JP5076343B2 - Fuel cell separator and fuel cell - Google Patents

Description

  The present invention relates to a polymer electrolyte fuel cell.

  In general, a polymer electrolyte fuel cell power generation (PEFC) system is a unit cell in which a porous anode and a cathode are arranged on both sides of a solid polymer electrolyte membrane. It is composed of a fuel cell stack stacked through separators to be separated, a fuel supply device (pump), and an air or oxygen supply device (blower).

  Applications of PEFC include business and household cogeneration systems and in-vehicle power supplies. And in order to apply to these, the further size reduction and the improvement of an output are calculated | required.

  Patent Document 1 discloses a technique in which a porous body is provided in a gas flow path for the purpose of improving the performance and size and weight of a fuel cell stack.

JP 2004-139825 A

  In order to reduce the size and improve the output of the fuel cell stack, it is necessary to effectively remove heat generated at the same time as increasing the electrical conduction between unit cells. For this purpose, it is necessary to increase the thermal conductivity. In order to achieve this, it is preferable to use the pores of the conductive porous body as a flow path.

  However, in this case, the water vapor generated during the power generation reaction is liquefied, which may block the pores near the electrode and inhibit the power generation reaction.

A separator for a fuel cell in which two or more porous layers having different average pore diameters are laminated on a flow path plate that separates two kinds of fluids, and the flow path plate introduces a reaction gas into the porous layer An inlet gas manifold and an outlet gas manifold for discharging the gas after reaction from the porous layer , wherein the two or more porous layers are directed from the porous layer farthest from the flow path plate toward the flow path plate. An average pore diameter is reduced, and is formed in at least one of the two or more porous layers, and has a fluid flow path having a representative diameter larger than the average pore diameter of the porous layer, The fluid channel includes a main channel into which a reaction gas introduced from an inlet gas manifold of the channel plate directly flows and a branch channel branched from the main channel, and the branch channel has a repetitive shape of two or more branches. Separator for fuel cell, characterized in that It is over data.

  According to the present invention, the produced water liquefied in the vicinity of the electrode can be quickly moved away from the electrode, and the fuel cell separator capable of promoting the power generation reaction in the vicinity of the electrode, and the fuel cell in which stable output is ensured by using the separator. And can be provided.

  In PEFC that employs porous pores in the fluid flow path, hydrogen as the anode gas (hereinafter referred to as An gas) and oxygen in the air as the cathode gas (hereinafter referred to as Ca gas) are consumed by the following reaction to produce water. And heat and power are generated.

2H ₂ + O ₂ → 2H ₂ O + (heat) + (electric power)
Since this reaction occurs while flowing from upstream to downstream along the flow path formed by the pores of the porous body, the reaction gas flow rate decreases as it flows. On the Ca gas side, reaction-generated water vapor flows, and An Permeated water also flows in on the gas side, and when the water vapor concentration increases and exceeds the saturated concentration, condensed water is generated, causing gas shortage or flooding due to condensed water, leading to a decrease in cell voltage and a decrease in service life. . At the same time, latent heat is released due to the generation of condensed water, causing uneven temperature and uneven temperature distribution, increasing the maximum temperature and lowering the fuel utilization rate from the viewpoint of protecting the membrane electrode assembly (hereinafter referred to as unit cell). It may be necessary to convert it.

  However, in order to increase the output density to the limit and increase the efficiency, that is, to reduce the cost, the fuel utilization rate must be increased to nearly 100%.

  For this reason, simply applying a porous material to the flow path reduces the uniformity of the flow distribution and the electrical resistance at the flow path part, thereby improving the performance. When the utilization rate is near 100%, downstream gas shortage and flooding occur. In addition, when a fluid flow path is provided in the porous body in order to mitigate pressure loss, the fluid mainly passes through the flow path with less pressure loss, and as a result, the supply of fuel is the entire power generation unit of the fuel cell. The output of the fuel cell is not stable.

