WO2013086752A1 - 一种用于水下的串联型金属/氧气电池堆 - Google Patents

一种用于水下的串联型金属/氧气电池堆 Download PDF

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WO2013086752A1
WO2013086752A1 PCT/CN2011/084482 CN2011084482W WO2013086752A1 WO 2013086752 A1 WO2013086752 A1 WO 2013086752A1 CN 2011084482 W CN2011084482 W CN 2011084482W WO 2013086752 A1 WO2013086752 A1 WO 2013086752A1
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plate
oxygen
rectangular parallelepiped
parallel
shaped
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孙公权
王二东
陈利康
舒朝著
谷顺学
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/647—Prismatic or flat cells, e.g. pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
    • H01M10/6557—Solid parts with flow channel passages or pipes for heat exchange arranged between the cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
    • H01M10/6567—Liquids
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to chemical power sources, and more particularly to a metal/oxygen battery stack for use in seawater or fresh water. Background technique
  • the metal/oxygen battery utilizes brine or lye as the electrolyte, and the anode used under water is magnesium, aluminum metal or alloy, and the cathode oxidant is oxygen or hydrogen peroxide.
  • the advantages of this type of battery are as follows: 1. High energy density. Since such batteries can supply electrolyte directly from seawater, their theoretical mass ratio energy is up to hundreds of watt-hours per kilogram. Second, the source of raw materials is rich. Magnesium and aluminum are all metal elements with large earth reserves and are inexpensive. Third, the storage performance is good. These batteries are inactive when they are not in contact with electrolytes (such as seawater). They have good storage performance and can last for several years.
  • the present invention is directed to the deficiencies of the prior art, and provides a metal/oxygen battery stack structure.
  • the battery stack structure can be used by using a closed design of the single battery and a liquid injection hole above the side of the single battery case.
  • the concentration of the electrolyte also solves the problem of leakage current caused by ion conduction; the hydrophobic gas permeable layer for dividing the outer seawater is disposed at the top, and the metal/oxygen battery is solved.
  • Exhaust problem in seawater or fresh water Separate the metal/oxygen battery cells, leave space for free access to and from the water between the cells, use the flow of seawater on the surface of the single cell to reduce the temperature of the stack, and ensure the stack Reliable operation.
  • the oxygen transmission chamber is a hollow closed cavity structure, and the n cells of the same structure and size are arranged in parallel in parallel, and the single cells are fixedly connected to the oxygen transmission cavity;
  • the unit cell includes a hollow rectangular parallelepiped shell, a plate-shaped metal anode and a plate-shaped inert cathode;
  • a plate-shaped metal anode is fixed around the periphery of the rectangular parallelepiped casing and parallel to one side surface of the casing, and two plate-shaped inert cathodes are placed in parallel on both sides of the plate-shaped metal anode, and the periphery thereof is fixed to the rectangular parallelepiped shell.
  • the wall of the rectangular parallelepiped housing perpendicular to the surface of the cathode plate respectively constitute two independent electrolyte chambers; respectively, the openings on the upper wall of the rectangular parallelepiped housing of the two independent electrolyte chambers are respectively provided, and the upper end openings of the rectangular parallelepiped housing are located at two Directly above the independent electrolyte chamber, and the opening is covered with a hydrophobic gas permeable layer; the two plate-shaped inert cathodes are respectively parallel to the metal anode side and parallel to the rectangular shell wall surface, and the rectangular parallelepiped shell perpendicular to the cathode plate surface
  • the walls respectively form two independent oxygen chambers; two plate
  • unit cells of the same structure are sequentially fixed in parallel to a side wall surface of the oxygen transmission chamber in parallel.
  • the two plate-shaped inert cathodes are placed in parallel in a symmetrical manner on both sides of the plate-shaped metal anode.
  • a liquid injection hole provided with a plug body is disposed above the wall surface of the rectangular parallelepiped housing of the electrolyte chamber for injecting an electrolyte.
  • the cavity of the oxygen transmission chamber is connected to an oxygen cylinder line of the outside or to an air outlet line of the oxygen pump; the current wires used when the n single cells are connected in series are placed in a protective cover.
  • the metal anode is made of one of Al, Mg, Li or Zn, or an alloy of two or more of them, and the inert cathode is made of carbon felt, carbon plate, copper alloy, carbon steel or One of them is a plate made of a composite material of a substrate.
  • the invention has the following advantages:
  • the closed single-cell structure allows the battery to use a higher concentration of brine or lye to improve battery performance and avoid leakage currents.
  • seawater can enter the surface of each battery, use the flow of seawater, remove the heat of the battery in time, and solve the heat dissipation problem of the battery.
  • Figure 1 shows the overall structure of a tandem metal/oxygen battery stack for underwater use.
  • Figure 2 is a top view of a tandem metal/oxygen battery stack for underwater use.
  • Figure 3 is a side view of a tandem metal/oxygen battery stack for underwater use.
  • Figure 4 is a schematic diagram of a series connection of a series metal/oxygen battery stack for underwater use.
  • Figure 5 is a schematic view of the internal structure of a tandem metal/oxygen battery stack for underwater use.
  • Fig. 6 shows the temperature change curve of the magnesium/oxygen battery stack during constant current operation.
  • Figure 7 shows the polarization and power curves of a magnesium/oxygen battery stack.
  • 1-3 is a type of metal/oxygen battery stack for underwater use according to the present invention, which comprises an oxygen transfer chamber 1 made of ABS plastic plate and 11 unit cells 2 of the same structure.
  • the oxygen transmission chamber 1 is a hollow closed cavity structure, and 11 identical cells 2 are sequentially parallel to the two identical oxygen transmission chambers of the single cell 2 which are perpendicular to the two side walls of the plate. 1 fixed; 11 identical cell when assembled on the oxygen transfer cavity, leaving a gap between the cells, as a seawater flow grid 3;
  • Fig. 5 is a schematic view showing the internal structure of a tandem metal/oxygen battery stack for underwater use.
  • the plate-shaped metal anode 6 is fixed inside the rectangular parallelepiped casing, and the two plate-shaped inert cathodes 7 are placed in parallel in a symmetrical manner on both sides of the plate-shaped metal anode 6, and are fixed inside the rectangular parallelepiped casing, and two plate-shaped inert cathodes 7
  • the wall of the rectangular parallelepiped casing respectively constitutes two independent electrolyte chambers 8, and openings are formed on the upper wall surface of the rectangular parallelepiped housing of the two independent electrolyte chambers, and the upper end opening of the
  • the opening is covered with a hydrophobic gas permeable layer 4; above the wall surface of the rectangular parallelepiped housing of the electrolyte chamber 8, a liquid injection hole 5 provided with a plug body is provided for injecting the electrolyte.
  • the gap between the two plate-shaped inert cathodes 7 and the rectangular parallelepiped casing respectively constitute two independent oxygen chambers 9; the two plate-shaped inert cathodes 7 are connected in series by a current wire W circuit, and the current wires 10 are placed in a protective cover;
  • the chamber of the oxygen transfer chamber 1 is connected to the oxygen cylinder line.
  • the metal anode of the stack is made of a magnesium alloy plate, and the inert cathode is made of a carbon felt.
  • the temperature variation curve of the battery under constant current discharge of 30 mA/cm 2 is shown in Fig. 6.
  • the temperature of the stack can be controlled at 4 (TC, It indicates that the grids which are favorable for the flow of seawater between the cells when connected in series can effectively help the stack to dissipate heat and control the temperature during the operation of the stack to maintain a proper range.
  • Figure 7 shows the polarization and power curves for a series of magnesium/oxygen stacks operating. As can be seen from the figure, the open circuit voltage of the stack is 17.7V, and the average open circuit voltage of the single cell is 1.61V. It shows that the closed cell structure is designed to avoid voltage loss caused by leakage current.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hybrid Cells (AREA)
  • Primary Cells (AREA)

