WO2007128202A1 - Pile à combustible sans plaques à bornes destinée à fonctionner à basse température - Google Patents

Pile à combustible sans plaques à bornes destinée à fonctionner à basse température Download PDF

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Publication number
WO2007128202A1
WO2007128202A1 PCT/CN2007/001236 CN2007001236W WO2007128202A1 WO 2007128202 A1 WO2007128202 A1 WO 2007128202A1 CN 2007001236 W CN2007001236 W CN 2007001236W WO 2007128202 A1 WO2007128202 A1 WO 2007128202A1
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WO
WIPO (PCT)
Prior art keywords
fuel cell
cell stack
wedge
plate
low temperature
Prior art date
Application number
PCT/CN2007/001236
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English (en)
French (fr)
Inventor
Binglun Tian
Hui Dong
Original Assignee
Binglun Tian
Hui Dong
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 Binglun Tian, Hui Dong filed Critical Binglun Tian
Priority to EP07720809A priority Critical patent/EP2012382A4/en
Priority to JP2009506896A priority patent/JP2009534802A/ja
Publication of WO2007128202A1 publication Critical patent/WO2007128202A1/zh
Priority to US12/233,714 priority patent/US20090053570A1/en

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Classifications

    • 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
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
    • H01M8/248—Means for compression of the 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
    • H01M8/002—Shape, form of a fuel cell
    • H01M8/004—Cylindrical, tubular or wound
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
    • 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
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0687—Reactant purification by the use of membranes or filters
    • 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
    • H01M8/2465—Details of groupings of fuel cells
    • 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
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • 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
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2484—Details of groupings of fuel cells characterised by external manifolds
    • H01M8/2485—Arrangements for sealing external manifolds; Arrangements for mounting external manifolds around a stack
    • 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

  • Endless plate fuel cell stack suitable for low temperature start-up
  • the present invention relates to a fuel cell, and more particularly to an endless fuel cell stack suitable for low temperature start-up. Background technique
  • the low-temperature cold start and low-temperature operation of fuel cells is a relatively advanced topic in the world, because the cold start performance of fuel cells directly affects the practicality of fuel cells and affects their range of use.
  • U.S. Patent 6,699,612 teaches a battery system in which a circulating antifreeze glycol cools the heat generated by the fuel cell. At the same time, the refrigerating liquid is also mixed with the fuel gas in the heat exchanger to remove the moisture in the fuel. There is also a water removal mechanism in the system to remove water from the chilled liquid to ensure the concentration of the chilled liquid. It is not difficult to see that the system is very complicated.
  • U.S. Patent 6,727,013 which utilizes the maintenance of the temperature of the fuel cell device in a standby state by heating the fuel cell stack using an external heating system. It is mainly heated by a resistive load, and then a hot air is blown onto the fuel cell stack by a fan. It can be seen that in order to ensure the temperature of the fuel cell stack, energy should be continuously consumed in the system.
  • the patent does not address the low temperature start-up of fuel cells.
  • a fuel cell stack special fuel lead plate and end plate are mentioned in U.S. Patent No. 6,764,786.
  • the patent states that the end plates of a fuel cell stack are often thick metal plates that are cumbersome and expensive, have high heat capacity and are prone to heat loss.
  • the battery at the end plate is easy to dissipate heat, and the performance is poor, which affects the low-temperature starting speed of the fuel cell, and is easy to back pressure when starting at a low temperature, causing permanent damage.
  • the patent proposes a high-strength, low-heat capacity low-heat-dissipation end plate, which partially solves the problems caused by the low-temperature start-up and low-temperature operation of the fuel cell stack.
  • U.S. Patent No. 6,824,901 proposes a method of applying a porous thermal insulation plate between the end cells of the fuel cell stack and the end plates to solve the problems caused by the low temperature rapid cold start of the fuel cell.
  • the thermal insulation plate mentioned in the patent is a porous graphite plate with a void ratio of -50-75%.
  • the porous graphite plate has a limited heat insulation effect, which only partially blocks the heat transfer from the end battery to the end plate, so the method only partially solves the low temperature quick start of the fuel cell system.
  • a cylindrical battery stack is proposed in U.S. Patent No. 5,595,834, which is characterized in that each of the battery plates is a circular piece and the battery has a partition extending a certain distance for heat dissipation.
  • the volume is relatively large, and there is a hydrothermal imbalance between the end battery and the internal battery, especially at relatively low temperatures.
  • U.S. Patent No. 5,470,671 describes a cylindrical fuel cell stack in which all of the cathode sides of the cells are arranged on the circumference of the battery unit to dissipate heat to the atmosphere.
  • the technical disadvantage is that the conventional battery stack structure cannot be used, the volume is large, and the battery voltage is relatively low. The battery power is relatively small.
  • U.S. Patent 5,595,834 describes a cylindrical fuel cell which is very compact and is formed by stacking a battery plate with a battery.
  • the battery is difficult to operate at relatively high ambient temperatures due to problems such as heat dissipation. Because there are two ends of the battery in the battery stack, the low-temperature start-up of the battery may also affect the low-temperature starting performance of the battery.
