The present invention relates to a coolant composition, a cooling system, and a method for producing the coolant composition. More specifically, it relates to a coolant composition that shows stable insulation properties, used for a fuel cell, particularly for a vehicle-mounted fuel cell.
Generally, a fuel cell stack has a stacked structure of a plurality of cells, in which cooling plates for cooling the stack (cells) are inserted between individual substacks, each substack composed of a few layers of cells. A coolant channel is formed inside the cooling plate, and the stack is cooled by the flow of coolant through the coolant channel. In this way, since such coolant for a fuel cell circulates between the stack where electric power is generated and the heat exchanger, high insulation performance is required in order to prevent electric leak to the outside of the stack and decrease in electrical efficiency caused by the resistance in the coolant (reduction of energy loss).
In order to meet such demands of ensuring insulation performance, cooling efficiency, and the like, pure water has been used as a coolant in conventional technologies. In addition to such demands, anti-rust properties are required for a fuel cell stack coolant in order to maintain a long product life of cooling plates. This requirement has been generally addressed by using a stainless-steel material with high anti-rust properties for cooling plates or by adding iron ions to the coolant, as disclosed in JP Patent Publication (Kokai) No. 2-21572 A (1990).
However, while such conventional approaches are effective for so-called fixed, stationary-type, medium-or large-size fuel cells, or constantly operating fuel cells, they are not necessarily effective for non-stationary, small fuel cells or intermittently operating fuel cells, such as fuel cells installed in vehicles.
For example, since the temperature of the coolant in intermittently operating, non-stationary fuel cells falls to ambient temperature when the cell is not in operation, anti-freezing properties are required for the coolant under conditions where the ambient temperature is the freezing point or lower. This is because, if the coolant freezes, the cooling circuit including cooling plates may be damaged. Furthermore, when the cooling circuit is damaged, possibly fuel cells do not operate sufficiently.
In this situation, taking anti-freezing properties into account, use of a coolant for cooling an internal combustion engine as a non-freezing coolant is an option. However, since such coolant for cooling an internal combustion engine is basically used in the area where no electricity is generated, low conductivity is not expected, and therefore, the coolant has extremely high electric conductivity. Meanwhile, since electricity flows through a cooling pipe of a fuel cell stack, when the coolant has a high electric conductivity, the electricity generated in the fuel cell flows into the coolant, thereby losing electricity. For this reason, such coolant is not suitable as a coolant for cooling a fuel cell stack.
Further, in the case of non-stationary fuel cells installed in vehicles or the like, reducing the weight of a fuel cell system including a cooling circuit is an important issue to be solved. Therefore, from the viewpoint of weight saving, light metals having high thermal conductivity, such as aluminum materials, are expected to be used for cooling plates, heat exchangers, and the like. Generally, the anti-rust properties of such light metals are not as high as those of stainless-steel materials, and therefore, the coolant itself is required to have anti-rust properties.
Given this, the present inventors invented a coolant containing a base composed of a mixed solution of water and glycol, and an anti-rust additive that maintains the conductivity of the coolant low and that maintains the hydrogen ion exponent of the coolant at approximately neutral, which was published as JP Patent Publication (Kokai) No. 2001-164244 A. Examples of such anti-rust additive include weak alkaline additives, weak acidic additives, and nonionic substances. Saccharides such as quercetin and nonionic surface active agent such as alkylglucoside are disclosed as nonionic substances.
Further, with the aim of reducing wasteful energy consumption as much as possible by controlling the conductivity of a primary coolant even when required electric power with respect to a fuel cell increases or decreases, JP Patent Publication (Kokai) No. 2002-100383 A discloses removing ions in the primary coolant by causing a portion of the primary coolant discharged from a heat exchanger to flow into an ion exchanger.
The coolant disclosed in JP Patent Publication (Kokai) 2001-164244 A is a fuel cell stack coolant having low conductivity, anti-rust properties, high heat transfer properties, and anti-freezing properties. However, since most of the additives are ionic, the coolant is problematic in its insulation properties. Further, the cooling system disclosed in JP Patent Publication (Kokai) No. 2002-100383 A is not necessarily effective for non-stationary, small fuel cells, such as vehicle-mounted fuel cells.