  In the following examples, a separator that does not inhibit the power generation reaction by keeping the generated water near the electrode away from the electrode using capillary action will be described. In addition, by providing fluid flow paths in two or more layers of porous material, the flow rate of the reaction gas is made uniform, pressure loss is reduced, and water management is achieved. In the case of a fuel cell stack, both the flow path plate and the porous layer are formed of a conductive material, so that the unit cells can be connected in series only by stacking the separator and the unit cells.

  According to this embodiment, the fuel utilization rate is high as PEFC, the auxiliary machine power is small, compact, and high output operation is possible.

  FIG. 1 shows an embodiment according to the present invention.

  The configuration of FIG. 1 will be described. The upper, middle, and lower views of FIG. 1 show one surface of the flow path plate 1 that forms a separator having both front and back surfaces. The reaction gas means An gas and Ca gas. The embodiment will be described with reference to the An gas flow path plate 1, but the Ca gas flow path plate 1 has substantially the same configuration.

  The lower view of FIG. 1 shows a cross-sectional view of the flow path plate 1. A two-layer porous layer and a channel network composed of a main channel and branch channels are formed on the channel plate 1 by a printing technique. The flow path network is finally formed with a precise shape by removing the printing medium by means of evaporation or volatilization. The representative diameter of the channel network is sufficiently larger than the average pore diameter of the porous layer. Here, the representative diameter means the length in the longest direction of the cross section of the channel network.

  The two-layered porous material is not shown, but when it is incorporated in a fuel cell stack, the porous material shown in the AA cross section closer to the unit cell (hereinafter referred to as A porous material 4) and the farther B material. -B cross section shown in the figure (hereinafter referred to as B porous 5), and a channel network is formed in each porous. The B porous 5 is a porous body having an average pore size smaller than that of the A porous 4 and subjected to a hydrophilic treatment so that the capillary force can be more exerted.

  In this embodiment, the porous layer has two layers. However, in the case of a fuel cell stack, if the pore diameter is set so that the capillary force acts in the direction to keep the generated water near the electrode away from the electrode, the two layers are formed. That's all.

  The upper part of FIG. 1 shows a cross-sectional portion of A porous 4. The configuration includes an inlet gas manifold 2 that is an inlet through which reaction gas is distributed and enters, and an A provided in the A porous 4 in order to distribute the reaction gas from the inlet gas manifold 2 to the entire A porous 4. A porous inner branch 6 for uniformly delivering the reaction gas from the A porous inner main flow path 6 and the A porous inner main flow path 6 to the unit cell via the A porous 4. A flow path 7 and an A porous body 4 that uniformly distributes gas and makes electric conduction and heat conduction uniform.

The diagram in FIG. 1 shows a B porous inner branch channel 10 of a B porous inner channel network 11 provided in the B porous 5 in order to collect the reaction gas after reaction to the outlet gas manifold 3; The B porous inner branch flow channel 10 for collecting the post-reaction gas that has flowed out to the B porous inner branch flow channel 10 is shown.

  The average pore diameter of the B porous 5 is made smaller than that of the A porous 4 so that the reaction gas can be easily supplied to the unit cell via the A porous 4, and the capillary force for the B porous 5 to absorb water is increased. It is a mechanism that makes it easy to act and sucks water generated by reaction and permeation.

  Here, the A porous internal flow channel network 8 and the B porous internal flow channel network 11 may be formed on the surface or boundary surface of each porous layer, but as shown in FIG. It is preferable to be formed inside the quality layer. The reaction gas is supplied to the unit cell through the A porous 4 by forming the A porous inner passage network 8 inside the A porous 4, so that the reaction gas is rectified and uniformly unitized. This is because it is supplied to the cell. Further, the formation of the B porous inner flow path network 11 inside the B porous 5 reduces the contact area of the interface between the A porous 4 and the B porous 5 and inhibits the exchange of generated water. This is also because it leads to a reduction in electrical resistance.