  • the low-temperature start of the fuel cell mainly includes: switching to anti-freezing medium; heating by external; special treatment of the end battery in the battery stack or improving the hydrothermal management of the entire battery stack, especially The water-heat balance of the end battery has a great influence on the rapid low-temperature cold start of the fuel cell.
  • the simplest and most ideal method is to hydrogen fuel Gas and air are directly added to the fuel cell system, and the battery is operated at a relatively low voltage, so that the heat generated by the battery itself rapidly heats the fuel cell stack to achieve a low temperature cold start of the fuel cell stack. It is not necessary to resort to an external auxiliary heating device. In fact, reducing the humidification of the fuel cell system is a very good method of low temperature start-up. As described in U.S. Patent 6,746,789, the use of air-cooled fuel cells can reduce the complexity of the fuel cell system by reducing humidification.
  • air-cooled fuel cells currently have a low power density of the stack, a relatively small power range, a typical power range of several hundred watts, and a few kilowatt-class fuel cells.
  • Large air-cooled fuel cells mainly have stack integration. It is more difficult, and the system power is relatively low, generally 100-150W/L.
  • large air-cooled fuel cell stacks such as those with powers ranging from a few kilowatts to more than a dozen kilowatts, it is more difficult to see. Therefore, large fuel cells generally use water or frozen liquid as a cooling medium.
  • a general air-cooled fuel cell also has a problem of water-heat balance of the terminal electrodes. Summary of the invention
  • An object of the present invention is to provide an endless fuel cell stack suitable for low temperature starting in order to solve the above problems.
  • An endless fuel cell stack suitable for low temperature start-up comprising a plurality of membrane electrodes, a plurality of bipolar plates, at least one pair of current collecting lead plates, at least one electrically insulating separator and two a fastening circle, the plurality of bipolar plates are wedge-shaped bipolar plates, and the wedge-shaped bipolar plates are provided with an air flow field, a hydrogen flow field and a cooling fluid flow field, and the at least one pair of current collecting lead plates
  • at least one electrically insulating spacer comprises at least one set of current output mechanisms by sandwiching an electrically insulating spacer between the pair of current collecting lead plates; said plurality of membrane electrodes, a plurality of wedge bipolar plates and at least one
  • the group current output mechanism encloses a cylindrical fuel cell stack and is integrally fastened by two fastening circles, and further includes an upper end cover and a lower end cover respectively connected to the upper and lower axial ends of the cylindrical fuel cell stack
  • the electrically insulating partition is a
  • the wedge bipolar plate may be a whole wedge-shaped bipolar plate, or may be composed of two wedge-shaped unipolar plates, or a wedge-shaped unipolar plate plus a planar unipolar plate, or Two flat unipolar plates and one wedge plate.
  • the wedge bipolar plate may be one or two groups of a metal plate, a graphite plate, and a flexible graphite plate. to make.
  • the current output mechanism is a group, and the current output mechanism is disposed between the first unit cell and the last unit cell of the cylindrical fuel cell stack.
  • the current output mechanism is two or more groups, and each group of current output mechanisms are respectively disposed at different positions of the cylindrical fuel cell stack, and the plurality of single cells in the fuel cell stack are equally divided into two or two corresponding groups. More than one battery pack.
  • the inner hole of the fastening circle is composed of two parts: a straight hole and a horn hole, and the two fastening circles are respectively tightly sleeved at two ends of the cylindrical fuel cell stack, and the plurality of sets of fastening nuts and fastening screws are adopted. Tightening, tightening the rounded surface of the circular horn to make the end of the cylindrical battery enter the straight hole portion of the fastening circle, thereby tightening the plurality of membrane electrodes and the plurality of bipolar plates in the stack .
  • the inner hole of the fastening circle is a straight hole, and the two fastening circles are respectively sleeved directly on both ends of the cylindrical fuel cell stack which has been tightened.
  • the thickness of the wedge-shaped bipolar plates adjacent to the current collecting lead plates may be smaller than the thickness of the other wedge-shaped bipolar plates.
  • the cylindrical fuel cell stack is surrounded by a ring of air filters, and a fan is mounted on the outer side of the circular upper end cover.
  • the bulky battery end plate in the conventional battery stack does not exist in the battery stack, and instead the fastening circle is used, which can be very light.
  • the bipolar plates in the stack are wedge-shaped, unlike the planar bipolar plates of conventional fuel cells. It is sandwiched between a pair of current collecting lead plates by an electrically insulating spacer to form a set of current output mechanisms.
  • the two current collecting lead plates are close together, and only one electrically insulating spacer is spaced apart.
  • the stack has a high pressure-increasing step-down and high integration.
  • the inner membrane electrode of the battery stack is very uniformly stressed everywhere, and there is no problem of end plate deformation.
  • Conventional battery stacks have a certain end plate deformation due to the strength of the end plates, resulting in uneven force in the plane direction of the membrane electrodes.
  • the first end of the stack has a very good water-heat balance, which is basically the same as other internal electrodes, and is suitable for low-temperature cold start below zero.
  • the flow cell of the air-cooled battery stack is generally wedge-shaped, which can reduce the air cooling flow.
  • the gas resistance of the tank increases the heat transfer area of the gas, which is beneficial to heat exchange and improve the heat distribution uniformity in the stack.
