapted to, other modifications, variations, applications, and practical applications of the embodiment. It will be appreciated that all other modifications, variations, applications, and embodiments are considered to be within the spirit and scope of the invention.
[Brief description of the drawings]
FIG. 1 is a perspective view of a fiber element structure showing the assembly of a microcell assembly.
FIG. 2 is a perspective view of a fiber element structure showing the assembly of the microcell assembly.
FIG. 3 is a perspective view of the fiber element structure showing the assembly of the microcell assembly.
FIG. 4 is a perspective view of a fiber element structure showing the assembly of the microcell assembly.
FIG. 5 is a perspective view of a connector connecting the current collector or electrode elements of the microcell fiber assembly.
FIG. 6 is a microcell assembly according to one embodiment of the invention, terminated at one end of the assembly.
FIG. 7 shows a perspective view of the microcell assembly in an exploded view, showing the continuously connected microcell sheets.
FIG. 8 is a schematic view of a layered arrangement of continuously connected microcell sheets.
FIG. 9 is a three-dimensional perspective view of an array in which microcell layers are continuously connected.
FIG. 10 shows an arrangement with a microcell sheet attached.
FIG. 11 is a perspective view of a tube with a double stack of electrochemical cells with perforations on the top and optionally the bottom.
FIG. 12 is a cross-sectional elevation view of a microcell fiber bundle attached to a container.
FIG. 13 is a side view of the container of FIG.
FIG. 14 is a cross-sectional elevation view in a case where microcell sheets are stacked in two stages.
FIG. 15 is a side view of a two-tiered microcell device in which sheets are arranged to be stacked on each side of a perforated tube.
FIG. 16 is a perspective view of a fiber attached to one side of a perforated delivery tube.
FIG. 17 shows a container with fibers placed on both sides of a perforated tube.
FIG. 18 is a side view of an electrochemical cell device constituting a microcell assembly.
FIG. 19 shows a perforated tubing used as a rotating shaft to form a microcell structure.
FIG. 20 shows a sheet of fibrous microcells and current collectors on the shell side that can be rotated or wrapped around the perforated tube of FIG. 19;
FIG. 21 illustrates a state where the sheet in FIG. 20 is being rotated.
FIG. 22 shows a state in which the sheet of FIG. 20 has been rotated.
FIG. 23 shows a fibrous microcell part, a sheet of a current collector on the shell side, and an insulating sheet (such as fiberglass or a porous plastic material).
FIG. 24 is a perspective view of a sheet assembly including two sheets of a fibrous microcell portion and a shell-side current collector.
FIG. 25 is a side view of a microcell assembly using a filled fiber layered sheet.
FIG. 26 is a cross-sectional view of a bundle of micro cells.
FIG. 27 is a side view of a case where the bundles of the lower structure of the microcell are continuously connected as one embodiment of the present invention.
FIG. 28 is a perspective view of a connector used to continuously connect a bundle of substructures of a microcell as a component.
FIG. 29 is a cross-sectional elevation view of an assembly having a plurality of bundles, in which a feed tube corresponding to each bundle is placed.
FIG. 30 is a cross-sectional elevation view of an assembly having a plurality of bundles when the respective bundles are connected in series.
FIG. 31 is a cross-sectional view of a fuel cell module in which a plurality of bundles of a lower structure are inserted, in which an airtightly sealed element closes a topsheet of a portion surrounding the module.
FIG. 32 is a side view of a fuel cell module having a plurality of bundles of a lower structure made of microcells and having a feed pipe branched and arranged.
FIG. 33 is a side view from a cross-section showing an internal volume of a module container including a microcell bundle having a lower structure passed through a pipe as one embodiment of the present invention.
FIG. 34 is a cross-sectional view of a microcell assembly in which heat transfer fibers and heat transfer tubes are dispersed in a microcell bundle.
FIG. 35 is a cross-sectional elevation view of the fuel cell module showing the air / fuel and heat transfer paths scattered between the substructure bundles.
FIG. 36 is a cross-sectional view of a microcell bundle in which a hollow fiber functions as an external electrode element and can exchange heat.
FIG. 37 is a cross-sectional side view of a fuel cell having hollow fibers for heat exchange / current collector.
FIG. 38 is a cross-sectional elevation view of a fuel cell module performing heat exchange from a current collector by heat conduction.
FIG. 39 is a circuit diagram of a fuel cell system as one embodiment of the present invention.
FIG. 40 is a cross-sectional view of a double membrane design using a conductive permselective membrane for the anode or cathode of the microcell.
FIG. 41 is a cross-sectional view of a double isolation design using a permselective membrane to protect the anode or cathode of the microcell.
FIG. 42 is a cross-sectional view of a dual isolation design using a permselective membrane covering both the anode and cathode of the microcell.
FIG. 43 is a cross-sectional view of a double isolation design using a permselective membrane covering both the anode and cathode of the microcell, and a porous, conductive internal separator.
FIG. 44 is a cross-sectional view of a dual isolation design using a permselective membrane covering both the anode and cathode of the microcell, and a reforming catalyst on the inner wall of the internal separator.
FIG. 45 is a schematic process diagram of a solution impregnation system for immersing membrane fibers in Nafion or an electrocatalyst.
FIG. 46 is a front view of a metal fiber having a polymer compound on the outer surface.
FIG. 47 shows fibers coated with pyrolyzed carbon on the outer surface after the pyrolysis of FIG. 46.
FIG. 48 shows a fibrous carbon current collector beside a coated metal fiber.
FIG. 49 shows a fiber assembly cut from the coated metal fibers of FIG. 48.
FIG. 50 shows a cross section of a hollow fiber and a microcell tube bundle. Here, flat hollow fiber elements are used to carry water from the assembly.
FIG. 51 shows a vertical, upward expansion of a microcell bundle arranged so that water drained from the module flows to the lower plenum space for removal.

Claims (247)

A microcell assembly in which each microcell is composed of an internal electrode, a microporous membrane separator in contact with the internal electrode, an electrolyte contained in the pores of the microporous membrane separator, and an external electrode, which are arranged in parallel. A first cell comprising a sheet membrane of a first microcell, comprising a plurality of microcell fibers interconnected with a substantially planar configuration, and an axial direction from an initial end of the first sheet membrane. Contacting at least one microcell fiber of the first sheet with an inner current collector of the aforementioned microcell fibers protruding, and a second sheet that is an outer current collector overlaid on the first sheet; An assembly as described above, comprising each current collector protruding at a second end opposite the first sheet, for electrically isolating the first cell from further cells overlying the insulating sheet. The edge sheet also includes a first microcell sheet comprising a plurality of microcell fibers arranged in parallel and interconnected in a substantially planar configuration, and a second microcell sheet adjacent a second end of the first sheet. The inner current collector of microcell fibers described above projecting axially from one end of the sheet, and a second sheet of outer current collector overlying the first sheet, and at least one microcell fiber of the first sheet. A second cell comprising each current collector in contact and protruding on the opposite side of the first sheet, wherein the inner current collector of the first cell is aligned with the outer current collector of the second cell and electrically A microcell assembly that contacts and simultaneously forms a continuous connection. The microcell assembly of claim 1, wherein the collectors are interconnected by soldering, brazing, welding, conductive bonding, or fusion bonding. The microcell assembly according to claim 1, wherein the microcell assembly includes a plurality of cell structures including a plurality of the first and second cells alternately arranged, and adjacent cells are connected in a corresponding manner. The microcell assembly of claim 1, wherein successive cells are attached to opposite ends, sealing the shell side and the pore side of the microcell. A gas supply chamber comprising a porous planar element, and, as in claim 1, arranged in the porous planar element, each end of which is connected to the container such that the sealing surface is adjacent therearound. A microcell module comprising a microcell assembly, wherein the microcell module is mounted with a binder forming respective sealing surfaces forming a structural arrangement of the shell and the tube, and a perforated planar element is disposed in the middle of the binder. . 6. The microcell module according to claim 5, wherein said shell and tube structural arrangement is circumscribed by a circle. A sheet assembly comprising a first microcell sheet, comprising a plurality of microcell fibers arranged in parallel and interconnected in a substantially planar configuration; and projecting axially from a first end of the first sheet. An inner current collector of the microcell fibers described above, and an outer current collector of a second sheet overlaid on the first sheet; and at least one microcell fiber in contact with the opposite side of the first sheet; 2 is a bundle of substructures of microcells consisting of each current collector protruding at two ends; here, the sheet assembly is axially rotated into a cylindrical preform, with a porous surface on the outer cylindrical surface. The winding of the insulator forms a bundle of substructures, and joining at each end of the cylindrical preform results in the bundle of substructures described above; Bundle of substructures microcells sheet element forms a cell. 8. The bundle of substructures of microcells according to claim 7, further comprising a central tube having a hole in the middle of the entire length between the connection ends, and a non-perforated center tube outside the other connection ends. A sheet assembly as described above further comprising a porous insulating sheet overlying the second sheet, and a third plurality of microcell fibers arranged in parallel and interconnected in a substantially planar configuration. A sheet element, an inner current collector of the microcell fibers protruding axially from a first end of the third sheet, and an outer current collector of a fourth sheet fiber overlying the third sheet element; And a current collector in contact with at least one microcell fiber of the third sheet and projecting from the second sheet opposite the second end. Where generally the current collectors of the first and third sheet elements are coextensive in length at each end with respect to each other, and the current collectors of the second and fourth sheet elements are The current collectors of the above-mentioned second and third sheet elements are electrically connected at each end, and the above-mentioned third and fourth Bundle of substructures of microcells, wherein the sheet elements form a second cell. 8. The bundle of substructures of microcells according to claim 7, comprising a plurality of microcell fiber sheets forming a plurality of cells. 