  The flow path network formed in the A porous 4 is surrounded by a porous body except that the portion adjacent to the inlet gas manifold 2 is opened to the inlet gas manifold 2. This is a device designed to prevent the reaction gas introduced from the inlet gas manifold into the flow path plate from passing through the A porous inner main flow path 6 and directly from the outlet gas manifold. Similarly, the channel network formed in the B porous 5 is surrounded by a porous body except that a portion adjacent to the outlet gas manifold 3 is opened to the outlet gas manifold 3. This is a device for preventing the reaction gas from flowing directly into the B porous 5 channel network. By combining these configurations, the reaction gas introduced from the inlet gas manifold to the flow path plate is first introduced into the A porous inner main flow path 6 and reaches the entire A porous 4 through the flow path network, and then B It penetrates into the porous 5 and is recovered from the outlet gas manifold 3.

  The action of capillary force is as follows. The reaction gas that has entered from the inlet gas manifold 2 enters the A porous inner main flow path 6 of the A porous internal flow path network 8 of the A porous 4, and the end is surrounded by the porous structure, and becomes thinner as going forward. It extends into the A porous inner main flow path 6 and further expands to the entire A porous 4 through the A porous inner branch flow path 7 connected to the A porous inner main flow path 6. At that time, the gas is uniformly supplied to the unit cell through the porous A 4 by the pressure of the reaction gas. At this time, the water generated in the vicinity of the electrode of the unit cell penetrates the pores of the A porous 4 and is sucked by capillary action in contact with the B porous 5. After that, it appears in the B porous inner branch flow channel 10 in the B porous 5, merges with the post-reaction gas, flows out to the main flow channel 9 that becomes thicker as it approaches the outlet gas manifold 3, and is discharged from the outlet gas manifold 3. .

  Water is generated on the cathode side by the reaction, but permeates the electrolyte membrane constituting the unit cell and appears on the anode side. Assuming that the reaction temperature of PEFC is around 70 ° C., if the reaction gas is within a saturation concentration of about 38% vol, it will be present as water vapor and no flooding will occur in the reaction gas. However, if this saturation concentration is exceeded, condensed water is produced.

  Condensate generation requires a core that provides the saturation concentration and location, and does not occur in a space that is empty, so it occurs around the porous material. For this reason, as shown in the present embodiment, if the reaction gas can be distributed from the porous body over the entire surface and evenly, the generated condensed water will not be concentrated locally, so that the balanced state of discharge and generation is maintained. It is difficult for flooding and gas shortage to occur.

  At the same time, in this embodiment, the appropriate humidity necessary for the reaction gas can be directly and directly covered by the water from the unit cell, so that the humidity is insufficient near the inlet and excessively humid near the outlet as in the prior art. Can be avoided. As a result, there is no need to humidify the reaction gas, and the humidifier can be omitted or downsized.

  The shape of the branch channel network is a bifurcated or repeated shape of two or more branches, that is, one branch channel branches into two or more thinner branch channels, and the narrow branch channel further Furthermore, it is good also as a shape repeated so that it may branch to two or more narrow branch flow paths. A larger number of branches can form a more uniformly distributed channel network. It is preferable that branching is repeated as the blood vessel flows through the human body as it approaches the end, and is supplied to every corner of the porous body. Further, a shape in which the representative diameter gradually decreases as it approaches the end is preferable.

  In addition, if the fractal dimension of the shape of the flow path network is set to 1.8 dimensions or more and less than 2 dimensions, the flow path design can be facilitated, and the flow path network can be formed throughout the entire porous body. The formation of the channel network is not limited to printing, but a biotechnological method such as crystal growth or protein crystal growth can also be applied, and a uniform channel network can be formed.

  In a flat development in which the reaction gas is consumed by the power generation unit while flowing through the porous body, increasing the fuel utilization rate to about 100% reduces the gas concentration and increases the water vapor concentration on the way from upstream to downstream. As the fuel concentration increases and condensate is generated, the fuel utilization rate must be limited to a small value. In this case, the increase in output will reach its peak. However, according to the present embodiment, the fuel gas introduced from the fluid inlet first passes through the fluid flow path and reaches the entire flow path plate, and then passes through the porous body to the entire power generation surface of the unit cell. Go around.

  Here, the definition of the fractal (similarity) dimension is as follows.