  • the power range of the battery stack expands rapidly, and the power and volume dimensions are in a 3 power relationship. For example: For a battery with a diameter of 8 cm and a cylinder height of 120 cm, the power will reach lkW for a battery with a diameter of 16 cm and a height of 16 cm. For a battery with a cylinder diameter of 32 cm and a height of 8 cm, the power will reach 8 kW.
  • the stack and system maintain high power density over a wide power range.
  • Conventional stack power increases generally in the one-dimensional direction, and integration increases as the increase in two- or three-dimensional space increases.
  • the wedge-shaped bipolar plate and the membrane electrode are pressed together, and with its unique wedge structure, the battery stack has strong ability to resist shock, impact and other external forces.
  • the flow channel of the wedge-shaped bipolar plate is generally a through-groove, and the production cost is extremely low, which is very suitable for mass production.
  • the electrode adopts a conventional rectangular structure, and the material utilization rate is very high.
  • the air filter of the battery stack can be directly placed outside the cylindrical battery stack with high system integration.
  • FIG. 1 is a schematic view showing an overall structure of an embodiment of an endless fuel cell stack suitable for low temperature starting according to the present invention
  • FIG. 2 is a perspective structural view of one embodiment of a wedge-shaped bipolar plate according to the present invention
  • FIG. 3 is a schematic perspective view of a set of current output mechanisms according to the present invention
  • FIG. 4 is a schematic exploded perspective view of another embodiment of a wedge-shaped bipolar plate in the present invention
  • FIG. 5 is a schematic view showing the entire structure of a second embodiment of an endless-plate fuel cell stack suitable for low-temperature startup
  • Fig. 6 is a schematic view showing the basic structure of a fuel cell stack and an auxiliary system according to the present invention. detailed description
  • an endless fuel cell stack suitable for low temperature start-up comprises a plurality of membrane electrodes 1, a plurality of wedge bipolar plates 2, at least one pair of current collecting lead plates 3, at least one electrically insulating partition plate 4, Two fastening circles 5, an upper end cover 6, a lower end cover 7, and a centrifugal fan 8. Among them, an electrical insulation The spacer 4 is sandwiched between a pair of current collecting lead plates 3 to constitute a set of current output mechanisms.
  • a plurality of membrane electrodes 1, a plurality of wedge bipolar plates 2 and at least one set of current output mechanisms enclose a cylindrical fuel cell stack and are fastened together by two fastening circles 5.
  • the upper end cover 6 and the lower end cover 7 are respectively connected to the upper and lower shaft ends of the cylindrical fuel cell stack, and the electrically insulating partition 4 is a planar structure (may also be a wedge-shaped structural member), and has a thickness of 0.05 mm (typically 0.01) — between 3mm).
  • the upper end cover 6 and the lower end cover 7 are provided with a hydrogen flow chamber, a hydrogen inlet 9 is arranged on the side of the upper end cover 6, and a hydrogen outlet 10 is arranged on the side of the lower end cover 7.
  • the current output mechanisms are a group, and the set of current output mechanisms are disposed between the first single cell and the last single cell of the cylindrical fuel cell stack.
  • the wedge-shaped bipolar plate in the present invention may be composed of one or both of a metal plate, a graphite plate, and a flexible graphite plate. It can be a whole wedge-shaped bipolar plate, or it can be composed of two wedge-shaped unipolar plates, or a wedge-shaped unipolar plate plus a flat unipolar plate, or two flat unipolar plates and A wedge plate is formed. In all of the wedge bipolar plates of the stack, the thickness of the wedge bipolar plates adjacent to the current collecting lead plates may be less than the thickness of the other wedge bipolar plates. Referring to FIG. 2, FIG. 2 is a schematic perspective view showing an embodiment of a wedge-shaped bipolar plate 2 according to the present invention.
  • the two sides of the wedge-shaped bipolar plate 2 are respectively provided with an air flow field and a hydrogen flow field, and air.
  • the flow field comprises a plurality of air flow grooves which are radially penetrated along the surface of the wedge-shaped bipolar plate, and the depth of the plurality of air flow grooves may correspond to the thickness of the wedge-shaped bipolar plate from thin to thick, from shallow to deep, or the entire groove The depth is uniform.
  • the hydrogen flow field includes a plurality of hydrogen flow channels extending axially along the surface of the wedge-shaped bipolar plates. As shown in Fig. 2, 21 is an air flow channel, 22 is a groove shoulder, 23 is a sealed wire groove, and the hydrogen flow groove is not visible in the drawing.
  • Figure 3 is a perspective view of a set of current output mechanisms of the present invention.
  • the current output mechanism of the present invention is composed of an electrically insulating partition 4 sandwiched between a pair of current collecting lead plates 3, and in a fuel cell stack, such a current output mechanism has at least one set.
  • the set of current output mechanisms are disposed between the first cell and the last cell of the cylindrical fuel cell stack.
  • each group of current output mechanisms are respectively disposed at different positions of the cylindrical fuel cell stack, and the plurality of single cells in the fuel cell stack are equally divided into two or two corresponding groups. The above battery pack.
  • Fig. 4 is a perspective exploded perspective view showing another embodiment of the wedge-shaped bipolar plate of the present invention, and 1 is a membrane electrode.