8. A bundle of microcell substructures according to claim 7, comprising a repeating arrangement of first and second sheet elements forming a diversity of cells; and wherein each cell is a porous insulating sheet. Bundle of substructures of microcells separated from adjacent cells by elements. An assembly having a bundle of at least two substructures and connected in series, as claimed in claim 7. 12. A microcell comprising a bundle of substructures of continuous microcells as claimed in claim 11, wherein the microcells are continuously connected in an anode to cathode arrangement and elongated. 14. A microcell as claimed in claim 13, wherein the connection comprises an integral hinge. 14. The microcell of claim 13, wherein the connection comprises soldering, brazing, welding, conductive bonding, or fusion bonding. 12. Microcells comprising a substructure bundle of continuous microcells and connected in an anode-to-cathode arrangement as claimed in claim 11, wherein the substructure bundles of components are connected to one another. Microcells that are arranged side by side next to each other and the axial dimension of the bundle is substantially equal to the axial dimension of each substructure of the bundle. 17. The microcell of claim 16, wherein the bundle is attached at each end. Microcells comprising a bundle of substructures of a plurality of microcells are arranged adjacent to each other, wherein the electrodes of the bundle of adjacent substructures are electrically connected from the anode to the cathode. Microcells that are linked and have microcells joined at each end. 19. The microcell of claim 18, wherein each substructure bundle is comprised of a central tube perforated outside its mid-length between the coupling ends, or otherwise intermediate the coupling ends. 20. The microcell of claim 19, further comprising a variety of fuel distribution systems coupled with and delivering fuel to the central tube of each of the plurality of substructures. The microcell of claim 11, wherein the coupling end defines each tube sheet, and the outer periphery of each wound sheet can be sealed. 22. A microcell module comprising a container to which a plurality of microcell substructure bundles are attached, as claimed in claim 21, wherein the containers correspond to the internal volumes each bundled at each end plate. A first end plate having an opening that can be hermetically fitted into the substructure bundle and the corresponding end plate opening of each end plate being coaxially aligned with each other; A second end volume bound by an end plate at one end of the container and arranged to carry fuel to the bundle of the substructure described above, bundled by an end plate at the other end of the container.送, having an outlet for discharging spent fuel from the interior volume, wherein the container is selectively open and the end plate is closed with at least one of the end volumes described above. Access and access to the bundle of substructures to which the above-mentioned endplates are connected, where the drainage takes place and an alternative bundle of substructures is attached; The micro cell module that connects the terminals firmly so that it does not leak out of the container. 23. The microcell of claim 22, further comprising a multiplicity of fuel distribution systems coupled to the conduit and coupled to a central tube of each of the plurality of substructures to deliver fuel. 23. The microcell module according to claim 22, wherein the conduit is longer than one end of the terminal volume and leads to a closed gas flow with the internal volume. Each end plate is attached, but the bundle of substructures is less than if they were completely complementary, and the openings in the end plates without the substructure bundles are now 23. The microcell module according to claim 22, wherein the corresponding opening of the microcell module is tightly sealed so as not to leak from the closed plate. A method of making an electrochemical cell device, comprising a first sheet of microcell elements arranged adjacent and in parallel with a first sheet, a layered structure of the sheet, and an external current collector of a second sheet Forming a second sheet spaced in parallel with the element, wherein the external current collector is longer than the edge of the first sheet, and the inner current collector of the fibrous microcell element is the second current collector; Pairing the first and second sheets in a longitudinally offset relationship to each other so as to be longer than the opposite end of the second sheet, the corresponding layers of the corresponding first and second sheets Was added to the first layers of the first and second sheets, and a porous insulating sheet was disposed between each layer to form a multi-layer structure. The above-described multi-layer structure was defined in advance. Molded into the shape of the lower structure layer, Combine them to form a permanent shape, in which case the localization of the inner and outer current collectors in the above-mentioned permanent shape is made, and a plurality of substructure bundles are processed in a corresponding manner Connecting the above-described substructure bundles to form a continuous arrangement of the substructure bundles; and forming the continuously connected substructure bundles to form a bundle-like assembly. How to become. A method of processing a microcell assembly, comprising: a first microcell sheet comprising a plurality of fibrous microcell elements arranged in parallel and interconnected in a substantially planar arrangement; A first layer including the internal current collector of the above-described fibrous microcell element protruding axially from a first end of the sheet element, and a second sheet element of an external current collector overlaid on the first sheet element Contacting each current collector with at least one microcell fiber of the first sheet, and disposing each current collector protruding at a second end opposite the first sheet; Disposing an insulating sheet in a layer, a first microcell sheet comprising a number of fibrous microcell elements arranged in parallel and interconnected in a substantially planar configuration; and a first sheet. Forming a second layer including the inner current collector of the above-described fibrous microcell element protruding axially from the first end, and the second sheet element of the outer current collector overlying the first sheet element; Placing each current collector in contact with at least one microcell fiber of the first sheet and opposite the first sheet and protruding beyond the second end; and an inner current collector and a second layer of the first layer. Electrically connecting the outer current collectors of the layers and additionally forming a continuous connection. 28. The method of claim 27, wherein the current collector is interconnected by soldering, brazing, welding, conductive bonding, or fusion bonding. 28. The method of claim 27, wherein said assembling an alternating first and second layer assembly is formed, and successive layers are alternately and successively electrically interconnected. 28. The method of claim 27, further comprising coupling the microcell assembly to seal the shell side and the pore side of the fibrous microcell element together. A method of processing a microcell module, comprising creating a gas supply chamber including a porous planar element, and defining a plurality of fibrous microcell elements and microcell diversity in a perforated plate element. When a microcell assembly consisting of an associated outer current collector is arranged, and the respective ends of the microcell assembly are joined by coupling elements forming each sealing surface, and the periphery of the sealing surface is placed adjacent to the container, A method comprising forming an arrangement of shell and tube structures on a sealing surface, wherein a perforated plate element is disposed intermediate the coupling surface. 32. The method of claim 31, wherein the microcell module of the container is circumscribed to form the shell and tube structure arrangement described above. A method for processing a bundle of substructures of microcells, comprising a first microcell sheet comprising a plurality of microcell fibers arranged in parallel and interconnected in a substantially planar configuration. An inner current collector of the microcell fibers protruding axially from a first end of the first sheet, and an outer current collector of a second sheet overlaid on the first sheet; Forming respective current collectors in contact with at least one microcell fiber of the sheet and protruding from a second end opposite to the first sheet; axially rotating the sheet assembly into a cylindrical preform; Wrapping a porous insulator over the outer cylindrical preform surface, and bonding at each end of the cylindrical preform to form the above-described substructure bundle. A method comprising, wherein the method of forming the cell by first and second sheet elements. 34. The method of claim 33, wherein the sheet assembly is pierced in the middle of the entire length between the coupling ends and wrapped around a central tube having no holes outside the coupling ends. A porous insulating sheet overlying the second sheet, and a third sheet element comprising a plurality of microcell fibers arranged in parallel and interconnected in a substantially planar configuration; An inner current collector of the microcell fiber protruding axially from the first end of the third sheet element of the above, and an outer current collector being a fourth sheet element overlying the third sheet element; Processing each current collector of a third sheet that contacts at least one microcell fiber of the sheet and protrudes at an opposite, second end of the fourth sheet, wherein generally the first and third sheets are processed. The current collectors of the elements are coextensive in length at each end with respect to each other, the current collectors of the second and fourth sheet elements are coextensive in length at each end with each other, and And a current collector of the third sheet element is electrically connected at each end to form a second cell in the third and fourth sheet elements described above, the method of claim 34, wherein. 