Fractal (similarity) dimension = log (number of self-similar parts) / log (enlargement factor)
For example, when each side of a certain cube is doubled (enlargement factor = 2), the resulting cube consists of 8 original cubes (number of self-similar parts = 8).

Then, the fractal (similarity) dimension = log (8) / log (2) = log ₂ 8 = log ₂ 2 ³ = 3.

  First, in order to form the B porous internal channel network 11 on the conductive thin plate constituting the separator, a mixture of metal particles and substance particles that sublimate, gasify or evaporate at high temperature is sprayed, sprayed or printed. Then, a masking member (sublimation at high temperature, gasification or evaporation) having a flow path shape of the B porous inner flow path network 11 is placed thereon, or the shape is printed or sprayed, and further, metal Thermally spraying or spraying or printing a mixture of particles and material particles that sublime, gasify or evaporate at high temperatures that sublime or evaporate at high temperatures. Next, in order to form the A porous internal channel network 8, the same processing is performed, and finally, the masking member and the plastic particles are sublimated, gasified or evaporated to form the channel network and the porous portion. . In the case of the A and B porous materials, the average pore size of the porous material is changed by changing the particle size of the metal particles or the material particles that are sublimated, gasified or evaporated at a high temperature.

<Specific manufacturing method of separator>
According to the above configuration, there is an effect that it is possible to provide a fuel cell capable of improving the fuel utilization rate, downsizing, high output, and no humidification.

  2 shows an A porous inner branch channel 7 in the A porous 4, an A porous inner channel network 8 and a B porous inner branch channel 10 in the B porous 5, The difference from the first embodiment is that the phase of the branch channel network is shifted so that the channel network 11 does not overlap when viewed from the vertical direction of the separator.

  By adopting such a configuration, there is an effect that the pressure loss and distribution in the whole can be made more uniform than in the first embodiment, the reaction gas can be made more uniform, and the pressure loss can be reduced.

  3 is different from the first embodiment in that the outlet gas manifold 2 side of the A porous 4 main flow path 6 in the first embodiment is opened. As a result, in the case of a reaction gas with a large amount of impurities in the reaction gas, such as in the case of a reaction gas with a high gas mixture ratio other than hydrogen, the pressure can be reduced by preventing a part of the reaction gas from passing through the porous part. Loss can be reduced.

  By adopting such a configuration, unlike the first embodiment, the reaction gas that does not pass through the B porous 5 is generated, thereby eliminating the retention of the unreacted gas and supplying the fresh reaction gas. And flooding can be prevented.

  4 is different from the first embodiment in that there is no main channel in the channel network and the entire channel channel is composed only of the branch channel channel network.

  In this way, when the flow channel network is created by printing, the flow channel cross-sectional area is unilaterally asymptotically increased on one of the inlet side or the outlet side on one side. It is easy to volatilize and remove the printed material to form a channel network.

  With this configuration, it is possible to provide a fuel cell that is easy to manufacture and has high utilization, compactness, and high output.

  Example 5 shows a stack 100 in which the separators of Examples 1 to 4 are stacked. The structure of this stack is as follows. A supply port 112 for supplying An gas, a supply port 111 for supplying Ca gas, a supply port 110 for supplying cooling water, insulating plates 109 at both ends, a current collecting plate 113 for taking out power to the outside, and the embodiment 1 is a stack 100 in which two separators 101 are alternately stacked with a cooling water flow path part 121 side back to back and a power generation part 105 sandwiching an electrolyte membrane 102 between electrodes 103 and a gas diffusion layer 106. , An outlet 104 for discharging An gas, an outlet 108 for discharging Ca gas, and an outlet 107 for discharging cooling water. The power generation portion 105 is in contact with the An gas flow path portion 120 and the Ca gas flow path portion 122 to supply hydrogen and oxygen to the power generation portion 105. At the same time, heat generated in the power generation portion 105 is absorbed by the cooling water flow channel portion 121 formed on the back side of each of the Au gas flow channel portion 120 and the Ca gas flow channel portion 122. A separator 131 and B porous 132 are printed on the separator 101.

