WO2011135932A1 - Dispositif de pile à combustible - Google Patents

Dispositif de pile à combustible Download PDF

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Publication number
WO2011135932A1
WO2011135932A1 PCT/JP2011/055492 JP2011055492W WO2011135932A1 WO 2011135932 A1 WO2011135932 A1 WO 2011135932A1 JP 2011055492 W JP2011055492 W JP 2011055492W WO 2011135932 A1 WO2011135932 A1 WO 2011135932A1
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WO
WIPO (PCT)
Prior art keywords
fuel cell
hydrogen
electrode
fuel
cell device
Prior art date
Application number
PCT/JP2011/055492
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English (en)
Japanese (ja)
Inventor
勝一 浦谷
和田　滋
雅之 上山
暢久 石田
Original Assignee
コニカミノルタホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタホールディングス株式会社 filed Critical コニカミノルタホールディングス株式会社
Priority to JP2012512712A priority Critical patent/JP5494799B2/ja
Publication of WO2011135932A1 publication Critical patent/WO2011135932A1/fr

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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
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04544—Voltage
    • H01M8/04559—Voltage of fuel cell stacks
    • 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
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04895—Current
    • H01M8/0491—Current of fuel cell stacks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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

Definitions

  • the present invention relates to a fuel cell device, and more particularly to a fuel cell device having a hydrogen generating member.
  • Patent Document 1 a hydrogen generating member that generates hydrogen by reacting water is provided in the fuel cell main body, and hydrogen generated by the hydrogen generating member is supplied to the fuel electrode.
  • Fuel cell systems have been proposed. In this fuel cell system, water necessary for hydrogen generation is supplied from water generated by power generation in the fuel cell body, so that it is not necessary to carry water. Then, the hydrogen generated in the hydrogen generating member is supplied to the fuel electrode, and water is generated on the oxidant electrode side by generating electricity, so there is no need to supply hydrogen from the outside. Power generation operation is possible.
  • the reduction control unit uses the regenerative power generated by the load when regenerating the load driven by the power supplied from the fuel cell device, to generate the hydrogen. Since the member is regenerated, the power generation life can be extended.
  • 2 is an equivalent circuit of a fuel cell main body. It is a characteristic view which shows the electrical characteristic of a fuel cell main body.
  • 1 is a schematic diagram showing a schematic configuration of a hybrid system of a fuel cell device and a power storage device according to an embodiment of the present invention.
  • FIG. 1 is a schematic diagram showing a schematic configuration of a fuel cell device according to an embodiment of the present invention.
  • the fuel cell device 1 includes a fuel cell main body 10 and a reduction control unit 20 as shown in FIG.
  • the fuel cell main body 10 is shown in a schematic sectional view
  • the reduction control unit 20 is shown in a block diagram.
  • the fuel cell body 10 includes an electrolyte membrane 101, a fuel electrode 102, an air electrode 103 that is an oxidant electrode, a hydrogen generation member 104, a heater 105, a temperature sensor 106, and a cover member 107.
  • the fuel cell main body 10 has an MEA (Membrane Electrode Assembly) structure in which a fuel electrode 102 and an air electrode 103 are bonded to both surfaces of an electrolyte membrane 101.
  • MEA Membrane Electrode Assembly
  • Each of the fuel electrode 102 and the air electrode 103 can be constituted by, for example, a catalyst layer in contact with the electrolyte membrane 101 and a diffusion electrode laminated on the catalyst layer.
  • the catalyst layer for example, platinum black or a platinum alloy supported on carbon black can be used.
  • the material of the diffusion electrode of the fuel electrode 102 for example, carbon paper, Ni—Fe cermet, Ni—YSZ cermet, or the like can be used.
  • As a material for the diffusion electrode of the air electrode 103 for example, carbon paper, La—Mn—O-based compound, La—Co—Ce-based compound, or the like can be used.
  • the hydrogen generating member 104 a material that generates hydrogen by a chemical reaction (for example, oxidation) (for example, Fe or Mg alloy) can be used. In this embodiment, Fe that generates hydrogen by oxidation is used. In addition, the hydrogen generation member 104 can not only generate hydrogen but also store (adsorb) hydrogen. Thereby, after generating hydrogen from the hydrogen generating member 104, the hydrogen generating member 104 can be used repeatedly by performing an occlusion (adsorption) operation. As a material capable of storing hydrogen as a fuel, a hydrogen storage alloy based on Ni, Fe, Pd, V, Mg, or the like can be used.