  • the wedge-shaped bipolar plate 2 is composed of two wedge-shaped unipolar plates 2A, 2B, wherein one side of the wedge-shaped unipolar plate 2A is provided with a reactive air flow field (facing the membrane electrode), and the other side is provided There is a cooling air flow field, one side of the wedge unipolar plate 2B' There is a hydrogen flow field (facing the membrane electrode), 2A in the figure, which is rotated by an angle of 2A. The purpose is to show the reaction air flow field on the other side.
  • the wedge-shaped unipolar plate 2A is cooled.
  • One side of the air flow field is fitted to one side of the wedge-shaped unipolar plate 2B having no flow field.
  • FIG. 5 is a schematic view showing the entire structure of a second embodiment of an endless fuel cell stack suitable for low temperature starting according to the present invention; this embodiment adopts a bipolar plate as shown in FIG. 200 pieces of such bipolar plates 2, corresponding number of MEAs, two sets of current output mechanisms (each set containing two current collecting lead plates 3 and one electrically insulating spacer), enclosing a diameter of ⁇ 340 ⁇ 340 ⁇ , hollow part It is a 10KW cylindrical fuel cell stack of ⁇ 220 X 340mm.
  • the length of the bipolar plate is 340 mm, and the effective area of the MEA is 180 cm 2 . Wherein the cooling air flow trough is separated from the reaction air flow trough.
  • a reaction air inlet 11 is provided on the upper end cover 6 of the battery stack and a cooling fan 8 is mounted, and a reaction air outlet 12 is provided on the lower end cover 7 of the battery stack.
  • a reaction air outlet 12 is provided on the lower end cover 7 of the battery stack.
  • the cylindrical fuel cell stack there are two sets of current output mechanisms, which divide the fuel cell into two battery ports, which can reduce the output voltage of the battery stack and increase the output current of the battery stack.
  • the structure of the fastening circle 5 in the present invention may have two forms, one of which is that the inner hole is composed of two parts of a straight hole and a horn hole in this order.
  • the fastening circle of this structure When the fastening circle of this structure is inserted into the cylindrical fuel cell stack, it is tightened by a plurality of sets of fastening nuts and fastening screws, and the cylindrical battery stack is made by the circular surface which is gradually contracted by the fastening ring flared hole. The end portion enters the straight hole portion of the fastening circle, thereby tightening the plurality of membrane electrodes and the plurality of bipolar plates in the battery stack.
  • Another type of fastening hole has a bore which is a straight hole.
  • FIG. 6 there is shown a basic structural diagram of a fuel cell stack and an auxiliary system incorporating the same.
  • the length of the bipolar plate in the fuel cell stack is 400 mm
  • the effective area of the MEA is 240 cm 2 .
  • a 25 kW cylindrical fuel cell stack is enclosed by 240 bipolar plates, a corresponding number of MEAs, and a set of current output mechanisms.
  • the auxiliary system includes a 31 hydrogen storage tank, a pressure reducing valve 32, a steam separator 33, a hydrogen circulation pump 34, a solenoid valve 35, an air filter 36, an air blower 37, a liquid circulation pump 38, a heat sink, and a heat radiating fan 39.
  • the air filter 36 is located around the battery stack to surround the battery stack.
  • the bipolar plate in the fuel cell stack is composed of two unipolar plates, one unipolar plate is a plane flexible graphite plate, and the other unipolar plate is a wedge-shaped graphite plate, and the wedge-shaped graphite plate is provided with a reverse Air flow trough should be combined with heat dissipation.
  • the corresponding number of MEA MEA effective area is 52cm 2
  • a set of current output mechanism to enclose a 1.2kW cylindrical fuel with a diameter of ⁇ 180 ⁇ 160 ⁇ and a hollow part of ⁇ 100 X 160mm Battery stack.
  • the low temperature cold start test process is as follows: The cold start temperature of the power generation system is -18 ° C, the hydrogen inlet solenoid valve is opened through the control circuit board, and the outlet solenoid valve is opened; the hydrogen outlet solenoid valve is closed after the hydrogen is filled in the battery stack; The electric energy is enough to drive the fan to run, providing the minimum amount of air required for the reactor to react; adding a relatively large load to the fuel cell, generally maintaining the voltage of the single cell of 0.2V and providing a short circuit operation; a large amount of heat in the battery stack, It heats up quickly. In 30 seconds, the stack warmed up to above 0 °C. We performed the low temperature cold start of the battery stack more than 100 times, and the batteries were working normally, and no deterioration in battery performance was observed.

