JP2007172953A - Fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance energy efficiency by reducing uneven pressure loss between cells and uniformizing a gas flow flowing in each cell, and to reduce production loss. <P>SOLUTION: This polymer electrolyte fuel cell is equipped with fluid passages 6, 7 in which a fuel gas and an oxidant gas are circulated respectively. An inclination having an angle of inclination of more than 0 degree and less than 40 degree made to the surface perpendicular to the laminated direction of cells are given to the top part of the projecting part 3 of an anode side separator and the top part of the projecting part 4 of a cathode side separator, and thereby, an MEA (membrane electrode assembly) 5 is stretched and pulled by the inclinations of the top parts, and the MEA 5 is inhibited from hanging down to the fluid passages 6, 7. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fuel cell using an MEA (membrane electrode assembly) composed of a pair of electrodes sandwiching a polymer electrolyte membrane.

  A fuel cell generates electric power and heat simultaneously by electrochemically reacting a fuel gas containing hydrogen and an oxidant gas containing oxygen such as air.

  The polymer electrolyte fuel cell is manufactured as follows.

  First, a catalytic reaction layer composed mainly of carbon powder carrying a platinum-based metal catalyst is formed on both sides of a polymer electrolyte that selectively transports hydrogen ions. Next, a diffusion layer is formed on the outer surface of the catalytic reaction layer by, for example, carbon cloth (carbon fiber woven fabric) or carbon paper having both air permeability of fuel gas and electronic conductivity. The diffusion layer and the catalytic reaction layer are combined to form a reaction electrode, a reaction electrode containing hydrogen is an anode (hydrogen electrode, fuel electrode), and a reaction electrode containing oxygen is a cathode (oxygen electrode, air electrode). ) Respectively.

  Next, a gas seal material is placed around the reaction electrode with a polymer electrolyte membrane so that the supplied fuel gas or oxidant gas does not leak outside or the fuel gas and oxidant gas are mixed with each other. And a gasket is placed. This sealing material or gasket is integrated with the reaction electrode and the polymer electrolyte membrane in advance, and is sometimes referred to as MEA (membrane electrode assembly) (hereinafter referred to as MEA).

  On the outside of the MEA, a conductive separator for mechanically fixing the MEA and electrically connecting adjacent MEAs to each other in series is disposed. A gas flow path for supplying the reaction gas to the reaction electrode and carrying away the generated gas and surplus gas is formed in a portion of the separator that contacts the MEA. Although this gas flow path can be provided separately from the separator, a structure in which a groove is provided on the surface of the separator to form a gas flow path is common.

  In order to supply the fuel gas to the groove as the gas flow path, a pipe for supplying the fuel gas branches to the number of separators to be used, and a piping jig for directly connecting the branch destination to the separator-like groove is required. It becomes. This jig is called a manifold, and the type that connects directly from the fuel gas supply pipe as described above is called an external manifold. There is a type of this manifold called an internal manifold with a simplified structure. The internal manifold is provided with a hole penetrating the separator in which the gas flow path is formed, through which the gas flow path is passed, and the fuel gas is directly supplied from the hole.

  Since the fuel cell generates heat during operation, it is necessary to cool the fuel cell with cooling water or the like in order to maintain the battery in a favorable temperature state. Usually, a cooling unit for flowing cooling water every 1 to 3 cells is inserted between the separator and the separator. However, a cooling water channel is often provided on the back surface of the separator to form a cooling unit.

  The MEA, separator, and cooling unit configured as described above are alternately stacked as cells, 10 to 400 cells are stacked, the cell stack is sandwiched between end plates via current collector plates and insulating plates, and both ends are fixed with fastening bolts. As a result, a polymer electrolyte fuel cell is manufactured.

  The fastening has the purpose of reducing the contact resistance between the laminated members such as the joint between the separator and the gas diffusion layer, in addition to maintaining the sealing performance so as not to leak the gas and the circulating water.

  Therefore, a relatively large fastening pressure of 0.5 MPa to 1.0 MPa is required as the surface pressure. Due to this fastening pressure, the amount of sag of the gas diffusion layer to the gas flow path tends to vary. Further, due to the variation in the sagging amount, the gas leak amount to the adjacent gas flow path through the gas diffusion layer varies.