  • the discharge surface 104a for releasing hydrogen of the hydrogen generating member 104 and the supply surface 102a for supplying hydrogen of the fuel electrode 102 face each other and are arranged in parallel at regular intervals by spacers such as beads (not shown). .
  • the discharge surface 104 a of the hydrogen generation member 104 discharges hydrogen in a planar shape, and this hydrogen is supplied uniformly to the supply surface 102 a of the fuel electrode 102.
  • the temperature of the entire hydrogen generation member 104 is uniformly increased by the heater 105 disposed in contact with the entire surface of the hydrogen generation member 104 (excluding the discharge surface 104a), so that hydrogen is discharged from the discharge surface 104a. It can be released in a planar form. As a result, the hydrogen generating member 104 can release hydrogen from substantially the entire surface of the discharge surface 104 a toward the substantially entire surface of the supply surface 102 a of the fuel electrode 102.
  • the power generated from the electrode is constant. That is, the amount of hydrogen consumption is constant regardless of the location. In this case, chemical equilibrium is shifted due to the consumed hydrogen, and hydrogen corresponding to the shift amount is newly generated from the hydrogen generating member 104. Since the amount of hydrogen consumption is constant regardless of location, the rate of hydrogen generation from the hydrogen generating member 104 is also constant regardless of location.
  • hydrogen may be sealed in advance in the space portion 111 between the fuel electrode 102 and the hydrogen generating member 104.
  • the encapsulated hydrogen diffuses naturally and the concentration in the encapsulated space 111 becomes constant, so that the hydrogen concentration can be made constant regardless of the location.
  • the discharge surface 104a for releasing hydrogen of the hydrogen generation member 104 and the supply surface 102a for supplying hydrogen of the fuel electrode 102 are arranged in parallel at regular intervals.
  • the discharge surface 104a for releasing hydrogen and the supply surface 102a to which hydrogen of the fuel electrode 102 is supplied may be overlapped and brought into close contact with each other.
  • the structure of the fuel cell device can be simplified and downsized.
  • the hydrogen generation member 104 is built in the fuel cell main body 10 (cover member 107). However, the hydrogen generation member 104 is provided outside the fuel cell main body 10 and connected by a flow path. May be adopted.
  • the cover member 107 is a container for covering components other than the cover member 107 of the fuel cell main body 10.
  • An air supply port 109 for supplying air to the air flow path 108 is disposed on the air electrode 103 side, and excess air is discharged.
  • An air discharge port 110 is provided.
  • an air supply port 109 and an air discharge port 110 are provided on the air electrode 103 side of the heater 105. Air is distributedly supplied to the entire air electrode 103 by passing air from the air supply port 109 through the air flow path 108.
  • An open / close valve (not shown) is installed in each of the air supply port 109 and the air discharge port 110, and each of the air supply port 109 and the air discharge port 110 can be shut off.
  • the fuel cell main body 10 generates power by an electrochemical reaction generated by supplying hydrogen from the hydrogen generating member 104 to the fuel electrode 102 and supplying air from the air flow path 108 to the air electrode 103. Further, during this power generation operation, iron (Fe), which is the hydrogen generating member 104, is oxidized and changed to iron oxide (Fe 3 O 4 ), and the proportion of iron (Fe) in the hydrogen generating member 104 gradually decreases. Go. Details of the power generation operation will be described later.
  • the reduction control unit 20 includes a voltage detection unit 201, a current detection unit 202, a determination unit 203, and a switch unit 204.
  • the reduction control unit 20 is configured to reduce and regenerate the hydrogen generating member 104 that has been oxidized along with the power generation operation of the fuel cell main body 10. Specifically, the reduction control unit 20 oxidizes hydrogen (H 2 ) generated by electrolyzing water (H 2 O) generated during the power generation operation of the fuel cell main body 10 in the fuel cell main body 10.
  • the oxidized hydrogen generating member 104 is reduced by reacting with the generated hydrogen generating member 104 (hydrogen generating member 104 in which the ratio of iron oxide (Fe 3 O 4 ) is increased).