35. The method of claim 34, wherein a plurality of microcellular fiber sheets forming a plurality of cells with a bundle of microcellular substructures are processed. 35. The method of claim 34, wherein the repeating arrangement of the first and second sheet elements forming the cell diversity is processed and a porous insulating sheet is disposed between successive cells. 35. The method of claim 34, wherein the two or more substructure bundles are electrically connected in series. 39. The method of claim 38, wherein said two or more substructure bundles are arranged in an anode-to-cathode manner and are connected and elongated. 39. The method of claim 38, wherein the step of serially connecting the two or more undercarriage bundles is performed by successively interconnecting the undercarriage bundles with an integral hinged connector. 39. The method of claim 38, wherein the step of serially connecting the two or more substructure bundles is performed by soldering, brazing, welding, conductive bonding, or fusion bonding. A method of manufacturing a microcell composed of a bundle of substructures of continuous microcells, wherein the substructure of a plurality of microcells having an anode and a cathode structure is processed, and the bundle of substructures described above is continuously processed. A plurality of bundles arranged side by side so as to be adjacent to each other, thereby forming a bundle of the substructure described above, and continuously and electrically interconnecting the bundles of the substructure. 43. The method of claim 42, further comprising attaching a bundle to each end. The microcell according to claim 1, wherein the membrane separator is made of a material selected from the group consisting of a semipermeable ion exchange membrane and a porous membrane coated on the shell side or pore side of the permselective polymer or the ion exchange polymer. assembly. The above-mentioned fibrous microcell element is composed of a porous membrane separator, and is selected from a group including a semipermeable ion exchange membrane, and a porous membrane coated with a permselective polymer or an ion exchange polymer on a shell side or a pore side. 28. The method according to claim 27, wherein the membrane separator is processed from the prepared material. At least one conductive fibrous element surrounded by a coated, impregnated and extruded porous membrane separator on the inner surface, the first electrocatalytic layer of which is a conductive hydrogen or oxygen selective permeable membrane An electrolyte disposed in a hole in a porous membrane separator, a structure having a central lumen therein and comprising at least one conductive fibrous element therein and an intermediate volume for flowing fuel into the lumen; And a fibrous microcell structure having a porous membrane as described above on the outer surface and in contact with the electrocatalyst and at least one conductive fiber. 47. The fibrous microcell structure according to claim 46, wherein the outer surface of the porous membrane separator is coated, impregnated, or extruded, onto which a second electrocatalytic layer has been extruded. 47. The fibrous microcell structure according to claim 46, wherein the electrocatalyst layer comprises an electrocatalyst and at least one combination of a conductive material and a hydrophobic material. 47. The fibrous microcell structure of claim 46, wherein the outer diameter is between about 100 microns and about 10 millimeters. 47. The fibrous microcell structure of claim 46, wherein the permselective membrane is applied to the porous membrane separator by a method selected from the group of electroless plating, electrochemical deposition, extrusion, deposition, solution deposition, and the like. 47. The fibrous microcell structure according to claim 46, wherein the permselective membrane comprises a material selected from the group of metals and conductive polymeric materials. 47. The fibrous microcell structure according to claim 46, wherein the permselective membrane comprises palladium. 47. The fibrous microcell structure according to claim 46, wherein the hydrophobic material comprises a fluoropolymer. 54. The fibrous microcell structure according to claim 53, wherein the hydrophobic material comprises polytetrafluoroethylene. An inner porous membrane separator is fixed in the central lumen, the inner surface is coated, impregnated and extruded, with a hydrogen or oxygen permselective membrane on the surface, the first electrocatalyst material and the outer surface The contacted at least one conductive fiber forms an internal structure, the internal structure is surrounded by an outer porous membrane separator, and at least contacts the second electrocatalyst material and an outer surface of the outer porous membrane separator. A fibrous microcell structure having one conductive fiber and electrolyte disposed in the pores of the outer porous membrane separator. 56. The fibrous microcell structure according to claim 55, wherein the hydrogen or oxygen selective permeable membrane is formed of a material selected from the group consisting of cellulose ester, polyimide, polysulfone, and palladium. 56. The fibrous microcell structure of claim 55, wherein the first electrocatalytic material is coated, impregnated, and extruded on the outer surface of the inner porous membrane separator. 56. The fibrous microcell structure of claim 55, wherein the second electrocatalytic material is coated, impregnated, and extruded on the outer surface of the outer porous membrane separator. 56. The fibrous microcell structure according to claim 55, wherein at least one of the first and second electrocatalyst layers is composed of a combination of an electrocatalyst, a conductive material, and a hydrophobic material. 56. The fibrous microcell structure of claim 55, wherein the outer diameter is between about 100 microns and about 10 millimeters. 56. The fibrous microcell structure of claim 55, wherein the permselective membrane is applied to the internal porous membrane separator by a method selected from the group of electroless plating, electrochemical deposition, extrusion, deposition, solution deposition, and the like. . 56. The fibrous microcell structure according to claim 55, wherein the permselective membrane comprises a material selected from the group of metals and conductive polymeric materials. 56. The fibrous microcell structure according to claim 55, wherein the permselective membrane comprises palladium. The fibrous microcell structure according to claim 59, wherein the hydrophobic material comprises a fluoropolymer. 65. The fibrous microcell structure according to claim 64, wherein the hydrophobic material comprises polytetrafluoroethylene. 59. The fibrous microcell structure according to claim 58, wherein a conductive hydrogen or oxygen selective permeable membrane is placed on the second electrocatalyst material. 67. The fibrous microcell structure of claim 66, wherein the inner membrane separator is conductive. 68. The fibrous microcell structure of claim 67, wherein there is no current collector fiber. An inner porous membrane separator is fixed in the central lumen, coated, impregnated and extruded on the inner surface, on which a reforming catalyst is placed and which has a permselective membrane for hydrogen or oxygen on its outer surface. The first electrocatalyst material and at least one conductive fiber in contact with the outer surface form an inner structure, the inner structure is surrounded by an outer porous membrane separator, and the second electrocatalyst material and the outer porous A fibrous microcell structure having at least one conductive fiber in contact with the outer surface of the permeable membrane separator and having electrolyte disposed in pores of the outer porous membrane separator. 70. The fibrous microcell structure according to claim 69, wherein the reforming catalyst comprises a metal oxide. 70. The fibrous microcell structure according to claim 69, wherein the reforming catalyst comprises a metal oxide selected from the group of copper oxide, zinc oxide, mixtures thereof, and the like. Reforming catalyst having a catalytic effect of changing the CO to CO _2, fibrous microcell structure according to claim 69. 70. The fibrous microcell structure according to claim 69, wherein the porous membrane separator is formed from a material selected from the group consisting of glass, ceramic, polymer material, and the like. 49. An electrochemical device comprising at least one fibrous microcell structure as described in claim 46. 56. An electrochemical device comprising at least one fibrous microcell structure as described in claim 55. 57. An electrochemical device comprising at least one fibrous microcell structure as described in claim 56. 58. An electrochemical device comprising at least one fibrous microcell structure as defined in claim 57. A method of making a fibrous microcell structure, comprising surrounding at least one conductive fibrous element with a porous membrane separator, and coating a first electrocatalytic layer with an inner surface of the porous membrane separator. Impregnating and extruding; forming a selectively permeable membrane of conductive hydrogen and oxygen in the first electrocatalyst layer; and disposing an electrolyte in the pores of the porous membrane separator. Wherein said structure includes a central lumen, at least one of said conductive fiber elements therein, and an internal volume through which fuel can flow through the lumen, Disposing an electrocatalyst and at least one conductive fiber on an outer surface of a permeable membrane separator. 79. The method of claim 78, wherein the outer surface of the porous membrane separator is coated, impregnated and extruded with a second electrocatalytic layer. 79. The method of claim 78, wherein the electrocatalyst layer comprises an electrocatalyst and a combination of at least one conductive material and a hydrophobic material. 79. The method of claim 78, wherein the outer diameter of the fibrous microcell structure is from about 100 microns to about 10 millimeters. 79. The method of claim 78, wherein the permselective membrane is applied to the porous membrane separator by a method selected from the group of electroless plating, electrochemical deposition, extrusion, deposition, solution deposition, and the like. 79. The method of claim 78, wherein the permselective membrane comprises a material selected from the group such as metals and conductive polymeric materials. 88. The method of claim 87, wherein the permselective membrane comprises palladium. 81. The method of claim 80, wherein the hydrophobic material comprises a fluoropolymer. 