  The phenomenon that the pressure loss of each cell differs due to the occurrence of the variation occurs. Many polymer electrolyte fuel cells have a configuration in which fuel gas and oxidant gas are distributed and supplied in parallel from the manifold on the side of the separator to each cell. The gas flow rate to be supplied is different for each cell. As a result, in a cell with a low gas flow rate, water droplets block the gas flow path, resulting in insufficient fuel supply to the electrode and catalyst after the blocked location, so the voltage gradually decreases and the water droplets are discharged. Then, since the flow path blockage is released, the fuel supply is recovered, and there is a problem that a voltage instability phenomenon (flooding) occurs in which the voltage rises.

  In order to solve such a problem, Patent Document 1 measures the pressure loss of a single cell, divides it into predetermined ranks, collects the single cells of the same rank, and manufactures a fuel cell. A fuel cell and a method of manufacturing the same that reduce flow rate variation and suppress flooding are disclosed.

Further, in Patent Document 2, the fiber direction of the gas diffusion layer is configured to be parallel to the gas flow direction, and the gas permeability of the gas diffusion layer in the direction orthogonal to the gas flow direction is the gas flow. By setting it to be smaller than the gas permeability of the gas diffusion layer in the direction, gas leakage that occurs in the adjacent gas flow path through the gas diffusion layer is prevented, and pressure loss loss of the reaction gas flowing through the gas flow path is reduced Thus, a fuel cell in which flooding is suppressed is disclosed.
JP 2003-151604 A JP 2004-185936 A

  However, in the configuration described in Patent Document 1, it takes time and effort to measure the pressure loss of a single cell and divide it into a predetermined rank. .

  Further, in the configuration described in Patent Document 2, since the fiber direction of the gas diffusion layer is parallel to the gas flow path, the rigidity in the direction orthogonal to the gas flow path is reduced, and as a result, the gas diffusion layer Tends to sag into the gas flow path. Therefore, there is a problem that variation in the amount of sag in the gas flow path of the gas diffusion layer between the cells cannot be reduced.

  The present invention solves the above-mentioned conventional problems, has a low production loss, reduces pressure loss variation between cells, and equalizes the flow rate of gas flowing to each cell, thereby improving the flooding resistance. An object is to provide a battery.

  In order to solve the problems and achieve the object, a fuel cell of the present invention comprises a polymer electrolyte membrane, an MEA comprising a pair of electrodes that sandwich the polymer electrolyte membrane, and a pair of separators that sandwich the MEA. A fuel cell comprising a plurality of cells each having a catalyst layer in contact with the polymer electrolyte membrane and a gas diffusion layer in contact with the separator as the electrode, wherein the separator has a convex portion and a concave portion serving as a fluid flow path. And an inclined portion is formed on the convex portion, whereby the sag of the gas diffusion layer into the concave portion of the gas flow path can be suppressed.

  According to the present invention, by extending the MEA including the gas diffusion layer, it is possible to suppress the gas diffusion layer from sagging into the concave portion serving as a fluid passage. Gas leakage to adjacent gas flow paths through the layers can be prevented.

  From the above, it is possible to improve the manufacturing quality and improve the performance such as stability and efficiency in the polymer electrolyte fuel cell.

  Hereinafter, embodiments according to the present invention will be described with reference to the drawings.

  FIG. 1 is a perspective view schematically showing a part of a unit cell (cell) which is a unit of a polymer electrolyte fuel cell which is an embodiment of a fuel cell according to the present invention, and FIG. It is line sectional drawing.

  As shown in FIGS. 1 and 2, the cell 8 includes an MEA (membrane electrode assembly) 5, an anode side separator 1, and a cathode side separator 2. The MEA 5 is a sheet-like material in which an electrode 11 having a catalyst layer on each of the front and back surfaces of the proton conductive polymer electrolyte membrane 9 and a reaction electrode 10 comprising a gas diffusion layer as a support for the electrode 11 are provided. is there.

  The type and shape of the proton conductive polymer electrolyte membrane 9 are not particularly limited as long as they are generally used for fuel cells. Further, the type and shape of the reaction electrode 10 are not limited, and may be a general reaction electrode in which platinum as a catalyst is supported on carbon cloth, carbon paper, or carbon mesh. The separators 1 and 2 may be any gas-impermeable conductive material. For example, a material obtained by cutting a resin-impregnated carbon material into a predetermined shape or a mixture of carbon powder and a resin material is generally used. .