  • the regenerative power generation unit 30 includes a motor 301 and a bidirectional inverter 302.
  • the fuel cell device 1 according to the embodiment of the present invention performs a power generation operation, and the bidirectional inverter 302 is output from the fuel cell device 1 according to the embodiment of the present invention.
  • DC power is converted into AC power and supplied to the motor 301.
  • the fuel cell device 1 according to an embodiment of the present invention performs a regeneration operation, and the bidirectional inverter 302 generates regenerative power (AC) output from the motor 301. Power) is converted into DC power and supplied to the fuel cell device 1 according to one embodiment of the present invention.
  • the fuel cell device 1 according to the embodiment of the present invention receives information on the state of the motor 301, A control unit that controls the entire fuel cell device 1 according to the embodiment of the present invention may be provided according to the information.
  • FIG. 2 the same parts as those in FIG. 2 (a) to 2 (d) are schematic diagrams showing the flow of power generation operation and regeneration operation performed in the fuel cell device 1 according to one embodiment of the present invention.
  • water (H 2 O) is generated at the fuel electrode 102 as shown in the chemical reaction formula (1).
  • the generated water (H 2 O) is supplied to the hydrogen generation member 104 (Fe) via the space 111, and the hydrogen generation member 104 (Fe) uses the supplied water (H 2 O) to perform the following chemistry.
  • the oxidation reaction shown in the reaction formula (2) occurs, and hydrogen (H 2 ) is generated by the oxidation reaction.
  • the generated hydrogen (H 2 ) is supplied to the fuel electrode 102 via the space 111, and the fuel electrode 102 oxidizes the supplied hydrogen (H 2 ) and generates power to generate water (H 2 O again). ) Is generated and the power generation operation is continued.
  • the hydrogen generating member 104 is changed to iron oxide (Fe 3 O 4 ) by oxidation of iron (Fe), and the proportion of iron (Fe) in the hydrogen generating member 104 gradually decreases. To go.
  • the hydrogen generated in the fuel electrode 102 (H 2) is via the space portion 111 is supplied to the hydrogen generating member 104, the hydrogen generating member 104, the following chemical reaction formula by the supplied hydrogen (H 2) ( 4) occurs, and by the reduction reaction, iron oxide (Fe 3 O 4 ) in the hydrogen generating member 104 is reduced to change to iron (Fe), and iron (Fe) in the hydrogen generating member 104 is reduced.
  • the rate gradually increases and the hydrogen generating member 104 is regenerated. 4H 2 + Fe 3 O 4 ⁇ 4H 2 O + 3Fe (4)
  • water (H 2 O) is generated in the hydrogen generating member 104 as shown in the chemical reaction formula (4).
  • the generated water (H 2 O) is supplied to the fuel electrode 102 via the space 111, and the fuel electrode 102 again generates hydrogen (H 2 ) by electrolyzing the supplied water (H 2 O).
  • the reproduction operation is continued in a cyclic usage form in which the image is generated.
  • restoration control part 20 is collect
  • FIG. 3 is an equivalent circuit of the fuel cell main body 10
  • FIG. 4 is a characteristic diagram showing electrical characteristics of the fuel cell main body 10.
  • Equivalent circuit of the fuel cell main body 10 shown in FIG. 3 includes a cathode terminal T1, a resistor R1, a capacitor C1, by a resistor R2, and the fuel cell voltage V FC, the fuel electrode terminal T2.
  • the fuel cell voltage V FC here means a voltage used for the reduction reaction.
  • the air electrode side terminal T1 is connected to one end of the parallel circuit of the capacitor C1 and the resistor R2 via the resistor R1.
  • the other end of the parallel circuit of the capacitor C1 and the resistor R2 is connected to the positive electrode side of the fuel cell voltage V FC, the anode side of the fuel cell voltage V FC is connected to the fuel electrode terminal T2.
  • the fuel cell current I FC flows into the air electrode side terminal T1. In this case, it is assumed that the voltage V A is applied to the air electrode side terminal T1.
  • Resistance R1 indicates the resistance component of the fuel electrode 102 itself and the resistance component of the air electrode 103 itself.
  • Capacitance C ⁇ b> 1 indicates a capacitance component due to the electric double layer generated at the interface between the electrolyte membrane 101 and the fuel electrode 102 and a capacitance component due to the electric double layer generated at the interface between the electrolyte membrane 101 and the air electrode 103.