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Description

适合低温启动的无端板燃料电池堆 技术领域
本发明涉及一种燃料电池， 尤其涉及一种适合低温启动的无端板燃料电 池堆。 背景技术
燃料电池低温冷启动和低温下运行是国际上一项比较前沿的课题， 因为 燃料电池冷启动性能直接影响燃料电池的实用化程度， 影响其使用范围。
对于常规燃料电池发电系统而言， 燃料电池运行需要水增湿， 而且燃料 电池堆的冷却都需要水冷却。 因而在温度低于零度的情况下， 燃料电池的低 温冷启动变得非常困难。 如果燃料电池的水管理不好， 在温度低于零度下启 动， 往往会造成电池系统不能正常启动。 零度下， 电池系统'内易结冰， 有的 情况下会给系统造成永久性的损害。
美国专利 6699612中提出了一种电池系统， 该系统中有一个循环的防冻 液乙二醇冷却燃料电池产生的热量。 同时冷冻液还在热交换器中同燃料气混 合， 移去燃料中的水分。 系统中还有除水机构以及时除去冷冻液中的水， 用 来保证冷冻液的浓度。 不难看出， 该系统非常复杂。
美国专利 6727013中提出了一种保持燃料电池温度的方法， 该方法主要 是利用燃料电池设备在待机状态时的温度维持， 该方法是利用外加热系统给 燃料电池堆加热的。 主要采用电阻负载加热， 然后通过风扇将热风吹到燃料 电池堆上面。 可以看出， 为了保证燃料电池堆的温度， 系统中应不断消耗能 量。 专利中并没有涉及燃料电池的低温启动情况。
美国专利 6746789中提出了一种方案， 主要是利用外接催化反应器， 在 低温下， 将氢气和空气直接冷燃烧产生热量和水分然后提供给燃料电池的空 气阴极或阳极。 燃料电池系统采用空气做氧化剂和冷却剂， 因而可以简化电 池系统， 并提高燃料电池的低温启动性， 不过系统也比较复杂。
美国专利 7014935中提出了一种解决燃料电池堆中的两个端电池存在的 问题的方法。 在电池运行过程中， 尤其是低温启动运行过程中， 燃料电池堆 中的两个端电池因为水热等因素的影响， 容易出现水热不均问题。 专利中提 出对两端的电池进行处理， 提高电池的抗腐蚀性， 从而提高电池堆的低温可 操作性。 专利中只是提高端电池的抗腐蚀性， 并没有从根本上解决燃料电池 堆中的两个端电池的水热不均问题。
美国专利 6764786中提到了一种燃料电池堆特殊燃料引线板和端板。 专 利中指出， 燃料电池堆的端板常常是厚的金属板， 比较笨重和比较昂贵， 而 且有高的热容和容易散失热量。 在燃料电池堆在运行温度比较低或者在低温 启动时， 端板处的电池散热容易， 性能较差， 影响燃料电池的低温启动速度， 而且低温下启动时容易反压， 造成永久性损伤。 专利中提出了一种高强度、 低热容低散热端板， 部分解决了燃料电池堆在低温启动和低温运行时所产生 的问题。
美国专利 6824901中提出了在燃料电池堆的端电池和端板之间加上多孔 热绝缘板的方法解决燃料电池低温快速冷启动所带来的问题。 专利中提到的' 热绝缘板为多孔石墨板， 空隙率为— 50-75%。但毕竟采用多孔石墨板隔热效果 有限， 只是部分阻隔了端电池向端板的传热， 因而该方法只是部分解决了燃 料电池系统的低温快速启动。
在美国专利 5595834提出了一种圆筒形电池堆， 其特征在于每个电池的 极板都是圆形的片，而且电池有隔板延伸一定的距离用来散热 ·。体积比较大， 而且端面电池同内部电池存在水热不平衡，尤其在比较低的温 下更是这样。
美国专利 5470671描述了一种圆筒形燃料电池堆， 其中电池的所有阴极 侧布置在电池装置的圆周上， 向大气散热。 该技术缺点在于不能采用传统电 池堆结构， 体积大， 而且电池电压比较低。 电池功率比较小。
美国专利 5595834描述了一个圆筒型燃料电池， 体积非常紧凑， 是由电 池极板同电池叠在一起而成的。 因为散热等问题， 该电池很难在比较高的环 境温度下运行。 因为该电池堆中存在两端电池， 因而该电池低温下启动也会 存在端电池水热不均衡等问题而影响其低温启动性能。
综观上述燃料电池的专利技术， 可以看出燃料电池低温启动主要有： 换 用抗冻介质； 靠外部加热； 对电池堆中的端电池进行特殊处理或提高整个电 池堆的水热管理， 尤其是端电池水热均衡情况对燃料电池的快速低温冷启动 影响比较大。
对于燃料电池低温冷启动而言， 最简单而且比较理想的方法是将燃料氢 气和空气直接加入到燃料电池系统中， 对电池在比较低的电压下运行， 使电 池本身产生的热量迅速加热燃料电池堆， 实现燃料电池堆的低温冷启动。 不 必借助外在的辅助加热装置。 实际上， 降低燃料电池系统增湿是一种非常好 的低温启动的方法。 如美国专利 6746789中提到的情况， 降低增湿， 采用空 气冷却燃料电池可以降低燃料电池系统复杂程度。
