CN113224365B - Catalyst-free self-hydrogen-production composite fuel cell system - Google Patents
Catalyst-free self-hydrogen-production composite fuel cell system Download PDFInfo
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- CN113224365B CN113224365B CN202110404224.9A CN202110404224A CN113224365B CN 113224365 B CN113224365 B CN 113224365B CN 202110404224 A CN202110404224 A CN 202110404224A CN 113224365 B CN113224365 B CN 113224365B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04052—Storage of heat in the fuel cell system
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
- H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
- H01M8/04164—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by condensers, gas-liquid separators or filters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
- H01M8/2495—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies of fuel cells of different types
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides a catalyst-free self-hydrogen-production composite fuel cell system, which comprises a metal air cell, a proton exchange membrane fuel cell and NaBH 4 A hydrogen supply unit and a metal-air battery hydrogen supply unit; the NaBH 4 The hydrogen supply unit comprises a first phase change energy storage body and a first water-gas separator, and the metal air battery hydrogen supply unit comprises an alkali removing box and a second water-gas separator; the invention releases hydrogen and NaBH through the discharge reaction of the metal-air battery 4 The hydrogen released by the hydrolysis reaction provides hydrogen required by the discharge reaction for the proton exchange membrane fuel cell, so that the sufficient hydrogen supply amount is ensured; further, due to the placement of NaBH 4 The container(s) is a first phase change energy storage body which can be NaBH 4 The hydrolysis reaction of (2) provides high temperature, so that an additional catalyst placing structure is not needed, and the hydrogen supply structure of the proton exchange membrane fuel cell is obviously simplified.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a catalyst-free self-hydrogen-production composite fuel cell system.
Background
A Proton Exchange Membrane Fuel Cell (PEMFC), which is a fuel cell and is equivalent to a reverse device for water electrolysis in principle, wherein a single cell comprises an anode, a cathode and a proton exchange membrane, the anode is a place where hydrogen fuel is oxidized, the cathode is a place where an oxidant is reduced, the anode and the cathode both contain a catalyst for accelerating the electrochemical reaction of the electrodes, and the proton exchange membrane is used as an electrolyte; the discharge operation is equivalent to a direct current power supply, the anode of the direct current power supply is the negative pole of the power supply, the cathode of the direct current power supply is the positive pole of the power supply, and the specific method comprises the following steps:
the anode (power supply cathode) reaction of the proton exchange membrane fuel cell is as follows: 2H 2 -4e→4H + ；
The cathode (power supply anode) reaction of the proton exchange membrane fuel cell is as follows: o is 2 +4e+4H + →2H 2 0；
Since the proton exchange membrane can only conduct protons, hydrogen protons can directly pass through the proton exchange membrane to reach the cathode, electrons can only reach the cathode through an external circuit, and direct current is generated when the electrons flow to the cathode through the external circuit.
In recent years, proton exchange membrane fuel cells are increasingly widely used, but a convenient and directly available hydrogen supply method and a safe, efficient, economical and portable hydrogen storage technology are lacked; in the patent "an integrated power generation system based on air battery" (CN 208819993U), the hydrogen gas generated by the metal-air battery is supplied to the proton exchange membrane fuel cell to solve the above-mentioned problems of hydrogen supply and storage, taking an aluminum-air battery as an example:
the discharge reaction equation of the aluminum air fuel cell is as follows: 2Al +6H 2 0→2Al(OH) 3 +3H 2 ；
Therefore, the hydrogen generated by the aluminum air battery reaction can be supplied to the proton exchange membrane fuel cell for use, but the problems of small hydrogen production and uncontrollable hydrogen production exist; in the presence of catalyst, sodium borohydride (NaBH) 4 ) Hydrolysis reaction can occur in alkaline aqueous solution to generate hydrogen and water-soluble sodium borate (NaBO) 2 ) The reaction equation is as follows:
NaBH 4 +2H 2 O →4H 2 +NaBO 2 ；
thus, NaBH can be utilized 4 As a source of hydrogen, but NaBH 4 The hydrolysis reaction is influenced by temperature obviously, in particular, under the condition of low temperature, NaBH 4 The hydrolysis reaction can take place in the presence of a catalystThe hydrolysis reaction can be carried out to release hydrogen under the high-temperature condition without a catalyst; therefore, in order to simplify the hydrogen supply structure of the proton exchange membrane fuel cell, i.e., the structure for removing the catalyst case, NaBH is required 4 Providing a high temperature hydrolysis environment, but this structure is not available in the prior art.