  The separators 1 and 2 are plate-like bodies that electrically connect the MEA 5 and the adjacent MEA of a unit cell (not shown) in series, and have fluid flow paths 6 and 7 through which fuel gas and oxidant gas flow. Many are arranged in parallel over the entire plate state. In addition, on the surface opposite to the surface on which the plate-like fluid flow paths 6 and 7 are provided in the separators 1 and 2, a flow path 12 for circulating a cooling fluid is provided.

  In the present embodiment, the top of the convex portion 3 of the anode-side separator 1 and the top of the convex portion 4 of the cathode-side separator 2 are each set at 0 degree to a plane perpendicular to the direction in which the unit cells 8 are stacked. 2 and inclined by less than 40 degrees, as shown in FIG. 2, the tops of the convex portions 3 and 4 are joined together, and the adjacent concave portions in the separators 1 and 2, and the convex portions The cross-sectional dimensions in the fluid flow direction are the same.

  Further, as in Modification 1 of the present embodiment shown in FIG. 3, the dimension L1 after the top of the convex portion 3 of the anode side separator 1 and the top of the convex portion 4 of the cathode side separator 2 are joined is as follows. You may make it the same and may form the convex part of the short dimension L2 and the convex part of the long dimension L3 alternately in each convex part.

  Further, as in the second modification of the present embodiment shown in FIG. 4, the fluid flow paths 6 and 7 are respectively provided at the top of the convex portion 3 of the anode side separator 1 and the top of the convex portion 4 of the cathode side separator 2. Alternatively, a gentle unevenness 13 may be formed so as to be parallel to the recessed portion, and the MEA sheet 5 may be dripped into the unevenness 13. In the second modification, the convex portions of the concave and convex portions 13 are inclined at 0 degree or more and less than 40 degrees on a plane perpendicular to the stacking direction of the unit cells, and the concave portions adjacent to the concave and convex portions 13 and the dimensions of the convex portions are arranged. They are formed so as to have the same shape.

  The reason why the present embodiment is configured as shown in FIGS. 2 to 4 will be described.

  FIG. 5 is a cross-sectional view showing the structure of a conventional unit cell as a comparative example. As shown in FIG. 5, conventionally, the top and the top of the convex portion 3 of the anode side separator 1 and the top of the convex portion 4 of the cathode side separator 2 often have the same cross-sectional dimensions and shapes. When a predetermined fastening pressure is applied to reduce the contact resistance, sag B of the MEA 5 into the fluid flow paths 6 and 7 is likely to occur. As a result, the sag B of the MEA 5 was likely to cause variations in pressure loss between the single cells.

  Therefore, in the present embodiment, as described above, the convex portions of the fluid flow paths 6 and 7 so that the MEA 5 extends in a plane perpendicular to the direction in which the unit cells 8 are stacked (the direction of arrow A in FIG. 1). By providing the separators 1 and 2 with the configuration in which the 3 and 4 are inclined, the sagging of the MEA 5 into the fluid flow paths 6 and 7 could be suppressed.

  In the present embodiment, the gas diffusion layer is included by defining the inclination angle of the tops of the convex portions 3 and 4 to be greater than 0 degrees and less than 40 degrees on a plane perpendicular to the stacking direction of the unit cells 8. The amount of sagging of the separators 1 and 2 in the MEA 5 into the recesses to be the fluid flow paths 6 and 7 became 0% or more and less than 20% of the depth of the recesses. The reason will be described below.

  FIG. 6 is an explanatory view showing a basic configuration for extending the MEA in the present embodiment. In the adjacent convex portions 3 and 4 in the fluid flow paths 6 and 7, the respective top portions are shifted to form an inclination θ. Thus, the MEA 5 is prevented from sagging in the fluid flow paths 6 and 7 by pulling and extending the MEA 5 in the vertical direction in the drawing.

  Therefore, a tensile test was performed on the MEA having the configuration of the present embodiment. After testing at a tensile speed of 1.6 mm / s as test conditions, each part of the MEA was observed in detail with an optical microscope to confirm whether or not damage occurred.