然而， 空气冷却燃料电池目前主要存在电池堆功率密度较低， 功率范围 比较小， 一般功率范围在几百瓦， 比较少的有几千瓦级燃料电池， 大的空气 冷却燃料电池主要存在电池堆集成比较困难， 而且， 系统功率比较低， 一般 为 100-150W/L。对于大型空气冷却燃料电池堆， 比如功率在几千瓦到十几千 瓦的电池堆更难见到。 所以大型燃料电池一般采用水或冷冻液做冷却介质。 而且， 一般的空气冷却型燃料电池也存在端电极的水热均衡问题。 发明内容
本发明的目的， 就是为了解决上述问题而提供一种适合低温启动的无端 板燃料电池堆。
本发明的目的是这样实现的： 一种适合低温启动的无端板燃料电池堆， 包括多个膜 ¾极、 多个双极板、 至少一对集流引线板、 至少一个电绝缘隔板 和两个紧固圆圈，'所述的多个双极板为楔形双极板， 楔形双极板上设有空气 流场、 氢气流场和冷却流体流场， 所述的至少一对集流引线板和至少一个电 绝缘隔板通过将一块电绝缘隔板夹在一对集流引线板之间， 组成至少一组电 流输出机构； 所述的多个膜电极、 多个楔形双极板和至少一组电流输出机构 围成一个圆筒形燃料电池堆， 并通过两个紧固圆圈紧固成一体， 还包括分别 连接在所述圆筒形燃料电池堆上下两轴端的上端盖板和下端盖板， 所述的电 绝缘隔板为平面结构或楔形结构件， 厚度为 0.01-3mm; 所述的上端盖板和下 端盖板内设有氢气或 /和空气或 /和冷却液的流腔， 并设有相应的流体进、 出 口。
所述的楔形双极板可以是一片整体的楔形双极板， 也可以由两片楔形单 极板组合而成， 或是由一片楔形单极板加上一片平面单极板构成， 或是由两 片平面单极板和一片楔形板构成。
所述的楔形双极板可由金属板、 石墨板、 柔性石墨板中的一种或两种组 成。
所述的电流输出机构为一组， 该组电流输出机构设置在圆筒形燃料电池 堆的第一片单电池和最后一片单电池之间。
所述的电流输出机构为两组或两组以上， 各组电流输出机构分别设置在 圆筒形燃料电池堆的不同位置， 将燃料电池堆中的多个单电池平分为相应的 两个或两个以上的电池组。
所述的紧固圆圈的内孔依次由直孔和喇叭形孔两部分组成， 两个紧固圆 圈分别紧套在圆筒形燃料电池堆的两端，通过多套紧固螺母和紧固螺杆拉紧， 利用紧固圆圈喇叭形孔逐渐收缩的圆面使圆筒形电池堆端部进入紧固圆圈的 直孔部分， 从而将电池堆中的多个膜电极和多个双极板收紧。
所述的紧固圆圈的内孔为直孔， 两个紧固圆圈分别直接套在已经收紧的 圆筒形燃料电池堆的两端。
所述的多个楔形双极板中， 与集流引线板相邻的楔形双极板的厚度可小 于其它楔形双极板的厚度。
所述的圆筒形燃料电池堆外围包有一圈空气过滤器， 所述的圆环形上端 盖板外侧安装有风扇。
本发明一种适合低温启动的无端板燃料电池堆由于采用了以上技术方 案， 使其与现有技术相比， 具有以下的优点和特点：
1'、 电池堆中不存在常规电池堆中的笨重的电池端板，取而代之的是紧固 圆圈， 可以非常轻巧。
2、 电池堆中的双极板是楔形的， 不同于常规燃料电池的平面双极板。 由 一块电绝缘隔板夹在一对集流引线板之间， 组成一组电流输出机构， 两个集 流引线板靠的很近， 只有一个电绝缘隔板相隔。 电池堆中一般设有一组以上 的电流输出机构。 电池堆增流降压容易， 集成度高。
3、 电池堆内膜电极各处受力非常均勾， 不存在端板变形问题。 常规电池 堆因端板强度的原因会有一定的端板变形， 导致膜电极在平面方向上受力不 均。
4、 电池堆的首末端电极水热平衡非常好， 同其它内部电极基本一致， 适 合零度以下低温冷启动。
5、空气冷却形电池堆的流槽一般为楔形结构，这样可以减少空气冷却流 槽气阻， 增加气体冷却传热面积， 有利于热交换和提高电池堆内热分布均匀 性。
6、 电池堆功率范围扩展迅速， 功率和体积尺寸成 3次方关系。 例如： 对 于直径和筒高为 8cm的电池，若其功率为 120W，对于圆筒直径为和高为 16cm 的电池， 其功率将达到 lkW。 对于圆筒直径为和高为 32cm的电池堆， 其功 率将达到 8kW。 结构紧凑， 电池堆及系统在很大的功率范围内都可以保持高 的功率密度。 常规电池堆功率增加一般在一维方向上增加， 在二维或三维空 间中增加时集成度将会降低。
7、楔形双极板和膜电极相互压紧在一起， 加上其特有的楔形结构， 电池 堆具有强的抗击震动， 撞击等外界力量的能力。
8、楔形双极板的流槽一般为贯通槽， 制作成本极低， 非常适合批量化生 产。
9、 电极采用常规的长方形结构， 材料利用率非常高。
10、 电池堆的空气过滤器可以直接设在圆筒电池堆的外部， 具有高的系 统集成度。 附图说明
图 1为本发明一种适合低温启动的无端板燃料电池堆的一实施例整体结 构示意图； '
图 2为本发明中的楔形双极板的一个实施例的立体结构示意图； 图 3为本发明中的一组电流输出机构的立体结构示意图；
图 4本发明中的楔形双极板的另一个实施例的立体结构分解示意图； 图 5为本发明一种适合低温启动的无端板燃料电池堆的第二实施例整体 结构示意图；