  • the resistor R2 indicates the resistance component of the electrolyte membrane 101 itself. The power consumed during the regeneration operation in the circuit portion including the resistor R1, the capacitor C1, and the resistor R2 is a loss in the fuel cell main body 10 during the regeneration operation.
  • the fuel cell current I FC -fuel cell voltage V FC characteristic is as shown by a characteristic curve 41 in FIG. If FC increases, the fuel cell voltage V FC decreases. In addition, an inflection point P1 exists in the fuel cell current I FC -fuel cell voltage V FC characteristic curve 41 as shown in FIG. Note that V A in FIG. 4 indicates an applied voltage applied between the fuel electrode 102 and the air electrode 103 of the fuel cell main body 10 by the reduction control unit 20 during the regeneration operation. Further, 42 in FIG. 4 indicates a fuel cell current I FC -regenerative power (I FC ⁇ V A ) characteristic line, and 43 in FIG. 4 indicates a fuel cell current I FC -recovered power (I FC ⁇ V FC). ) Characteristic curve is shown.
  • the voltage detection unit 201 detects the fuel cell voltage V FC
  • the current detection unit 202 detects the fuel cell current I FC
  • the determination unit 203 calculates the recovered power (I FC ⁇ V FC ) using the detection results of the voltage detection unit 201 and the current detection unit 202
  • the fuel cell current I FC is the current limit value I LIM (recovered power (I
  • the switch section 204 is turned on until the current value FC / V FC ) reaches the maximum value), and when the fuel cell current I FC exceeds the current limit value I LIM , the switch section 204 is turned off and the fuel cell current is reached.
  • the regeneration operation is prevented from continuing in a state where I FC exceeds the current limit value I LIM .
  • the reduction control unit 20 during the regeneration operation performs the reduction reaction control as described above, whereby the hydrogen generation member 104 can be regenerated using the regenerative power generated in the regenerative power generation unit 30 and the power generation life is extended. be able to. Further, the reduction control unit 20 during the regeneration operation performs the reduction reaction control as described above, whereby the power recovery efficiency can be improved.
  • the fuel cell In order to effectively use the regenerative power generated in the regenerative power generation unit 30 during the period when the switch unit 204 is in the OFF state, for example, as shown in FIG. 5, the fuel cell according to one embodiment of the present invention is used.
  • a hybrid system of the device 1 and the power storage device 50 is constructed so that the switch unit 204 and the switch unit 501 are turned ON / OFF in a complementary manner, and the switch unit 501 is turned ON when the switch unit 204 is in the OFF state.
  • the regenerative power may be stored in the storage battery 502.
  • a solid oxide electrolyte is used as the electrolyte membrane 101, and water is generated on the fuel electrode 102 side during power generation. According to this configuration, water is generated on the side where the hydrogen generating member 104 is provided, which is advantageous for simplification and miniaturization of the apparatus.
  • a solid polymer electrolyte that allows hydrogen ions to pass through can be used as the electrolyte membrane 101.
  • a flow path for propagating this water to the hydrogen generation member 104 may be provided.
  • the fuel cell device according to the present invention can be used, for example, as a driving battery for portable electronic devices such as a mobile phone, a portable information terminal, a notebook personal computer, a portable audio, and a portable visual device.
  • portable electronic devices such as a mobile phone, a portable information terminal, a notebook personal computer, a portable audio, and a portable visual device.
  • Fuel cell apparatus which concerns on one Embodiment of this invention 10 Fuel cell main body 101 Electrolyte membrane 102 Fuel electrode 102a Supply surface 103 Air electrode 104 Hydrogen generating member 104a Release surface 105 Heater 106 Temperature sensor 107 Cover member 108 Air flow path 109 Air supply Port 110 Air discharge port 111 Space portion 20 Reduction control portion 201 Voltage detection portion 202 Current detection portion 203 Determination portion 204 Switch portion 30 Regenerative power generation portion 301 Motor 302 Bidirectional inverter 41 Fuel cell current-fuel cell voltage characteristic curve 42 Fuel cell Current-regenerative power characteristic line 43 Fuel cell current-recovered power characteristic curve 50 Power storage device 501 Switch unit 502 Storage battery C1 Capacity I FC fuel cell voltage LD Load P1 Inflection point R1, R2 Resistance T1 Air electrode Side terminal T2 Fuel electrode side terminal VA applied voltage V FC fuel cell voltage