Disclosure of Invention
The invention aims to provide a catalyst-free self-hydrogen-generating composite fuel cell system, which aims to solve the problem.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst-free self-hydrogen-production composite fuel cell system comprises a metal air cell and a proton exchange membrane fuel cell, wherein the metal air cell consists of a pile box, an electrolyte box and a circulating pump, and the circulating pump is used for circulating electrolyte in the electrolyte box between the pile box and the electrolyte box through a pipeline; also included are NaBH 4 A hydrogen supply unit and a metal-air battery hydrogen supply unit;
the NaBH 4 The hydrogen supply unit comprises a first phase change energy storage body and a first water-gas separator, wherein the first phase change energy storage body consists of a shell, a cooling pipe, a phase change material layer and a heat insulation layer; phase change material layer and heat preservation from interior to exterior set gradually in the shell, the cooling tube passes proton exchange membrane fuel cell and coils and form closed circuit outside phase change material layer after getting into the shell, be provided with coolant in the cooling tube, place NaBH in the synthetic cavity of phase change material layer enclosure 4 The end part of the shell is provided with a water inlet and a gas outlet, the water inlet of the first phase change energy storage body is communicated with the water outlet of the proton exchange membrane fuel cell, the gas outlet of the first phase change energy storage body is communicated with the gas inlet of the first water-gas separator, the gas outlet of the first water-gas separator is communicated with the gas inlet of the proton exchange membrane fuel cell, and the water outlet of the first water-gas separator is communicated with the water inlet of the first phase change energy storage body;
the hydrogen supply unit of the metal air battery comprises an alkali removal box and a second water-gas separator, wherein an air outlet on the galvanic pile box is communicated with an air inlet of the second water-gas separator through the alkali removal box, an air outlet of the second water-gas separator is communicated with an air inlet of the proton exchange membrane fuel battery, and a water outlet of the second water-gas separator is communicated with a water inlet of the first phase change energy storage body.
The shell of the first phase change energy storage body is cylindrical, and a phase change material layer and a heat preservation layer are sequentially arranged in the cylindrical shell from inside to outside by taking the central axis of the shell as the center.
The position that corresponds with the water inlet in the shell of the first phase change energy storage body be provided with the samming dish, evenly seted up a plurality of apertures on the samming dish.
The phase change material layer is paraffin, and the cooling medium is water.
The first water-gas separator and the second water-gas separator both adopt condensation type water-gas separators, each condensation type water-gas separator comprises an air inlet pipe, an air outlet pipe, a condensation cavity, an water outlet pipe and a guide plate, the air inlet pipes, the condensation cavity and the air outlet pipes are sequentially communicated, the cross sectional area of the condensation cavity is larger than that of the air inlet pipes, the air inlet of the air inlet pipes is used as the air inlet of the condensation type water-gas separators, the air outlet of the air outlet pipes is used as the air outlet of the condensation type water-gas separators, the water outlet pipes are communicated with the lower portion of the condensation cavity and downwards incline, the water outlet of the water outlet pipes is used as the water outlet of the condensation type water-gas separators, the guide plates are arranged at the connecting positions of the air inlet pipes and the condensation cavity in the air inlet pipes, and the water outlet ends of the guide plates incline towards the water outlet pipes.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to hydrogen and NaBH released by the discharge reaction of a metal-air battery 4 The hydrogen released by the hydrolysis reaction provides hydrogen required by the discharge reaction for the proton exchange membrane fuel cell, so that the sufficient hydrogen supply amount is ensured; further, due to the placement of NaBH 4 The container(s) is a first phase change energy storage body which can be NaBH 4 The hydrolysis reaction of (2) provides high temperature, so that an additional catalyst placing structure is not needed, and the hydrogen supply structure of the proton exchange membrane fuel cell is obviously simplified.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a functional block diagram of the present invention;
FIG. 2 is a schematic structural diagram of a first phase change energy storage body according to the present invention;