81. The method of claim 80, wherein the hydrophobic material comprises polytetrafluoroethylene. The inner porous membrane separator is fixed in the central lumen and its inner surface is coated, impregnated and extruded, making this surface a permselective membrane for hydrogen or oxygen, contacting the first electrocatalyst material and the outer surface The at least one conductive fiber is disposed to form an internal structure, the internal structure is surrounded by an external porous membrane separator, and the second electrocatalyst material and the outer surface of the outer porous membrane separator are A method of forming a fibrous microcell structure by placing at least one conductive fiber in contact and placing an electrolyte in pores of a porous membrane separator. 88. The method according to claim 87, wherein the hydrogen or oxygen selective permeable membrane is formed of a material selected from the group consisting of cellulose ester, polyimide, polysulfone, and palladium. 91. The method of claim 87, wherein the outer surface of the inner porous membrane separator is coated, impregnated, and extruded with the initial electrocatalytic material. 90. The method of claim 87, wherein the outer surface of the outer porous membrane separator is coated, impregnated, and extruded with a second electrocatalytic material. 88. The method of claim 87, wherein at least one of the first and second electrocatalyst layers comprises an electrocatalyst in combination with at least one of a conductive material and a hydrophobic material. 88. The method of claim 87, wherein the outer diameter of the fibrous microcell structure ranges from about 100 microns to about 10 millimeters. 88. The method of claim 87, wherein the permselective membrane is applied to the inner porous membrane separator by a method selected from the group of electroless plating, electrochemical vapor deposition, extrusion, vapor deposition, solution deposition, and the like. 90. The method of claim 87, wherein the permselective membrane is comprised of a material selected from the group such as metals and conductive polymeric materials. 88. The method of claim 87, wherein the permselective membrane comprises palladium. The method of claim 91, wherein the hydrophobic material comprises a fluoropolymer. The method of claim 91, wherein the hydrophobic material comprises polytetrafluoroethylene. 91. The method of claim 90, wherein the second electrocatalyst material is provided with a conductive hydrogen or oxygen selective permeable membrane. 100. The method of claim 98, wherein the inner membrane separator is conductive. 100. The method of claim 99, wherein no current collector fibers are used. A method for making a fibrous microcell structure, in which an inner porous membrane separator is fixed to a central lumen, coated, impregnated, and extruded on the inner surface, a reforming catalyst is placed on this surface, and the Forming a permselective membrane of hydrogen or oxygen on the outer surface, and arranging the first electrocatalyst material and at least one conductive fiber in contact with the outer surface to form an inner structure; Enclosing, arranging at least one conductive fiber in contact with the second electrocatalyst material and the outer surface of the outer porous membrane separator, and disposing an electrolyte in the pores of the outer porous membrane separator A method comprising: 102. The method of claim 101, wherein the reforming catalyst comprises a metal oxide. 102. The method of claim 101, wherein the reforming catalyst comprises a metal oxide selected from the group of copper oxide, zinc oxide, mixtures thereof, and the like. Reforming catalyst is to have a catalytic effect of changing the CO to CO _2, claim 101 method described. 102. The method of claim 101, wherein the porous membrane separator is formed from a material selected from the group consisting of glass, ceramic, polymer material, and the like. A supply of microcell precursors containing at least one current collector in a porous membrane separator disposed in contact with a liquid positioned to receive the microcell precursor from the supply described above. A unit in which the microcell precursors distributed therein are in contact with at least one of an electrolyte, an electrocatalyst, a reducing agent of the electrocatalyst, a hydrophobic material, and optionally a microcell precursor from a unit in contact with a liquid. A processing system comprising a drying unit arranged to receive the substance, drying the precursor of the microcell, and a collection method of collecting the precursor after contacting with a liquid and optionally drying. 107. The processing system of claim 106, wherein the unit in contact with the liquid comprises a liquid tank for contacting the precursor with the ion exchange polymer solution. 107. The processing system of claim 106, wherein the unit in contact with the liquid comprises a liquid tank for contacting the precursor with the electrocatalyst solution. 107. The processing system of claim 106, wherein the unit in contact with the liquid comprises a liquid tank for contacting the precursor with a reducing agent solution of the electrocatalyst. 107. The processing system of claim 106, wherein the unit in contact with the liquid comprises a liquid tank for contacting the precursor with a solution of the electrocatalyst platinate. 107. The processing system of claim 106, wherein the unit in contact with the liquid comprises a liquid tank for contacting a precursor and a reducing agent of an electrocatalyst comprising sodium borohydride. 107. The processing system of claim 106, wherein the unit in contact with the liquid comprises a liquid tank for contacting the precursor with a hydrophobic material comprising a PTFE emulsion. 107. The processing system according to claim 106, wherein the unit in contact with the liquid comprises a liquid tank for bringing the precursor into contact with an ink solution comprising a carbon powder of an electrocatalyst, an ion exchange polymer, and a hydrophobic material. Placing the electrolyte in the pores of the microcell precursor, drying the precursor, applying the electrocatalyst material in a solution or ink slurry to the precursor, drying the precursor, converting the electrocatalyst material into a catalytically active form A method for producing a fibrous microcell comprising the step of reducing. 115. The method of claim 114, wherein the electrocatalytic material comprises an ink slurry, and the slurry is applied to the precursor by extrusion. 115. The method of claim 114, wherein the precursor of the microcell is formed by passing it through a chain of fibrous current collectors and through a tube that forms a hole that extrudes a hollow fiber with a gaseous or liquid flocculant. By using a current collector fiber or chain, applying a porous film forming material to the fiber or chain, processing the fiber or chain coated with the porous film forming material, and forming a hole therein, 115. The method of claim 114, forming a microcell precursor. 118. The method of claim 117, wherein the porous membrane-forming material is perforated suitable for an application selected from the group of ultrafiltration, microfiltration, reverse osmosis, and the like. 118. The method of claim 117, wherein the porous film-forming material is formed from a material selected from the group consisting of a polymeric material, glass, ceramic, and combinations thereof. 118. The method of claim 117, wherein a method selected from the group of spinning and melt spinning is applied to the porous film forming material. 118. The method of claim 117, wherein the porous film-forming material is comprised of a dope that includes a skeletal component and a leachable component, which when peeled away by leaching results in cavities that become pores in the porous film. 118. The method of claim 117, wherein the porous film forming material comprises a dope, wherein a coagulant is applied to at least one of an inner surface and an outer surface of the dope used. 118. The method of claim 117, wherein the porous film forming material is applied by melt spinning, wherein the fibers or chains of the melt spun material are contacted with a quencher. 127. The method of claim 122, wherein the electrocatalytic ink paste is co-extruded with the flocculant on the inner surface. 118. The method of claim 117, further comprising the step of coating the porous membrane separator with either a permselective membrane material or an ion exchange polymer. Furthermore, the microcell module comprising a large number of precursors is processed, where the precursors are combined and sealed to form a structure composed of shells and tubes in which the precursors are arranged side by side. 118. The method according to claim 117, wherein an electrocatalyst solution, an electrocatalyst ink, or a reducing agent is flowed through at least one of the shell side and the tube side of the resulting configuration. Furthermore, the microcell module comprising a large number of precursors was processed, where the precursors were combined and sealed to form a shell-and-tube configuration in which the precursors were arranged in parallel with each other. 118. The method according to claim 117, wherein the electrocatalyst material is applied to one of the shell side and the tube side of the tube made structure. 130. The method of claim 127, wherein the electrocatalytic material is applied to the shell and tube arrangement by a method selected from the group of electroless plating, electrochemical deposition, extrusion, deposition, solution deposition, and the like. 118. The method of claim 117, wherein the membrane separator comprises a membrane selected from the group such as a semipermeable membrane and an ion exchange membrane. The electrochemical cell module is composed of various microcells of the assembly, each microcell constituting the internal electrode, the microporous membrane separator in contact with the internal electrode, the electrolyte in the pores of the microporous membrane separator, A microcell assembly comprising an external electrode and including a number of hollow tubular heat exchange elements arranged for flowing a coolant through a central lumen, wherein the hollow tubular heat exchange elements are distributed to said assembly; Removing the heat from the assembly during the electrochemical reaction during operation of the module; there is also a coolant source as described above, and the flow circuit interconnects the coolant and the source of the hollow tubular heat exchange element as described above. Electrochemical cell module. 130. The electrochemical cell module according to claim 130, wherein said coolant is a liquid coolant. 130. The electrochemical cell module according to claim 130, wherein said coolant is a gas. The flow circuit described above has various configurations at each opposite end of the microcell assembly described above, and the hollow tubular heat exchange element described above has been coupled at its opposite end to the corresponding configuration and the flow circuit described above. 