In existing fuel cell vehicles, from the viewpoint of heat transfer characteristics, a water-based coolant is adopted, and ion exchange resin or the like is mounted in a vehicle to deal with insulation properties, thereby removing ionic products based on elution from parts or degradation of the coolant. The ion exchange resin is contained in a container with a capacity of 100 to 500 cc, and the cooling water path is provided with a bypass circuit due to large pressure loss. Ionic products are removed by causing a certain amount (small amount) of coolant to flow through the portion. Further, in order to suppress an increase in conductivity due to eluted substance from parts in the initial stages, the inside of parts in the cooling system is washed with pure water before assembling the parts, and also, the coolant is caused to circulate for a certain period of time after assembling a vehicle, so as to remove the ionic products.
In the system in which ion exchange resin is installed as in conventional technologies, since the ion exchange resin is disposed in a bypass circuit of a cooling water system, an increase in conductivity due to ionic products eluted from parts in the initial stages cannot be suppressed. Thus, measures, such as washing the inside of each part of the cooling system, are necessary. Furthermore, parts (pipes, containers, and the like) or space for mounting the ion exchange resin, and control of the flow rate are necessary.
The present invention has been made to solve the above problems, and an object thereof is to stably maintain insulation properties of coolant by using the present invention as a fuel cell stack coolant from the viewpoint of high-voltage safety and removing eluted substance from the cooling system parts in the initial stages and with the passage of time.
In the present invention, the above problems are solved by allowing a coolant composition itself to have a function of removing ionic eluted substance in a timely manner.
Namely, in a first aspect, the present invention is an invention of a coolant composition itself, and it is characterized in that ion exchange resin is uniformly dispersed in a water-based coolant. It is preferable that the density of the coolant is approximately the same as that of the ion exchange resin, and the ion exchange resin is miniaturized, so as to improve the dispersibility of the ion exchange resin. One or more kinds of carbides for adjusting density, such as metal powder, metal oxide powder, inorganic oxide powder, and silicon carbide, can be mixed with the coolant, in order to make the density of the coolant approximately the same as that of the ion exchange resin.
It is preferable that (1) the ion exchange resin has a heat resistance of 80° C. or higher, (2) the average particle diameter thereof is 300μ or less, and (3) the dispersion amount thereof is 30 vol % or less. Further, use of both anion exchange resin and cation exchange resin as the ion exchange resin is effective in removing all ionic eluted substance in a timely manner.
Glycol and/or alcohol can be added to the water-based coolant for the purpose of improving anti-freezing properties. Further, nonionic surface active agent can be added to the water-based coolant, so as to improve the dispersibility of the ion exchange resin.
The above coolant is suitably used for a fuel cell. Particularly, it is suitably used for a vehicle-mounted fuel cell.
In a second aspect, the present invention is a fuel cell cooling system including a cooling circuit in which the above coolant composition and inert gas if desired are included. In this cooling system, the vehicle can be filled with the coolant in which the above ion exchange resin is dispersed in advance, and ions eluted from parts in the cooling system in the initial stages can be removed in a timely manner by the ion exchange resin dispersed in the coolant. Further, high insulation properties can be obtained in this cooling system. Also, it is possible to prevent deterioration in quality of the coolant composition in the cooling circuit over a long period of time. By performing deoxygenation treatment in which inert gas such as nitrogen (N2) is injected, dissolved oxygen in the coolant composition decreases, thereby suppressing corrosion of aluminum material and maintaining insulation properties for long periods of time. Thus, by subjecting the coolant composition to deoxygenation treatment using nitrogen gas or the like, aluminum material used as material for forming the coolant circuit can be prevented from corrosion.
In a third aspect, the present invention is a fuel cell cooling system including a cooling circuit in which the above coolant composition and inert gas if desired are included, and an ion exchange resin container as a bypass circuit of the above cooling circuit. This means that the coolant composition of the present invention is used in a conventional fuel cell cooling system including such ion exchange resin container as a bypass circuit of the cooling circuit. The ion exchange resin container referred to in the present invention is a container that has an inlet port and an outlet port for the coolant and that has a cylindrical shape or the like. The inside of the container is filled with pellet-type ion exchange resin. Alternatively, an ion exchange resin film is disposed in the inside of the container, for example.