fig. 3 is a schematic structural diagram of the condensation type water separator.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, 2 and 3: the invention relates to a catalyst-free self-hydrogen-production composite fuel cell system, which comprises a metal air cell 1 and a proton exchange membrane fuel cell 2, wherein the metal air cell 1 consists of a pile box 11, an electrolyte box 12 and a circulating pump 13, and the circulating pump 13 is used for circulating electrolyte in the electrolyte box 12 between the pile box 11 and the electrolyte box 12 through a pipeline; also comprises a NaBH4 hydrogen supply unit 3 and a metal-air battery hydrogen supply unit 4; the NaBH4 hydrogen supply unit 3 comprises a first phase change energy storage body 31 and a first water-gas separator 32, wherein the first phase change energy storage body 31 consists of a shell 311, a cooling pipe 312, a phase change material layer 313 and a heat insulation layer 314; the phase change material layer 313 and the heat preservation layer 314 are sequentially arranged in the shell 311 from inside to outside, the cooling pipe 312 penetrates through the proton exchange membrane fuel cell 2, enters the shell 311, is coiled outside the phase change material layer 313 to form a closed loop, a cooling medium is arranged in the cooling pipe 312, and NaBH is placed in a cavity 315 enclosed by the phase change material layer 313 4 The end of the housing 311 is provided with a water inlet and an air outlet, and the water inlet and the mass of the first phase change energy storage body 31The water outlet of the proton exchange membrane fuel cell 2 is communicated, the air outlet of the first phase change energy storage body 31 is communicated with the air inlet of the first water-gas separator 32, the air outlet of the first water-gas separator 32 is communicated with the air inlet of the proton exchange membrane fuel cell 2, and the water outlet of the first water-gas separator 32 is communicated with the water inlet of the first phase change energy storage body 31; the hydrogen supply unit 4 of the metal air battery comprises an alkali removal box 41 and a second water-gas separator 42, an air outlet on the galvanic pile box 11 is communicated with an air inlet of the second water-gas separator 42 through the alkali removal box 41, an air outlet of the second water-gas separator 42 is communicated with an air inlet of the proton exchange membrane fuel battery 2, and a water outlet of the second water-gas separator 42 is communicated with a water inlet of the first phase-change energy storage body 31.
The working principle of the catalyst-free self-hydrogen-production composite fuel cell system provided by the invention is as follows:
when the metal-air battery 1 is operated, taking an aluminum-air battery as an example: the discharge reaction equation of the aluminum air fuel cell is as follows: 2Al +6H 2 0→2Al(OH) 3 +3H 2 (ii) a That is, hydrogen is released when the metal-air battery 1 performs a discharge reaction, and since the electrolyte of the metal-air battery 1 is generally alkaline, in order to prevent the alkaline electrolyte from damaging the proton exchange membrane fuel cell 2 along with the hydrogen, the hydrogen released by the metal-air battery 1 firstly passes through the alkali removal tank 41, the alkali removal agent is placed in the alkali removal tank 41, the hydrogen after alkali removal enters the second water-gas separator 42, water vapor mixed in the hydrogen is condensed into liquid water through the condensation effect of the second water-gas separator 42, and enters the first phase change energy storage body 31, which is NaBH 4 The hydrolysis reaction of the hydrogen supply system provides water, and the hydrogen dried by the second water-gas separator 42 enters the proton exchange membrane fuel cell 2 to provide hydrogen required by the discharge reaction for the proton exchange membrane fuel cell 2; further, water generated during the discharging reaction of the pem fuel cell 2 also enters the first phase-change energy storage body 31, which is NaBH 4 To ensure NaBH in the first phase change energy storage body 31 4 The phase change material used in the phase change material layer 313 has a phase change temperature of about 70 degrees, in which case NaBH is used 4 Without catalyst, hydrolysis reaction can occur to release hydrogen and releaseThe hydrogen enters the proton exchange membrane fuel cell 2 after being dried by the first water-gas separator 32, the hydrogen required by the discharge reaction is provided for the proton exchange membrane fuel cell 2, and the condensed water in the first water-gas separator 32 also enters the first phase change energy storage body 31 to be NaBH 4 The hydrolysis reaction of (a) provides sufficient water; in the above process, the cooling medium in the cooling tube 312 of the first phase change energy storage body 31 supplies energy to the phase change material by absorbing the heat released during the discharge reaction of the pem fuel cell 2, and the insulating layer 314 prevents the heat from dissipating, thereby ensuring NaBH 4 The hydrolysis reaction of (3) proceeds smoothly.