130. The electrochemical device according to claim 130, wherein the coolant is flowed in conjunction with a pump to flow the coolant through the hollow tubular heat exchange element of the module to remove heat generated from the assembly by a microcell electrochemical reaction. Cell module. 130. The electrochemical cell module of claim 130, wherein the assembly is mounted to the container, aligned with the container axially, and flowing liquid from the first end with the first binder attached to the open end of the microcell fibers. One binder separates the shell side and the pore side of the microcell fiber, the current collector projects axially of the first binder, and the above-described tubular heat exchange element further separates from the first binder. And the first and second binders are connected to the closed volume of the container, the inlet of the container is connected to the closed volume, and the fuel is introduced into the closed volume. Flow through the assembly on the pore side of the cell fibers, where the second binder and the terminal volume closed by the container are defined, and the tubular heat exchange element extends along the second binder, End volume closed at open end of exchange element A coolant inlet leading to the closed end volume introduces coolant into the closed end volume and allows the coolant to flow axially along the tubular heat exchange element of the assembly; The two ends bind to the first opposite binder, from which liquid flows into the opening at the opposite end of the microcell fiber, where the first opposite binder separates the shell side and the pore side of the microcell fiber. The current collector projects axially with the first opposing binder and the tubular heat exchange element described above further couples to the opposite side of the second binder at a distance from the first opposing binder. , Between the first and second opposite binders is a closed opposing volume of the container, the outlet of the container leading to the closed container, from which spent fuel is discharged from the closed container, Two opposite binders and the opposite end volume at which the container is closed are defined. The tubular heat exchange element described above extends along the second binder and terminates in a closed end volume at the open end of the heat exchange element and communicates with the opposing end volume at the coolant outlet. Evacuating the coolant from the closed opposing end volume and removing heat from the electrochemical reaction from the assembly; also, the above-described current collectors at each end are connected to each other in series or in parallel and project out of the container. To form a tightly sealed terminal; furthermore, to allow fuel to flow, an electrochemical device having a tubing tightly connected to the shell side of the microcell in the above-described assembly in a leaktight manner. Cell module. 134. The electrochemical cell module according to claim 133, wherein the flues extend axially into the container and pass through the first and second binders. A current collector that protrudes axially from the first binder is either a hole-side or shell-side current collector, while a current collector that protrudes axially from the first opposite binder is a shell-side or hole-side current collector. 143. The electrochemical cell module of claim 133, wherein one of the current collectors is opposite a current collector that protrudes axially from the first binder. Each of the aforementioned opposing current collectors terminates at (a) a corresponding closed volume between the first and second binders and differs from the tubular heat exchange element described above, or (b) terminates at a terminal volume. 133. The electrochemical cell module of claim 133, wherein said tubular heat exchange element is a tubular heat exchange element, wherein each of said opposite current collectors is connected in series or in parallel with the other current collector end. An electrochemical cell module that forms a tightly coupled terminal that protrudes out of the container and does not leak. Further, (i) an oxidant inlet opposite to the fuel receiving site, leading to the assembly of the container and flowing the oxidant to either the shell side or the pore side of the microcell fibers of the assembly; and (ii) the container. 136. The electrochemical cell module of claim 133, comprising a spent oxidant outlet that leads to the assembly of and a flow of spent oxidant out of the container. 135. The electrochemical cell module of claim 133, wherein the container is comprised of a separable assembly from which the separable portion can be removed and has access to the module's internal volume and components. 144. The electrochemical cell module of claim 133, wherein the cross-sectional diameter of the heat exchange element is from about 100 microns to about 10 centimeters. 134. The electrochemical cell module according to claim 133, wherein the heat exchange element and the current collector are separable and distinct elements. The electrochemical cell module comprises a number of microcells in the assembly, each microcell constituting an internal electrode, a microporous membrane separator in contact with the internal electrode, an electrolyte in the pores of the microporous membrane separator, and the outside. The assembly comprises electrodes, the assembly is attached to the container, the container is axially aligned, liquid flows through the first end bonded to the first binder, to the open end of the microcell fibers, The binder separates the shell side and the hole side of the microcell fiber, the current collector constitutes a heat exchange element and projects axially from the first binder, and the second binder further comprises the first binder And a space between the first binder and the second binder is defined as a closed volume of the container, which leads to a closed volume of the inlet of the container. Assembly at the fiber hole side The flow and also the second binder and the container described above define a closed end volume, and in the configuration of the current collector, the heat exchange element protrudes through the second bond and the closed end of its open end. Terminating in volume, the coolant inlet leads to a closed end volume, and coolant is introduced into the closed end volume to flow through a current collector consisting of heat exchange elements to remove heat from the electrochemical reaction from the assembly. Liquid also flows through the second end of the assembly bound by the opposite binder and into the opening at the opposite end of the microcell fiber, with the opposite binder between the shell side and the pore side of the microcell fiber. Divided, the opposite current collector protrudes in the axial direction of the opposite binder, the current collector constitutes a heat exchange element terminating in the opposite binder, the outlet of the container leads to a closed volume and the used Fuel and cooling Is discharged from the closed container and removes the heat from the electrochemical reaction from the assembly; and the above-mentioned current collectors at each end are connected in series or in parallel with each other to protrude out of the container and securely prevent leakage. An electrochemical cell module that forms terminals that are fastened. The electrochemical cell module is a variety of microcells in the assembly, the microcells that make up the internal electrodes, the microporous membrane separator in contact with the internal electrodes, the electrolyte in the pores of the microporous membrane separator, the outside Consisting of electrodes, the assembly is attached to the container, aligned in the axial direction of the container, the liquid flows to the open ends of the microcell fibers through the first end bonded to the binder, which binds the shell of microcell fibers. Side and bore side, forming a closed end volume, the current collector constituting a heat exchange element, projecting in the axial direction of the binder into the closed end volume and connecting with at least one of the heat transfer paths of the container Arranging the at least one heat transfer path, flowing coolant therethrough, leading to the closed end volume of the inlet of the container, introducing fuel into the closed end volume, and providing the pore side of the microcell fiber. Through the assembly; and through the second end of the assembly bound by the opposite binder, liquid flows into the opening at the opposite end of the microcell fiber, and the opposite binder is attached to the shell side of the microcell fiber. To form a closed end volume separating the shell side and the hole side of the microcell fiber, and the current collector composed of the heat exchange element protrudes in the axial direction of the opposite binder to form the closed end. End volume that enters the volume, couples with at least one of the second heat transfer paths of the container, arranges at least one of the second heat transfer paths to flow coolant therethrough, and the outlet of the container is closed. The spent fuel is drained from the closed container; and the above-mentioned current collectors at each end are connected in series or in parallel to each other and protrude out of the container and are secured tightly to prevent leakage. Formed terminals Electrochemical cell module that. 144. The electrochemical cell module according to claim 142, wherein the first and second heat transfer paths are interconnected to each other. 146. The electrochemical cell module of claim 142, wherein the assembly is comprised of a number of components of a microcell substructure bundle, wherein the substructure bundles are sequentially coupled to one another in the above-described arrangement. 130. The electrochemical cell module according to claim 130, wherein as heat exchange elements within the bundle of microcell substructures, tubular heat exchange elements are distributed between the substructure bundles. The electrochemical cell module is composed of a number of microcells in the assembly, each microcell consisting of the active material of the internal electrode, the microporous membrane separator in contact with the active material of the internal electrode, and the microporous membrane separator. The active element of the inner electrode and the outer electrode comprises at least one of an electrode, a current collector, and an electrocatalytic component, wherein the active element of the inner electrode and the outer electrode comprises at least one of an electrode, a current collector, and an electrocatalytic component. A component comprising an electrode or current collector protruding outwardly into a portion; the assembly also includes a container containing a tank of coolant, a coolant in the tank of coolant, and the electrode or current collector described above. The terminal part of the component is conjugated with the above-mentioned coolant so that heat can be stably conducted, and the microcell From the assembly, through the above-mentioned electrodes or components of the current collector, to allow a stable heat transfer to the coolant, thereby producing the heat generated by the electrochemical reactions performed in the above-mentioned microcells during the operation of the module Get rid of electrochemical cell module. 