Since the ion exchange resin container is provided as a bypass circuit of the cooling circuit, (1) the vehicle is filled with the coolant in which the above ion exchange resin is dispersed in advance, (2) ions eluted from parts in the cooling system in the initial stages are removed in a timely manner by the ion exchange resin dispersed in the coolant, (3) the ion exchange resin dispersed in liquid is collected by the filter effect of the vehicle-mounted ion exchange resin in the bypass circuit of the cooling system, and (4) degraded substance or eluted substance gradually generated or eluted with the passage of time is removed by the vehicle-mounted ion exchange resin.
In a fourth aspect, the present invention is an invention of a method for producing the above coolant composition, and it is characterized in that a water-based coolant is adjusted so that ion exchange resin is dispersed in the above coolant. It is possible to improve the dispersibility of the ion exchange resin by making the density of the coolant and that of the ion exchange resin approximately the same. Specifically, this can be achieved by mixing one or more kinds of carbides for adjusting density, such as metal powder, metal oxide powder, inorganic oxide powder, and silicon carbide, with the coolant, or by selecting ion exchange resin having a density approximately the same as that of the coolant.
In a fifth aspect, the present invention is an invention of a method for storing a coolant composition, and it is characterized in that ion exchange resin is allowed to coexist in a water-based coolant. The present invention is a preservation method by which an increase in conductivity due to decomposition of ethylene glycol or the like is suppressed by allowing the coolant composition to coexist with the ion exchange resin in advance.
In the present invention, in terms of handling, it is preferable that the ion exchange resin is allowed to coexist in the water-based coolant in a state in which the ion exchange resin is contained in a meshed or fabric package, instead of dispersing it in the base.
Preferably, the water-based coolant to which the present invention is applied contains 0 to 70 wt % of glycol and 0 to 60 wt % of alcohol with respect to water.
In a sixth aspect, the present invention is an invention of an apparatus for collecting, exchanging, and reproducing the above coolant composition in which the ion exchange resin is dispersed in the water-based coolant with respect to a fuel cell body. The apparatus for collecting, exchanging, and reproducing a coolant composition includes a filter for separating collected coolant into a base and ion exchange resin, a filling tank for storing the separated base, a pure water tank for collecting the separated ion exchange resin and separating it into anion exchange resin and cation exchange resin based on the difference in specific gravity, a processing bath for chemically reproducing the separated anion exchange resin and cation exchange resin, a means of injecting the reproduced ion exchange resin into the filling tank and agitating it therein, and a pump for filling the fuel cell body with the reproduced coolant composition.
The fuel cell body as used herein constitutes a fuel cell vehicle, and it is preferable that the apparatus of the present invention for collecting, exchanging, and reproducing a coolant composition is installed at a fuel supply station for fuel cells.
By uniformly dispersing ion exchange resin in a water-based coolant, the coolant composition itself is allowed to have the function of removing ionic eluted substance in a timely manner. Thus, when the coolant composition of the present invention is used for a fuel cell stack, eluted substance from parts in the cooling system in the initial stages and with the passage of time is removed, whereby the insulation properties of the coolant can be stably maintained and an expected purpose of obtaining high-voltage safety can be accomplished.
Further, by allowing the ion exchange resin to coexist in ethylene glycol aqueous solution, the insulation properties of the coolant in a fuel cell system can be improved during a storage period, whereby an increase in conductivity during the storage period can be suppressed.
A coolant composition of the present invention will be hereafter described with reference to examples and comparative examples.
Ion exchange resin was added to ethylene glycol (EG) 50% aqueous solution and it was then dispersed (example 1). On the other hand, instead of dispersing the ion exchange resin in ethylene glycol (EG) 50% aqueous solution, a test equipment was equipped with the ion exchange resin in a bypass circuit (comparative example 1). The ion exchange resin used in comparative example 1 was as follows: the cell size; φ50×200, the flow rate; 40 ml/min, the amount of ion exchange resin; 330 ml, and the arrangement of ion exchange resin; lying position (simulation using an actual vehicle).
Table 1 shows several properties of the coolant compositions in example 1 and comparative example 1.