Preferably: the shell 311 of the first phase change energy storage body 31 is cylindrical, the phase change material layer 313 and the heat preservation layer 314 are sequentially arranged in the cylindrical shell 311 from inside to outside by taking the central axis of the shell 311 as the center, and the water inlet hole of the first phase change energy storage body 31 is correspondingly formed in the central position of the end part of the shell 311 so as to ensure that the water entering the shell 311 can be matched with NaBH 4 Contacting NaBH 4 The hydrolysis reaction proceeds smoothly.
Preferably: the position that corresponds with the water inlet in the shell 311 of the first phase change energy storage body 31 is provided with the liquid-equalizing disc 316, a plurality of apertures are evenly opened on the liquid-equalizing disc 316 to guarantee that the water entering the shell 311 can be sufficient enough to NaBH 4 And (4) contacting.
Preferably: the phase change material layer 313 is paraffin, and the cooling medium is water.
Preferably: the first water-gas separator 32 and the second water-gas separator 42 both adopt condensation type water-gas separators, each condensation type water-gas separator comprises a gas inlet pipe 52, a gas outlet pipe 53, a condensation cavity 51, a water outlet pipe 54 and a flow guide plate 55, the gas inlet pipe 52, the condensation cavity 51 and the gas outlet pipe 53 are sequentially communicated, the cross sectional area of the condensation cavity 51 is larger than that of the gas inlet pipe 52, a gas inlet of the gas inlet pipe 52 serves as a gas inlet of the condensation type water-gas separator, a gas outlet of the gas outlet pipe 53 serves as a gas outlet of the condensation type water-gas separator, the water outlet pipe 54 is communicated with the lower part of the condensation cavity 51 and inclines downwards, a water outlet of the water outlet pipe 54 serves as a water outlet of the condensation type water-gas separator, the flow guide plate 55 is arranged at the connecting position of the gas inlet pipe 52 and the condensation cavity 51 in the gas inlet pipe 52, and a water outlet end of the flow guide plate 55 inclines towards the water outlet pipe 54; therefore, after the hydrogen mixed with the water vapor meets the enlarged condensation cavity 51 through the air inlet pipe 52, the pressure is reduced, the temperature is reduced, and the water vapor is condensed into liquid water and flows out of the water outlet pipe 54 under the flow guiding effect of the flow guiding pipe.