142. The electrochemical cell module according to claim 142, wherein said heat exchange element is formed of a constituent material selected from the group consisting of a metal, a metal coated with a corrosion resistant material, graphite, a polymeric material, and the like. 146. The electrochemical cell module of claim 142, wherein said microcells have a size from about 100 microns to about 10 mm. 146. The electrochemical cell module of claim 142, wherein said microcells have a size from about 100 microns to about 10 mm. 142. The electrochemical cell module according to claim 142, wherein the coolant is a gas or a liquid. 143. The electrochemical cell module according to claim 142, wherein said binder is formed of a component material selected from the group of epoxy, polyurethane, bismaleimide, rubber, elastomeric materials, and the like. The microcell module is composed of microcell assemblies, where each microcell has an active material for the internal electrode, a microporous membrane separator in contact with the active material for the internal electrode, and a hole in the microporous membrane separator. Containing an electrolyte, an external electrode, wherein each active element of the internal and external electrodes comprises at least one of an electrode, a current collector, an electrocatalytic component, and the microcell described above comprises an elongated electrode or current collector; The method of extracting heat from the assembly comprises: (a) a hollow tubular heat exchange element protruding through the microcell assembly, wherein the tubular heat exchange element does not constitute a current collector; A hollow tubular heat exchange element protruding through the microcell assembly, comprising a current collector, (c) a microcell assembly or Protruding, microcell module is selected from the group consisting of conjugated stable current collector to allow coolant heat exchanger. A method for producing electrochemical energy, comprising: (A) various microcells of an assembly, each microcell constituting an internal electrode, a microporous membrane separator in contact with the internal electrode, a microporous membrane separator Making an electrochemical cell module consisting of electrolyte and external electrodes in the perforations of the plate; this microcell assembly includes a number of hollow tubular heat exchange elements arranged to flow coolant through a central lumen. The hollow tubular heat exchange element is distributed to the assembly and removes heat from the assembly during the electrochemical reaction during module operation; and there is a coolant supply as described above and a flow circuit Is internally connected to the above-mentioned coolant and the supply of the hollow tubular heat exchange element, and (B) the shell side of the above-mentioned micro cell assembly of the electrochemical cell module or (C) supplying an oxidizing agent to either the shell side or the hole side of the above-described microcell assembly of the electrochemical cell module, that is, to the side receiving the fuel. Supplying simultaneously to achieve an electrochemical reaction that generates electrical energy and heat; (D) discharging spent fuel from the electrochemical cell module; (E) supplying the above-mentioned coolant to the same supply as above. Removing the heat from the electrochemical cell module through a flow source and through the above-described flow circuit and the above-mentioned hollow tubular heat exchange element; and (F) discharging the above-mentioned coolant from the module. (G) flowing the discharged coolant through a heat exchanger and removing any appreciable heat therefrom to reduce the temperature of the coolant; (H) recirculating the cooled coolant to the module to form a hollow tube 156. The method of claim 154, further comprising passing a heat exchange element of 155. The method of claim 154, wherein said coolant is water. 155. The method of claim 154, wherein the cooling agent is a water-soluble glycol solution. 155. The method of claim 154, wherein excessive atmospheric pressure is applied to at least one of the shell side or the hole side. Many microcells of the assembly, each microcell making up the internal electrode, microporous membrane separator in contact with the active material of the internal electrode, microporous, managing heat during operation of the electrochemical cell module A method of comprising an electrolyte in a hole in a membrane separator, an external electrode, wherein the microcell assembly has a number of hollow tubular heat exchange elements arranged for flowing a coolant through a central lumen, This hollow tubular heat exchange element is distributed to the assembly described above to remove heat from the assembly during the electrochemical reaction during module operation and to remove the hollow tubular heat during the electrochemical reaction in the microcell assembly. A method of flowing a coolant through a heat exchange element. 160. The method of claim 159, wherein said coolant is a liquid coolant. 160. The method of claim 159, wherein said coolant is a gas. 160. The method of claim 159, wherein the assembly is attached to the container, the container is axially aligned, and a liquid is flowed from the first end where the first binder was attached to the open end of the microcell fiber. A binder separates the shell side and the pore side of the microcell fiber, and a current collector protrudes in an axial direction of the first binder to space the second binder and the first binder to form the first and second binders. The closed volume of the container between the second binders is connected to the closed volume of the inlet of the container, and the fuel is introduced into the closed volume and flows to the assembly on the pore side of the microcell element, where A closed end volume between the second binder and the container, wherein the heat exchange element extends through the second bond and terminates in the closed end volume at the open end of the heat exchange element; The coolant inlet connected to the closed end volume A coolant is introduced into the plugged end volume and the coolant flows axially through the heat exchange element of the assembly; and the second end of the assembly binds to the first opposite binder, from which micro- Liquid flows into the opening at the opposite end of the cell element, a first opposite binder separates the shell side and the pore side of the microcell fiber, and a current collector projects axially with the first opposite binder, A second opposing binder and a first opposing binder are spaced apart to provide a closed opposite volume of the container between the first and second opposing binders, and the outlet of the container is the closed container. Draining the spent fuel from the closed container, wherein a second opposing binder and an opposing end volume closing the container are defined, wherein the heat exchange element described above connects to the second binder. And ends at the opposite end volume, which is closed at the open end of the heat exchange element. And a coolant outlet communicates with the closed opposing end volume, drains the coolant from the obstructed opposing end volume, and removes heat from the electrochemical reaction from the assembly; The current collectors may be connected in series or in parallel to each other to protrude out of the container and form tightly sealed terminals; furthermore, the above-described assembly allows fuel to flow to the shell side of the microcell, How to have a tightly coupled flue so that there is no. 163. The method of claim 162, wherein the flues extend axially into the container and pass the first and second binders. The current collector projecting axially from the first binder is either the hole-side or shell-side current collector, while the current collector projecting axially from the first opposite binder is the hole- or shell-side current collector. 163. The method of claim 162, wherein one of the collectors is opposite a current collector that protrudes axially from the first binder. Each of the above-mentioned current collectors terminates at its outer end, a corresponding closed volume between the first and second binders, said end being connected in series or in parallel with the end of the other current collector, 163. The method of claim 162, further comprising forming a terminal that secures against leakage protruding out of the housing. And (i) an oxidant inlet opposite to the fuel receiving site, leading to the assembly of the container and flowing the oxidant to one of the shell side or the hole side of the microcell element of the assembly; and (ii) the container. 163. The method of claim 162, wherein the method comprises providing a spent oxidant outlet for flowing spent oxidant out of the container. 163. The method of claim 162, wherein the container is fabricated as a separable assembly from which the separable portion can be removed to provide access to the interior volume and components of the module. 163. The method of claim 162, wherein the heat exchange element comprises a current collector of the assembly. 163. The method of claim 162, wherein the cross-sectional diameter of the heat exchange element is from about 100 microns to about 10 centimeters. 