A circulation bench test simulating a cooling system was conducted using the coolant compositions of example 1 and comparative example 1. Taking into account that aluminum and aluminum alloy are used as materials for cooling plates, a heat exchanger in a cooling circuit, and the like, when a fuel cell is mounted in a vehicle, particularly, aluminum materials were used in the example and comparative example in the present invention. Test conditions of the evaluation equipment are as follows:
The results in
A fuel cell stack cooling system including the above coolant composition as a refrigerant will be hereafter described with reference to
Referring to
In the present example, the separator 24 is provided either as an end separator 40 or as a central separator 50. Each of the cooling separator 30, and these separators 40 and 50 has a shape of a plate whose surface to be stacked is square. Each of the cooling separator 30, the end separator 40, and the central separator 50 is provided with coolant holes 81 and 82 having circular cross-sections formed in two portions (upper corners in
The cooling separator 30 is connected to an external cooling circuit 32 via a coolant path to form a cooling circuit 34 including the cooling separator 30. A plurality of parallel, groove-shaped ribs 63 communicating between the opposing oxidation gas holes 85 and 86 are formed on one side of the cooling separator 30 (on the rear side in
A plurality of parallel, groove-shaped ribs 62 communicating between the opposing fuel gas holes 83 and 84 are formed on one side of the end separator 40 (on the front side in
A plurality of parallel, groove-shaped ribs 62 communicating between the opposing fuel gas holes 83 and 84 are formed on one side of the central separator 50 (on the front side in
While the above-described separators 24 (40 and 50) are formed of compact carbon, the separators may be formed of another material having conductivity. For example, from the viewpoint of rigidity and heat transfer properties, the separators may be formed of metal, such as copper alloy or aluminum alloy.
The above coolant composition is used as the coolant in the cooling circuit. When the coolant composition is included in the cooling circuit 34, inert gas, e.g., nitrogen gas is included therein together. Therefore, dissolved oxygen in the air and the coolant composition in the cooling circuit 34 is replaced with nitrogen gas, and thus deterioration of the coolant composition caused by dissolved oxygen can be prevented.
The schematic diagrams of the fuel cell stack cooling system shown in
Further, in the above example, particularly an aluminum material was used for the cooling circuit including the cooling plates. However, use of another material for the cooling circuit is not excluded.
Coolants having the composition shown in Table 2 below were left to stand in airtight containers in a constant-temperature bath at 30° C. The conductivity was measured at 5-week intervals.
Regarding the cause of such increase in conductivity in a state of storage, it is known that a mixed solution comprised of ethylene glycol and ion-exchange water deteriorates by oxidation at high temperatures and generates formic acid and glycolic acid, thereby increasing conductivity. However, the conductivity was increased even in the state of storage at 30° C. As a result of examining the composition, it was found that formic acid alone was generated. Thus, it can be thought that conductivity was increased because a slight amount of ester of formic acid contained in the ethylene glycol generated formic acid on hydrolysis after mixed with the ion-exchange water.
The exchanging unit is provided with a filter 3 for separating ion exchange resin when a coolant is collected from a vehicle. Upon completion of resin collection, when the vehicle is filled with the coolant in which ion exchange resin is dispersed, the coolant is not allowed to pass through the filter 3. The exchanging unit is provided with a filling tank 7 in which reproduced or new ion exchange resin is dispersed.
The reproducing unit is provided with a pure water (separation) tank 4 for separating the ion exchange resin collected from the filter 3 into cation exchange resin and anion exchange resin. Separation is conducted based on difference in specific gravity between the resins. The reproducing unit is provided with tanks 5 and 6 for reproducing the separated resins.
The following problems can be solved with the apparatus of the present invention for collecting, exchanging, and reproducing a coolant composition.
An example of a specific procedure of collecting, exchanging, and reproducing a coolant, with the use of the apparatus of the present invention for collecting, exchanging, and reproducing a coolant composition, will be hereafter described.
1. Collect Ion Exchange Resin from the Coolant in the Vehicle.
When a coolant composition obtained by uniformly dispersing ion exchange resin in a water-based coolant is used for a fuel cell stack, as in the present invention, eluted substance from parts in the cooling system is removed in the initial stages and with the passage of time, whereby insulation properties of the coolant can be stably maintained and a coolant composition for a fuel cell that is safe at high voltage can be obtained. Thus, the present invention is effective in spreading fuel cell vehicles.
Number | Date | Country | Kind |
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2004-215420 | Jul 2004 | JP | national |
2005-212563 | Jul 2005 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP05/13895 | 7/22/2005 | WO | 1/22/2007 |