  As a result, as shown in FIG. 7, it was found that the MEA 5 was damaged when it was stretched 30% or more from the initial length. That is, when the MEA 5 is stretched by 30% or more by the separators 1 and 2 of the present embodiment, there is a possibility that problems such as breakage may occur.

  Therefore, the inclination angle θ of the top part of the convex part when the length of the top part of the convex parts 3 and 4 after the inclination is 1.3 times the length of the top part of the convex parts 3 and 4 before the inclination. It was about 40 degrees when asked. Therefore, this angle is the upper limit of the tilt angle.

  After producing the unit cell 8 having the configuration of the present embodiment as described above and stacking a large number (for example, 100 layers) of the unit cell 8 while securing a cooling water channel to form a battery stack, both end portions of the cell stack are formed. A polymer electrolyte fuel cell is manufactured by providing a current collector plate and an insulating plate made of an electrically insulating material, and further fixing with an end plate and a fastening rod.

  In this way, in the polymer electrolyte fuel cell composed of the unit cells 8, the MEA 5 is stretched, so that the fluid channel 6 that is the anode-side fuel channel and the fluid channel 7 that is the cathode-side oxidizing material channel are used. The sag of the MEA 5 can be suppressed. That is, the pressure loss variation between the single cells is reduced, and the gas flow rate flowing through the single cells can be evenly distributed.

  Next, an embodiment according to the present invention will be described with reference to FIG.

  First, a method for producing the reaction electrode 10 including the catalyst layer will be described. That is, an electrode catalyst was prepared by supporting 25% by weight of platinum particles having an average particle diameter of about 30% on acetylene black powder. A dispersion solution in which perfluorocarbon sulfonic acid powder was dispersed in ethyl alcohol was mixed with a solution in which the catalyst powder was dispersed in isopropanol to form a catalyst paste.

  On the other hand, the carbon paper which becomes a support body of an electrode was water-repellent treated. That is, after impregnating a carbon nonwoven fabric (made by Toray, TGP-H-120) having an outer dimension of 14 cm × 14 cm and a thickness of 36 μm into a fluororesin-containing aqueous dispersion (manufactured by Daikin Industries, NEOFLON ND1), this is dried. Heating at 400 ° C. for 30 minutes gives water repellency. A reaction electrode 10 having a catalyst layer 11 on one surface of the carbon nonwoven fabric is formed by applying the paste-like catalyst to one surface of the water-repellent carbon nonwoven fabric using a screen printing method.

At this time, a part of the catalyst layer is embedded in the carbon nonwoven fabric. Incidentally, the coating amount of the paste-like catalyst by screen printing, the amount of platinum contained in the reaction electrode 10 after formation 0.6 mg / cm ^2, the amount of perfluorocarbon sulfonic acid such as a 1.2 mg / cm ² It is adjusted to.

  Next, the reaction electrode 10 is placed on both sides of the proton conductive polymer electrolyte membrane 9 having an outer dimension of 15 cm × 15 cm so that the catalyst layer is in contact with the sides of the proton conductive polymer electrolyte membrane 9. It joins with a press and MEA5 is created. In the case of this example, a proton-conductive polymer membrane obtained by thinning perfluorocarbon sulfonic acid to a thickness of 30 μm was used.

  Next, the manufacturing method of the electroconductive separators 1 and 2 which are the points of this invention is demonstrated.

  First, an artificial graphite powder having an average particle diameter of about 50 μm to 100 μm is prepared, and 20% of a thermosetting phenol resin is extruded and kneaded by 80% by weight of the artificial graphite powder with a kneader. And this kneaded powder is thrown into the metal mold | die which made the shape where the convex parts 3 and 4 of the fluid flow paths 6 and 7 incline so that it may extend to the surface orthogonal to the direction where MEA5 laminates. This mold is processed so as to mold the cooling water channel groove and the manifold in addition to the molding of the fluid channels 6 and 7.

After the kneaded powder is put into this mold, it is hot pressed to obtain separators 1 and 2. The conditions for this hot pressing are a mold temperature of 150 ° C. and a pressure of 100 kg / cm ² for 10 minutes. The obtained separators 1 and 2 have an outer dimension of 20 cm × 20 cm, a thickness of 3.0 mm, the groove-like fluid flow paths 6 and 7, and the cooling water flow path are both square and 1.0 mm × 1. It is adjusted to be 0 mm. Therefore, the thickness of the thinnest part of the separators 1 and 2 is 1.0 mm.