The catalyst-free self-hydrogen-generating composite fuel cell system has the beneficial effects that:
in the invention, hydrogen and NaBH released by discharge reaction of the metal-air battery 1 4 The hydrogen released by the hydrolysis reaction provides the hydrogen required by the discharge reaction for the proton exchange membrane fuel cell 2, so that the sufficient hydrogen supply amount is ensured; further, due to the placement of NaBH 4 The container of (1) is a first phase change energy storage body 31, which can be NaBH 4 The hydrolysis reaction of (2) provides high temperature, so that an additional catalyst placing structure is not needed, and the hydrogen supply structure of the proton exchange membrane fuel cell (2) is obviously simplified.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A catalyst-free self-hydrogen-production composite fuel cell system comprises a metal air cell and a proton exchange membrane fuel cell, wherein the metal air cell consists of a pile box, an electrolyte box and a circulating pump, and the circulating pump is used for circulating electrolyte in the electrolyte box between the pile box and the electrolyte box through a pipeline; the method is characterized in that: also included are NaBH 4 A hydrogen supply unit and a metal-air battery hydrogen supply unit;
the NaBH 4 The hydrogen supply unit comprises a first phase change energy storage body and a first water-gas separator, wherein the first phase change energy storage body consists of a shell, a cooling pipe, a phase change material layer and a heat preservation layerLayer composition; phase change material layer and heat preservation from inside to outside set gradually in the shell, the cooling tube passes proton exchange membrane fuel cell and coils after getting into the shell and forms closed circuit outside the phase change material layer, be provided with coolant in the cooling tube, placed NaBH in the synthetic cavity of phase change material layer periphery 4 The end part of the shell is provided with a water inlet and a gas outlet, the water inlet of the first phase change energy storage body is communicated with the water outlet of the proton exchange membrane fuel cell, the gas outlet of the first phase change energy storage body is communicated with the gas inlet of the first water-gas separator, the gas outlet of the first water-gas separator is communicated with the gas inlet of the proton exchange membrane fuel cell, and the water outlet of the first water-gas separator is communicated with the water inlet of the first phase change energy storage body;
the hydrogen supply unit of the metal air battery comprises an alkali removal box and a second water-gas separator, wherein an air outlet on the galvanic pile box is communicated with an air inlet of the second water-gas separator through the alkali removal box, an air outlet of the second water-gas separator is communicated with an air inlet of the proton exchange membrane fuel battery, and a water outlet of the second water-gas separator is communicated with a water inlet of the first phase change energy storage body.
2. The catalyst-free self-hydrogen-generating composite fuel cell system according to claim 1, characterized in that: the shell of the first phase change energy storage body is cylindrical, and a phase change material layer and a heat preservation layer are sequentially arranged in the cylindrical shell from inside to outside by taking the central axis of the shell as the center.
3. The catalyst-free self-hydrogen-generating hybrid fuel cell system according to claim 2, characterized in that: the position that corresponds with the water inlet in the shell of the first phase change energy storage body be provided with the samming dish, evenly seted up a plurality of apertures on the samming dish.
4. The catalyst-free self-hydrogen-generating hybrid fuel cell system according to claim 3, characterized in that: the phase change material layer is paraffin, and the cooling medium is water.
5. The catalyst-free self-hydrogen-generating hybrid fuel cell system according to claim 4, wherein: the first water-gas separator and the second water-gas separator both adopt condensation type water-gas separators, each condensation type water-gas separator comprises an air inlet pipe, an air outlet pipe, a condensation cavity, a water outlet pipe and a guide plate, the air inlet pipes, the condensation cavity and the air outlet pipes are sequentially communicated, the cross sectional area of the condensation cavity is larger than that of the air inlet pipes, the air inlet of the air inlet pipes serves as the air inlet of the condensation type water-gas separators, the air outlet of the air outlet pipes serves as the air outlet of the condensation type water-gas separators, the water outlet pipes are communicated with the lower portions of the condensation cavities and incline downwards, the water outlets of the water outlet pipes serve as the water outlets of the condensation type water-gas separators, the guide plates are arranged at the connecting positions of the air inlet pipes and the condensation cavities in the air inlet pipes, and the water outlets of the guide plates incline towards the water outlet pipes.
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| CN102055046A (en) * | 2009-11-06 | 2011-05-11 | 天津市斗星机械设备有限公司 | Bifuel battery unit of electric vehicle |
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| CN203112493U (en) * | 2012-11-07 | 2013-08-07 | 陈尧春 | Solar fuel cell vehicle system |
| CN103579652A (en) * | 2013-06-25 | 2014-02-12 | 哈尔滨工业大学（威海） | Fuel-cell power generation system for supplying hydrogen by hydrolyzing magnesium hydride |
| CN107799789A (en) * | 2016-09-05 | 2018-03-13 | 北京晟泽科技有限公司 | A kind of unmanned plane fuel cell reaction water management system |
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