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

Le dispositif de pile à combustible décrit comprend un corps de pile à combustible (10) et une unité de commande de réduction (20). Le corps de pile à combustible (10) comprend une électrode de combustible (102), une électrode d'air (103), un film d'électrolyte (101) maintenu entre l'électrode de combustible (102) et l'électrode d'air (103), et un élément générateur d'hydrogène (104) qui génère de l'hydrogène en provoquant une réaction avec l'eau produite lors de la production d'énergie. Pendant l'utilisation régénérative d'un moteur (301) entraîné par le courant délivré par le dispositif de pile à combustible mentionné ci-dessus, l'unité de commande de réduction (20) utilise l'énergie de régénération produite par le moteur (301) pour régénérer l'élément générateur d'hydrogène (104).
PCT/JP2011/055492 2010-04-28 2011-03-09 Dispositif de pile à combustible WO2011135932A1 (fr)

Priority Applications (1)

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JP2012512712A JP5494799B2 (ja) 2010-04-28 2011-03-09 燃料電池装置

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JP2010-103469 2010-04-28
JP2010103469 2010-04-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013104716A (ja) * 2011-11-11 2013-05-30 Konica Minolta Holdings Inc 鉄の酸化状態検出装置及びそれを備えた燃料電池装置
JP2019514190A (ja) * 2016-04-14 2019-05-30 エヌイー．エム．イー．エスワイエス．エスアールエル 電気エネルギー生成用の充電式電気化学デバイス

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JP2004149394A (ja) * 2002-11-01 2004-05-27 Uchiya Thermostat Kk 水素発生装置
JP2006108061A (ja) * 2004-09-30 2006-04-20 Denso Corp 充放電システム
JP2007157586A (ja) * 2005-12-07 2007-06-21 Toyota Motor Corp 燃料電池システムおよびその制御方法
JP2009099491A (ja) * 2007-10-19 2009-05-07 Sharp Corp 燃料電池システムおよび電子機器

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JPS50158017A (fr) * 1974-06-10 1975-12-20
JPS50158016A (fr) * 1974-06-10 1975-12-20
JP3136015B2 (ja) * 1992-12-28 2001-02-19 本田技研工業株式会社 自動車用反応ガス圧縮システム
JP2001332271A (ja) * 2000-05-24 2001-11-30 Mitsubishi Heavy Ind Ltd 蓄発電装置
JP5001761B2 (ja) * 2007-09-10 2012-08-15 Ｊｘ日鉱日石エネルギー株式会社 水蒸気発生器及び燃料電池システムの運転方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004149394A (ja) * 2002-11-01 2004-05-27 Uchiya Thermostat Kk 水素発生装置
JP2006108061A (ja) * 2004-09-30 2006-04-20 Denso Corp 充放電システム
JP2007157586A (ja) * 2005-12-07 2007-06-21 Toyota Motor Corp 燃料電池システムおよびその制御方法
JP2009099491A (ja) * 2007-10-19 2009-05-07 Sharp Corp 燃料電池システムおよび電子機器

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013104716A (ja) * 2011-11-11 2013-05-30 Konica Minolta Holdings Inc 鉄の酸化状態検出装置及びそれを備えた燃料電池装置
JP2019514190A (ja) * 2016-04-14 2019-05-30 エヌイー．エム．イー．エスワイエス．エスアールエル 電気エネルギー生成用の充電式電気化学デバイス

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JPWO2011135932A1 (ja) 2013-07-18

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