  As the conductive carbon material, artificial graphite is used in the present embodiment, but natural graphite, carbon black, ketjen black, and the like can also be applied. In this embodiment, a mechanism in which the convex portions 3 and 4 of the fluid flow paths 6 and 7 are inclined so as to extend in a plane perpendicular to the direction in which the MEA is laminated on the mold is cut. The mechanism may be formed by processing.

  As a comparative example for comparison with the present embodiment, the separator having no inclined convex portion is used, and an anode side separator is superimposed on one surface of the MEA and a cathode side separator is superimposed on the back surface, as shown in FIG. A single battery 8 was produced.

Then, after stacking two cells of the cells 8 of both the present example and the comparative example, the two-cell stacked battery is sandwiched by a separator in which a cooling channel groove is formed, and this pattern is repeated to form a battery of 100-cell stacked A stack was made. Furthermore, the both ends of the battery stack were fixed with a stainless steel current collector plate, an insulating plate made of an electrically insulating material, and an end plate and a fastening lot. The fastening pressure at this time was 15 kg / cm ² per separator area.

  The polymer electrolyte fuel cells of both examples thus prepared were held at 80 ° C., and the anode side separator was heated and heated to a dew point of 75 ° C. with hydrogen gas from the other cathode side separator. Air that was humidified and heated to a dew point of ° C. was supplied. As a result, a battery open voltage of 96 V was obtained at no load when no current was output to the outside. Moreover, when the internal resistance of the whole laminated battery at this time was measured, it was about 45 mΩ.

Furthermore, 10 unit cells 8 were prepared for each example, and the variation in pressure loss between the cells was evaluated. As the power generation conditions, power generation was performed at a fuel utilization rate (Uf) of 60%, an oxygen utilization rate (Uo) of 50%, and a current density of 0.2 A / cm ² , and the pressure loss on each anode side and cathode side was measured. As shown in FIG. From this result, it can be seen that the variation of the pressure loss in this example is smaller than that of the comparative example.

  Next, FIG. 9 shows the result of measuring the sag of the MEA into the gas flow path section with an optical microscope by cutting the unit cells 8 of both examples along the II line shown in FIG. From this figure, it can be seen that the present embodiment can suppress the amount of sagging relative to the comparative example.

Next, in order to obtain the limit fuel utilization rate (limit Uf), the following operations were performed on the polymer electrolyte fuel cells of both examples. That is, the fuel utilization rate of the fuel cell was increased by 5% from 50% under conditions of an oxygen utilization rate of 40% and a current density of 0.15 A / cm ² . At this time, the fuel utilization rate is increased by 5% when all the cell voltages are stably operated during the operation of the fuel utilization rate for 5 hours. Then, when the cell voltage became 600 mV or less during the operation for 5 hours, the test was stopped, and the highest oxygen utilization rate at which all the cell voltages could be stably operated was defined as the limiting oxygen utilization rate (limit Uf).

  Next, in order to obtain the limiting oxygen utilization rate (limit Uo), the following operations were performed on the polymer electrolyte fuel cells of both examples. That is, the oxygen utilization rate of the fuel cell was increased from 30% to 5% at a fuel utilization rate of 60% and a current density of 0.3 A / cm 2. At this time, the oxygen utilization rate is increased by 5% when all the cell voltages can be stably operated during the 5-hour operation. Then, when the cell voltage became 600 mV or less during the operation for 5 hours, the test was stopped, and the highest oxygen utilization rate at which all the cell voltages could be stably operated was defined as the critical oxygen utilization rate (limit Uo).

  A polymer electrolyte fuel cell having a larger limit fuel utilization rate (limit Uf) and a greater oxygen utilization rate (limit Uo) has higher stability, and it can be said that the product made of anti-flooding is better. This value was used as an index for evaluating battery characteristics of the polymer electrolyte fuel cell. The results of evaluation in this way are shown in FIG. Thus, it was confirmed that both the critical fuel utilization rate and the critical oxygen utilization rate were greatly improved over the comparative example.