163. The method of claim 162, wherein the heat exchange element and the current collector are separable and distinct elements. A method of generating electrochemical energy, comprising processing an electrochemical cell module comprising a plurality of fibrous microcell elements of an assembly including outwardly projecting inner and outer current collectors, the electrochemical cell module comprising: Operating to generate electrochemical energy, and extracting heat from at least one of the inner and outer current collectors and removing heat from the electrochemical cell module from the electrochemical cell module during the operation. A method comprising: 172. The method of claim 171, wherein the current collector is conjugated to at least one heat transfer path, and further coolant flows through the heat transfer path. 172. The method of claim 171, wherein said assembly comprises a continuous array of microcells. The electrochemical cell module consists of various microcells of the assembly, each microcell consisting of the active material of the internal electrode, the microporous membrane separator in contact with the active elements of the internal electrode, the pores of the microporous membrane separator , The active elements of the internal electrode and the external electrode are composed of one or more electrodes, current collectors and electrocatalytic components, and the electrodes or current collectors are assembled in the above-mentioned assembly. Generating electrochemical energy in an electrochemical cell module as they protrude out of the assembly and into the terminal portion; the ends of the aforementioned electrode or current collector components disposed in a tank. Attach the assembly to a container that contains a tank of coolant in part; in addition, coolant enters the tank of coolant The terminal portion of the electrode or current collector component is immersed in a coolant to allow stable heat transfer from the microcell assembly described above through the electrode or current collector component to the coolant. A method for removing heat generated by the electrochemical reaction performed in the microcell during the operation of the microcell. A micro-cell module is a thermal management method comprising a micro-cell assembly, in which each micro-cell is provided with an internal electrode active material, a microporous membrane separator in contact with the internal electrode active material, and a micropore. The active element of the internal and external electrodes comprises at least one of an electrode, a current collector, and an electrocatalytic component, wherein the microcell has an elongated electrode. Alternatively, a current collector is included; and a method of extracting heat from the assembly comprises: (d) a hollow tubular heat exchange element protruding into the microcell assembly, wherein the tubular heat exchange element described above does not constitute a current collector; A) a hollow tubular heat exchange element protruding into the microcell assembly, wherein said tubular heat exchange element constitutes a current collector; Protrudes out of the B cell assemblies, the coolant conjugated with stable way utilizing a method selected from the group consisting of the current collector to allow heat exchange. The electrochemical device is composed of hollow water-permeable membrane fibers placed in the assembly, the assembly contains a number of microcells at each end, the hollow fibers are placed in a container, and each binding end Are bonded to the interior volume therebetween, with hollow fibers arranged in parallel with the microcells of the assembly, with the first open end of each hollow fiber extending through the tube sheet out of the interior volume and the other end opposite the binder. Terminating at or in front of, the hollow fiber is arranged and absorbs the water generated by the electrochemical reaction by the wick phenomenon and pushes the water out of the electrochemical reaction site by penetrating the hollow fiber wall, An electrochemical device that flows through a hole in a hollow fiber to a collection point on a container outside of its internal volume. Orient the container so that the microcell element and the hollow fiber are arranged vertically, so that the collection location of the container is under the container, and the water in the hole of the hollow fiber flows down by gravity, and 177. The electrochemical device according to claim 176, wherein said device is adapted to come. 177. The electrochemical device of claim 176, wherein each hollow fiber is coated on its outer surface with a hydrophilic drug. 177. The electrochemical device of claim 176, wherein each hollow fiber is formed from a material selected from the group consisting of a polymeric material, glass, ceramic, and the like. 177. The electrochemical device of claim 176, wherein the hollow fiber has holes suitable for an application selected from the group of ultrafiltration, microfiltration, reverse osmosis, and the like. 177. The electrochemical device of claim 176, wherein the outer diameter of the hollow fiber ranges from about 100 microns to about 10 millimeters. 177. The electrochemical device according to claim 176, wherein each hollow fiber is formed of a hydrophilic material. An electrochemical cell module has entered the components of a number of microcell substructure bundles, the microcells that make up the internal electrodes, the microporous membrane separator in contact with the internal electrodes, and the pores of the microporous membrane separator It consists of a number of microcells in an assembly consisting of an electrolyte and an external electrode; this microcell assembly has a number of hollow tubular heat exchange elements arranged to flow a water-soluble coolant through a central lumen. The hollow tubular heat exchange element is distributed to the assembly and removes heat from the assembly during the electrochemical reaction during module operation; and there is a source of the water soluble coolant described above and When the circuit is interconnected with the water-soluble coolant and the source of the hollow tubular heat exchange element, the hollow tubular heat exchange element is connected to a water permeable porous membrane separator. Ri, that is water from a water-soluble coolant penetrates into the flow of fuel from the bore through the membrane separator wall, electrochemical cell module to wet the circumference of the electrochemical reaction. 183. The electrochemical cell module according to claim 183, wherein the assembly is attached to the container, the container is axially aligned, and the liquid is applied from the first end where the first binder is attached to the open end of the microcell fiber. The first binder separates the shell side and the pore side of the microcell fiber, the current collector protrudes in the axial direction of the first binder, and the heat exchange element further includes the first binder and the first binder. Is connected to the second binder at intervals, and the space between the first and second binders is a closed volume of the container, which is connected to the closed volume of the inlet of the container, and the fuel is introduced into the closed volume. Flow to the assembly on the pore side of the microcell fibers, wherein the second binder and the terminal volume closed by the container are defined, and the heat exchange element extends through the second binder. Closed at the open end of the heat exchange element A coolant inlet terminating in the volume and leading to the closed end volume introduces a water-soluble coolant into the closed end volume, allowing the coolant to flow axially through the heat exchange element of the assembly; The second end of the assembly couples to a first opposite binder, from which liquid flows to the opening at the opposite end of the microcell fiber, where the first opposite binder forms a hole with the shell side of the microcell fiber. Dividing the sides, the current collector protrudes in the axial direction of the first opposing binder, and the above-mentioned heat exchange element is further spaced from the first opposing binder on the opposite side of the second binder. Coupling the first and second opposite binders into a closed opposing volume of the container, the outlet of the container leading to the closed container and discharging the spent fuel from the closed container; With the second opposite binder and the opposite end volume with the container closed A heat exchange element as defined and extends through the second binder and terminates at a closed end volume at the open end of the heat exchange element and communicates with an opposing end volume at which the coolant outlet is closed. Evacuating the coolant from the closed opposing end volume and removing heat from the electrochemical reaction from the assembly; also, the above-described current collectors at each end are connected to each other in series or in parallel and project out of the container. To form a tightly-sealed terminal, and furthermore, to allow fuel to flow, an electrochemical tubing tightly coupled to the shell side of the microcell with the above-described assembly to prevent leakage Cell module. 183. The electrochemical cell module of claim 183, wherein each hollow tubular heat exchange element is formed of a material comprising a material that selectively permeates water. 183. The electrochemical cell module according to claim 183, wherein the substance that selectively permeates water comprises an ion exchange fluoropolymer. 183. The electrochemical device of claim 183, wherein the hollow fiber has holes suitable for an application selected from the group of ultrafiltration, microfiltration, reverse osmosis, and the like. 183. The electrochemical device of claim 183, wherein the outer diameter of the hollow fiber ranges from about 100 microns to about 10 millimeters. A method for managing water in an electrochemical device, comprising a plurality of microcells connected to respective ends and arranged in a container, each end connected in the container being connected to an inner volume therebetween; A hollow fiber that absorbs the water generated by the chemical reaction by the wicking phenomenon is arranged, water is removed from the electrochemical reaction site by penetrating the hollow fiber wall, and the water passes through the hole of the hollow fiber and out of the internal volume. A method of flushing a container to a collection location. 189. The microcell element and hollow fiber arranged vertically so that the collection site of the container is at the lower end of the container so that water in the holes of the hollow fiber flows down by gravity and comes to the collection site. The described method. 189. The method of claim 189, wherein the outer surface of each hollow fiber is coated with a hydrophilic drug. 189. The method of claim 189, wherein each hollow fiber is formed from a material selected from the group consisting of a polymeric material, glass, ceramic, and the like. 189. The method of claim 189, wherein the hollow fiber has pores suitable for an application selected from the group of ultrafiltration, microfiltration, reverse osmosis, and the like. 189. The method of claim 189, wherein the outer diameter of the hollow fiber ranges from about 100 microns to about 10 millimeters. 190. The method of claim 189, wherein each hollow fiber is formed from a hydrophilic material. A method for making an electrochemical cell module consisting of the following components: a number of microcell substructure bundle components, each microcell constituting an internal electrode, and microporous contact with the active material of the internal electrode. Consists of multiple microcells in an assembly consisting of a membrane separator, electrolyte in the pores of a microporous membrane separator, and external electrodes, arranged for flowing a water-soluble coolant through a central lumen A method of processing a microcell assembly, comprising a number of hollow tubular heat exchange elements, wherein the hollow tubular heat exchange elements are distributed to the assembly described above and remove heat from the assembly during an electrochemical reaction during module operation. Wherein said hollow tubular heat exchange element comprises a porous membrane separator permeable to water, wherein water derived from a water-soluble coolant passes through the membrane separator wall and fuel By penetrating the LES, a method to wet the circumference of the electrochemical reaction. 