图 6为含有本发明的燃料电池堆及辅助系统的基本结构示意图。 具体实施方式
参见图 1， 本发明一种适合低温启动的无端板燃料电池堆， 包括多个膜 电极 1、 多个楔形双极板 2、至少一对集流引线板 3、至少一个电绝缘隔板 4、 两个紧固圆圈 5、 上端盖板 6、 下端盖板 7和离心风机 8。 其中， 一块电绝缘 隔板 4夹在一对集流引线板 3之间， 组成一组电流输出机构。 多个膜电极 1、 多个楔形双极板 2和至少一组电流输出机构围成一个圆筒形燃料电池堆， 并 通过两个紧固圆圈 5紧固成一体。 上端盖板 6和下端盖板 7分别连接在圆筒 形燃料电池堆的上下两轴端， 电绝缘隔板 4为平面结构 （也可以为楔形结构 件）， 厚度为 0.05mm (—般在 0.01— 3mm之间）。 上端盖板 6和下端盖板 7 上设有氢气流腔， 在上端盖板 6侧面设有氢气进口 9， 在下端盖板 7侧面设 有氢气出口 10。 在本实施例中， 电流输出机构为一组， 该组电流输出机构设 置在圆筒形燃料电池堆的第一片单电池和最后一片单电池之间。
本发明中的楔形双极板可由金属板、 石墨板、 柔性石墨板中的一种或两 种组成。可以是一片整体的楔形双极板，也可以由两片楔形单极板组合而成， 或是由一片楔形单极板加上一片平面单极板构成， 或是由两片平面单极板和 一片楔形板构成。 在电池堆的所有楔形双极板中， 与集流引线板相邻的楔形 双极板的厚度可小于其它楔形双极板的厚度。 参见图 2， 图 2为本发明中的 楔形双极板 2的一个实施例的立体结构示意图， 在本实施例中， 楔形双极板 2 的两面分别设有空气流场和氢气流场， 空气流场包括多条沿楔形双极板的 表面径向贯通的空气流槽， 多条空气流槽的深度可相应于楔形双极板的厚度 由薄变厚而由浅变深， 也可以整条槽深度均一。 氢气流场包括多条沿楔形双 极板的表面轴向贯通的氢气流槽。 图 2中所示， 21为空气流槽， 22为槽肩， 23为密封线槽， 氢气流槽在图中不可见。
参见图 3， 图 3为本发明中的一组电流输出机构的立体结构示意图。 本 发明中的电流输出机构由一块电绝缘隔板 4夹在一对集流引线板 3之间组成， 在一个燃料电池堆中， 这种电流输出机构至少有一组。 当采用一组电流输出 机构时， 该组电流输出机构设置在圆筒形燃料电池堆的第一片单电池和最后 一片单电池之间。 当采用两组或两组以上电流输出机构时， 各组电流输出机 构分别设置在圆筒形燃料电池堆的不同位置， 将燃料电池堆中的多个单电池 平分为相应的两个或两个以上的电池组。
参见图 4， 图 4本发明中的楔形双极板的另一个实施例的立体结构分解 示意图， 图中所示， 1为膜电极。 在本实施例中， 楔形双极板 2由两片楔形 单极板 2A、 2B组成， 其中， 楔形单极板 2A的一个侧面设有反应空气流场. (面向膜电极）， 另一个侧面设有冷却空气流场， 楔形单极板 2B的一个侧面' 设有氢气流场 （面向膜电极）， 图中的 2A， 是由 2A旋转一个角度的形状， 目的是为了展示另一面的反应空气流场， 在组装时， 是将楔形单极板 2A有 冷却空气流场的一面与楔形单极板 2B没有流场的一面贴合。
参见图 5 , 图 5为本发明一种适合低温启动的无端板燃料电池堆的第二 实施例整体结构示意图； 该实施例采用了如图 4所示的双极板。 由 200片这 种双极板 2、 相应数量的 MEA、 两组电流输出机构 （每组含两块集流引线板 3 和一块电绝缘隔片）， 围成直径为 Φ 340 Χ 340ηιηι， 中空部分为 Φ 220 X 340mm 的 10KW 圆筒形燃料电池堆。 其中双极板长度为 340mm， MEA有效面积为 180cm2。 其中冷却空气流槽同反应用空气流槽分开的。 在 电池堆的上端盖板 6上设有反应空气进口 11并安装有散热风扇 8， 在电池堆 的下端盖板 7上设有反应空气出口 12。 在该圆筒形燃料电池堆中， 存在两组 电流输出机构，将燃料电池分为两个电池缉，这样可降低电池堆的输出电压， 增加电池堆的输出电流。
本发明中的紧固圆圈 5的结构可以有两种形式， 一种是其内孔依次由直 孔和喇叭形孔两部分组成。这种结构的紧固圆圈在套入圆筒形燃料电池堆时， 是通过多套紧固螺母和紧固螺杆拉紧， 利用紧固圆圈喇叭形孔逐渐收缩的圆 面使圆筒形电池堆端部进入紧固圆圈的直孔部分， 从而将电池堆中的多个膜 电极和多个双极板收紧。 另一种紧固圆圈的内孔为直孔， 这种结构的紧固圆 圈在套入圆筒形燃料电池堆时， 是分别直接套在已经收紧的圆筒形燃料电池 堆的两端。
参见图 6， 图 6为含有本发明的燃料电池堆及辅助系统的基本结构示意 图。 本实施例中燃料电池堆中的双极板长度为 400mm， MEA 有效面积为 240cm2。采用 240片双极板、相应数量的 MEA和一组电流输出机构围成 25kW 圆筒形燃料电池堆。 辅助系统包括 31储氢罐、 减压阀 32、 汽水分离器 33、 氢气循环泵 34、 电磁阀 35、 空气过滤器 36、 空气风机 37、 液体循环泵 38、 散热片和散热风扇 39。 其中， 空气过滤器 36位于电池堆周围， 将电池堆围 拢。