  As described above, according to the configurations of the above-described embodiments and examples, in the polymer electrolyte fuel cell, the convex portion of the fluid flow path is inclined so as to extend in a plane perpendicular to the direction in which the MEAs are stacked. By providing the separator in the separator, it is possible to suppress the pressure loss variation between the individual cells (cells) and to improve the battery characteristics. For this reason, in the polymer electrolyte fuel cell, the manufacturing quality can be improved, and the stability and efficiency can be improved.

  INDUSTRIAL APPLICABILITY The present invention can be applied to polymer electrolyte fuel cells, and in particular to polymer electrolyte fuel cells for portable power supplies, electric vehicle power supplies, household power supplies, domestic cogeneration systems, portable power supplies, building cogeneration, etc. can do.

The perspective view which shows typically a part of cell (unit cell) which is one unit of the polymer electrolyte fuel cell which is embodiment of the fuel cell which concerns on this invention FIG. 1 is a cross-sectional view taken along line II in FIG. Sectional drawing which shows the structure of the modification 1 of this embodiment. The perspective view which shows the structure of the principal part of the modification 2 of this embodiment. Sectional drawing which shows the structure of the conventional cell as a comparative example Explanatory drawing which shows the basic composition for extending MEA in this embodiment The figure which shows the result of the tensile strength test of MEA in this embodiment Comparison diagram of pressure loss in the embodiment according to the present invention and the comparative example Comparison diagram of amount of sag of MEA into gas flow path in embodiment and comparative example according to present invention The figure which shows the result of the battery characteristic evaluation in the Example which concerns on this invention, and a comparative example

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Separator on the anode side 2 Separator on the cathode side 3, 4 Projection 5 MEA (membrane electrode assembly)
6, 7 Fluid flow path 8 Single cell 9 Proton conductive polymer electrolyte membrane 10 Reaction electrode (gas diffusion layer)
11 Electrode (catalyst layer)
13 Concavities and convexities at the top of the convex part

Claims (11)

A polymer electrolyte membrane, an MEA (membrane electrode assembly) composed of a pair of electrodes sandwiching the polymer electrolyte membrane, and a pair of separators sandwiching the MEA, and in contact with the polymer electrolyte membrane as the electrodes In a fuel cell formed by laminating a plurality of cells each having a catalyst layer and a gas diffusion layer in contact with the separator,
A fuel cell, wherein the separator is provided with a convex portion and a concave portion serving as a fluid flow path, and an inclined portion is formed on the convex portion.   2. The fuel cell according to claim 1, wherein a sagging amount of the gas diffusion layer into a recess serving as a fluid flow path of the separator is not less than 0% and less than 20% of a depth of the recess.   The cross-sectional dimensions in the fluid flow direction of each of the convex portions facing each other in the fluid flow path of the separator are different, and the cross-sectional dimensions in the fluid flow direction of the entire convex portion when the convex portions are joined are the same. The fuel cell according to claim 1 or 2.   The slope of 0 degree or more and less than 40 degree | times was formed in the top part of the said convex part of the said separator with respect to the surface orthogonal to the lamination direction of the said cell. The fuel cell as described.   The fuel cell according to any one of claims 1 to 4, wherein the recesses adjacent to each other have the same cross-sectional dimension in the fluid flow direction.   The fuel cell according to any one of claims 1 to 5, wherein the convex portions adjacent to the separator have the same cross-sectional dimension in the fluid flow direction.   The fuel cell according to any one of claims 1 to 6, wherein unevenness is formed on at least a part of the top of the convex portion of the separator.   The fuel cell according to claim 7, wherein a convex portion of the concave and convex portions at the top of the convex portion is inclined by 0 degree or more and less than 40 degrees on a plane perpendicular to the stacking direction of the cells.   The fuel cell according to claim 7 or 8, wherein the concave and convex portions adjacent to the concave and convex portions at the top of the convex portion have the same dimensional shape.   The fuel cell according to any one of claims 7 to 9, characterized in that the size and shape of the convex portions adjacent to the concave and convex portions at the top of the convex portion are the same.   The fuel cell according to claim 1, wherein the gas diffusion layer is made of carbon cloth or carbon paper, and the MEA has an elongation of 0% or more and less than 30%.

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