197. The method of claim 196, further comprising: attaching the assembly to a container, aligning the assembly along an axis of the container, and flowing a liquid from the first end where the first binder is attached to the open end of the microcell fibers. The first binder separates the shell side and the hole side of the microcell fiber, the current collector protrudes in the axial direction of the first binder, and the above-mentioned heat exchange element further moves away from the first binder. And the first and second binders are connected to the closed volume of the container, and the inlet of the container is connected to the closed volume, and the fuel is introduced into the closed volume. Flowing through the assembly on the pore side of the microcell fibers, wherein the second binder and the terminal volume closed by the container are defined, and the heat exchange element extends through the second binder, End volume closed at the open end of the heat exchange element A coolant inlet that terminates and leads to a closed end volume introduces a water-soluble coolant into the closed end volume and allows the coolant to flow axially through a heat exchange element of the assembly. Also, the second end of the assembly couples to the first opposite binder, from which liquid flows into the opening at the opposite end of the microcell fiber, and the first opposite binder is connected to the shell side of the microcell fiber. The current collector protrudes axially with the first opposing binder, and the heat exchange element described above further opposes the second binder at a distance from the first opposing binder. Side, with a closed opposing volume of the container between the first and second opposing binders, the outlet of the container leading to the closed container to drain spent fuel from the closed container. Where the second opposite binder and the opposite end of the container are closed A volume is defined, wherein the heat exchange element described above extends through the second opposing binder and terminates in a closed end volume at the open end of the heat exchange element, and the opposing closed end of the coolant outlet. Connects to the terminal volume, drains coolant from the opposing closed terminal volume, and removes heat from the electrochemical reaction from the assembly; the current collectors at each of the above-mentioned ends are connected in series or in parallel with each other to allow the And forming a tightly sealed terminal so as to leak out; and furthermore, tightly connecting the tubing tightly to the shell side of the microcell with the above-described assembly so as to flow fuel. 197. The method of claim 197, wherein each hollow tubular heat exchange element is formed of a material comprising a material that is selectively permeable to water. 197. The method of claim 197, wherein the substance that selectively permeates water comprises an ion exchange fluoropolymer. 197. The method of claim 197, wherein the hollow fibers have holes suitable for an application selected from the group of ultrafiltration, microfiltration, reverse osmosis, and the like. 197. The method of claim 197, wherein the outer diameter of the hollow fiber ranges from about 100 microns to about 10 millimeters. A continuous carbonaceous coating of coated fiber and of pyrolyzed organic material with a thickness that renders the metal fiber corrosion resistant, consisting of metal fibers formed of a material that is inherently corrosive . 207. The coated fiber of claim 202, wherein said continuous coating of thermally decomposed organic material is amorphous. 202. The coated fiber of claim 202, wherein said continuous coating of pyrolyzed organic material is crystalline. 207. The coated fiber of claim 202, wherein said continuous carbonaceous coating has micropores on the surface. Continuous carbonaceous coating on the surface of the above, as measured by BET adsorption isotherm, at least the coating material per gram 10 m ^2, claim 202 coated fiber according. 202. The coated fiber of claim 202, wherein the coated fiber has an outer diameter from about 50 micrometers to about 10 millimeters. 202. The coated fiber of claim 202, wherein said continuous carbonaceous coating is comprised of a vitreous carbon material. 202. The coated fiber of claim 202, further comprising an electrocatalyst over the continuous carbonaceous coating of the pyrolyzed organic material. A fibrous microcell structure comprising an internal electrode, a microporous membrane separator in contact with the internal electrode, an electrolyte in the pores of the microporous membrane separator, and an external electrode; and at least one of the internal electrode and the external electrode But a current collector consisting of coated fibers, including metal fibers formed of a material that is inherently susceptible to corrosion, and a continuum of pyrolyzed organic material with a thickness that renders the metal fibers corrosion resistant Fibrous microcell structure with typical carbonaceous coating. 210. An electrochemical cell device as in claim 210, wherein there are multiple fibrous microcell structures. 224. The electrochemical cell device according to claim 211, comprising a fuel cell. 220. The electrochemical cell device according to claim 211, comprising a battery cell. An electrochemical device with a current collector formed of a corrosive metal and a continuous carbonaceous coating of a pyrolyzed organic material with a thickness that renders the metal current collector resistant to corrosion. 220. The electrochemical device according to claim 211, comprising a fuel cell. 224. The electrochemical device according to claim 211, comprising a battery cell. 227. The electrochemical device according to claim 214, wherein said current collector has a plate structure. 226. The electrochemical device of claim 214, wherein said current collector has a fibrous structure. 227. The electrochemical device according to claim 214, wherein said current collector is sheet or fiber. 226. The electrochemical device of claim 214, wherein said continuous carbon coating is amorphous. 224. The electrochemical device of claim 214, wherein said continuous carbon coating is crystalline. 227. The electrochemical device of claim 214, wherein said continuous carbon coating is characterized by vitreous carbon. A fuel cell made of microcellular fiber elements, including current collectors or electrodes coated with an amorphous metal composition. A fuel cell made of microcell fibrous elements, including a current collector or electrode coated with a metal composition capable of retaining hydrogen. A microcell structure comprising an internal electrode, a microporous membrane separator in contact with the internal electrode, an electrolyte in the pores of the microporous membrane separator, and an external electrode;
A microcell structure in intimate contact with a non-carbon or non-graphite current collector, wherein at least one of the inner and outer electrodes comprises a carbon or graphite current collector, which is susceptible to disassembly and electrical disconnection there. 225. An electrochemical cell as in claim 225, wherein there are multiple microcell structures. The metal fiber itself is made of a material that is inherently susceptible to corrosion, and the above-mentioned fiber is coated with an organic material with the thickness of a pyrolysis product that gives the metal fiber corrosion resistance. A method of processing anticorrosive fibers by pyrolyzing the above-mentioned organic material and forming a continuous carbonaceous coating thereon. 228. The method of claim 227, wherein said continuous coating of pyrolyzed organic material is amorphous. 228. The method of claim 227, wherein said continuous coating of pyrolyzed organic material is crystalline. 228. The method of claim 227, wherein said continuous carbonaceous coating has micropores on its surface. A continuous carbonaceous coating on the surface of the above, as measured by BET adsorption isotherm, and at least the coating material per gram 10 m ^2, The method of claim 227. 229. The method of claim 227, wherein the outer diameter of the coated fibers ranges from about 50 micrometers to about 10 millimeters. 228. The method of claim 227, wherein said continuous carbonaceous coating comprises a vitreous carbon material. 228. The method of claim 227, further comprising forming an electrocatalyst on the continuous carbonaceous coating of the pyrolyzed organic material. This is a method for producing a fibrous microcell structure comprising an internal electrode, a microporous membrane separator in contact with the internal electrode, an electrolyte in a hole of the microporous membrane separator, and an external electrode. A series of metal fibers formed of a material that is inherently susceptible to corrosion, where at least one of the electrodes and the external electrode includes a current collector, and a thermally decomposed organic material with a thickness that provides the metal fibers with corrosion resistance A method of forming the current collector as described above as a coated fiber, comprising a typical carbonaceous coating. A method of processing an electrochemical device that forms a current collector of a corrosive metal and coats a continuous carbonaceous coating of a pyrolyzed organic material with a thickness that imparts corrosion resistance to the metal current collector. 237. The method of claim 236, wherein said electrochemical device comprises a fuel cell. 237. The method of claim 236, wherein said electrochemical device comprises a battery cell. 237. The method of claim 236, wherein said electrochemical device comprises a plate-shaped current collector. 237. The method of claim 236, wherein said electrochemical device comprises a fibrous current collector. 250. The method of claim 240, wherein said electrochemical device comprises a sheet or fiber type current collector. 237. The method of claim 236, wherein said continuous carbon coating is amorphous. 237. The method of claim 236, wherein said continuous carbon coating is crystalline. 237. The method of claim 236, wherein said continuous carbon coating is vitreous carbon. 237. The method of claim 236, wherein said current collector or electrode is coated with an amorphous metal composition. A method of processing a fuel cell made of coated microcell fiber elements, including a current collector or electrode coated with a metal composition capable of retaining hydrogen. A method of processing a microcell structure comprising an internal electrode, a microporous membrane separator in contact with the internal electrode, an electrolyte in a hole of the microporous membrane separator, and an external electrode, wherein at least the internal electrode and the external electrode are processed. On the other hand, a method of creating a carbon or graphite current collector, disassembling it and bringing it into close contact with a non-carbon or graphite current collector that is easily electrically disconnected there.