我们对采用本发明的无端板燃料电池堆组成的发电系统进行了低温冷启 动测试。 其中， 燃料电池堆中的双极板由两个单极板组合而成， 一个单极板 是平面柔性石墨板， 另一个单极板是楔形石墨板， 楔形石墨板上设有兼具反 应和散热功能的空气流槽。 用这种双极板 80片、 相应数量的 MEA ( MEA有 效面积为 52cm2 ) 和一组电流输出机构围成直径为 Φ 180 Χ 160ΠΙΙΏ、 中空部 分为 Φ 100 X 160mm的 1.2kW圆筒形燃料电池堆。低温冷启动测试过程如下： 发电系统冷启动温度为 -18°C， 通过控制电路板将氢气进口电磁阀， 出口电磁 阀打开； 氢气充满电池堆后关闭氢气出口电磁阀； 此时电池堆产生的电能足 以带动风机运转， 提供给电池堆反应所需最小量的空气； 给燃料电池加上比 较大的负载，一般维持单电池的电压为 0.2V和提供瞬时短路等操作； 电池堆 内大量发热， 升温迅速。 在 30s 内电池堆升温到达到 0°C以上。 我们对该电 池堆进行了 100次以上的低温冷启动， 各片电池工作正常， 没有观察到电池 性能下降的现象。

Claims

权 利 要 求 书
1. 一种适合低温启动的无端板燃料电池堆， 包括多个膜电极、 多个双极板、 至少一对集流引线板、 至少一个电绝缘隔板和两个紧固圆圈， 所述的多个 双极板为楔形双极板， 楔形双极板上设有空气流场、 氢气流场和冷却流体 流场，所述的至少一对集流引线板和至少一个电绝缘隔板通过将一块电绝 缘隔板夹在一对集流引线板之间， 组成至少一组电流输出机构； 所述的多 个膜电极、多个楔形双极板和至少一组电流输出机构围成一个圆筒形燃料 电池堆， 并通过两个紧固圆圈紧固成一体， 其特征在于： 还包括分别连接 在所述圆筒形燃料电池堆上下两轴端的上端盖板和下端盖板，所述的电绝 缘隔板为平面结构或楔形结构件， 厚度为 0.01-3mm; 所述的上端盖板和 下端盖板内设有氢气或 /和空气或 /和冷却液的流腔，并设有相应的流体进、 出口。
2. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的楔形双极板可以是一片整体的楔形双极板，也可以由两片楔形单极板 组合而成， 或是由一片楔形单极板加上一片平面单极板构成， 或是由两片 平面单极板和一片楔形板构成。
3. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的楔形双极板可由金属板、 石墨板、 柔性石墨板中的一种或两种组成。
4. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的电流输出机构为一组， 该组电流输出机构设置在圆筒形燃料电池堆的 第一片单电池和最后一片单电池之间。
5. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的电流输出机构为两组或两组以上，各组电流输出机构分别设置在圆情 形燃料电池堆的不同位置，将燃料电池堆中的多个单电池平分为相应的两 个或两个以上的电池组。
6. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 戶/ 述的紧固圆圈的内孔依次由直孔和喇叭形孔两部分组成，两个紧固圆圈^ 别紧套在圆筒形燃料电池堆的两端， 通过多套紧固螺母和紧固螺杆拉紧， 利用紧固圆圈喇叭形孔逐渐收缩的圆面使圆筒形电池堆端部进入紧固 11 圈的直孔部分， 从而将电池堆中的多个膜电极和多个双极板收紧。
7. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的紧固圆圈的内孔为直孔，两个紧固圆圈分别直接套在已经收紧的圆筒 形燃料电池堆的两端。
8. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的多个楔形双极板中， 与集流引线板相邻的楔形双极板的厚度可小于其 它楔形双极板的厚度。 .
9. 如权利要求 1所述的适合低温启动的无端板燃料电池堆， 其特征在于： 所 述的圆筒形燃料电池堆外围包有一圈空气过滤器， 所述的圆环形上端盖板 外侧安装有风扇。
PCT/CN2007/001236 2006-04-26 2007-04-16 Pile à combustible sans plaques à bornes destinée à fonctionner à basse température WO2007128202A1 (fr)

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