  When the gas diffusion layer is sandwiched between the unit cell and the separator as in this example, the average pore diameter of the gas diffusion layer is larger than the average pore diameter of the porous layer formed on the outermost surface of the separator. It is preferable to design larger. This is to efficiently use the mechanism of water removal using capillary action.

  In addition, although there is no cooling water flow path part and the flow path of the reaction gas is back-to-back, and a stack configured to cool the water by blowing water mist into the reaction gas is not shown, it is a modification of this embodiment.

  In this way, the separator of the present invention makes it possible to generate power over the entire power generation area by making the flow distribution of the reaction gas flow path of the entire stack not uniform, but also by making the flow distribution even higher. It is possible to make a compact stack with high output by making the contribution level uniform and strengthening the output.

It is explanatory drawing which showed the structure of the separator. Example 1 It is explanatory drawing which showed the structure of the separator. (Example 2) It is explanatory drawing which showed the structure of the separator. (Example 3) It is explanatory drawing which showed the structure of the separator. Example 4 It is explanatory drawing which showed the structure of the stack. (Example 5)

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Channel plate, 2 ... Inlet gas manifold, 3 ... Outlet gas manifold, 4,131 ... A porous, 5,132 ... B porous, 6 ... A porous inner main flow path, 7 ... A porous inside Branch channel, 8 ... A porous internal channel network, 9 ... B porous internal channel, 10 ... B porous internal branch channel, 11 ... B porous internal channel network, 100 ... stack, 101 ... separator , 102 ... electrolyte membrane, 103 ... electrode,
DESCRIPTION OF SYMBOLS 104 ... An gas discharge port, 105 ... Power generation part, 106 ... Gas diffusion layer, 107 ... Cooling water discharge port, 108 ... Ca gas discharge port, 109 ... Insulating plate, 110 ... Cooling water supply port, 111 ... Ca gas supply port 112 ... An gas supply port, 113 ... Current collector plate, 120 ... An gas flow path part, 121 ... Cooling water flow path part, 122 ... Ca gas flow path part.

Claims (8)

A fuel cell separator in which two or more porous layers having different average pore diameters are formed on a flow path plate that separates two kinds of fluids,
The flow path plate has an inlet gas manifold that introduces a reactive gas into the porous layer, and an outlet gas manifold that discharges a post-reaction gas from the porous layer,
The two or more porous layers have a smaller average pore diameter from the porous layer farthest from the flow path plate toward the flow path plate,
Wherein formed on at least one of the two or more porous layers, having a fluid flow path having a large representative diameter than the average pore size of the porous layer,
The fluid flow path includes a main flow path into which a reaction gas introduced from an inlet gas manifold of the flow path plate directly flows and a branch flow path branched from the main flow path,
The fuel cell separator according to claim 1, wherein the branch channel has a repeated shape of two or more branches.   2. The fuel cell separator according to claim 1, wherein the fluid flow path is formed in any two of the two or more porous layers. 3. The fuel cell separator according to claim 2, wherein the two porous layers in which the fluid flow path is formed have a phase difference in the arrangement of the branch flow paths. The fluid flow path is provided in the two or more porous layers, and a porous layer formed with a main flow path connected to the inlet gas manifold and a main flow path connected to the outlet gas manifold are formed. The fuel cell separator according to claim 1, wherein the porous layer is different.   The fuel cell separator according to claim 1, wherein the branch channel has a smaller representative diameter than the main channel.   3. The fuel cell separator according to claim 2, further comprising a communication hole for connecting the fluid flow paths of the two porous layers in which the fluid flow paths are formed.   2. The fuel cell separator according to claim 1, wherein a fractal of 1.8 dimensions or more is used as the shape of the fluid flow path.   2. The fuel cell separator according to claim 1, wherein a unit cell in which an anode and a cathode are formed via a proton conductive solid polymer electrolyte membrane and a separator for separating a fluid are laminated, wherein the separator is a fuel cell separator according to claim 1. The fuel cell characterized by the above-mentioned.

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