Abstract

本发明涉及一种用于水下的串联型金属/氧气电池堆，包括氧气传输腔和n个结构相同的单体电池；单体电池包括中空的长方体壳体、板状金属阳极和板状惰性阴极。本发明与现有技术相比，电池堆结构通过对单体电池的封闭设计并在单体电池外壳侧面上方设置注液孔，使电池可使用较高浓度的电解液（氯化钠或氢氧化钾），同时也解决了由于离子导通而引起的漏电流的问题；在顶部设置用于分割外界海水的疏水透气层，解决了金属/氧电池在海水或淡水中的排气问题；将金属/氧电池单体间进行分割，在单体间留出海水可自由进出的空间，利用海水在单池表面的流动降低电堆温度，保证电池堆的可靠运行。

Description

一种用于水下的串联型金属 /氧气电池堆
舰
本发明涉及化学电源， 具体地说是一种用于海水或淡水中的金属 /氧气电池堆。 背景技术
随着海洋及淡水水下探测的日益深入，水下用电子设备对电源的需求日益增加。种类繁 多的电子设备要求电池具有容量大、 功率高、 稳定性好等特点。 常规的一次电池， 如锌锰、 锌银等， 价格高、 而且质量和体积比能量低， 储存性能差。 如果用铅酸、 镍氢、 锂离子等二 次电池， 一方面， 受其额定容量限制， 电池的水下连续使用时间有限； 另一方面， 在深海工 作时， 需将电池密封于耐压容器中进行保护， 尤其是锂离子电池， 增加了系统的复杂性。
金属 /氧气电池利用盐水或碱液作为电解质， 具有在水下使用的阳极为镁、 铝金属或合 金， 阴极氧化剂为氧气、 过氧化氢。 该类电池的优点有： 一、 能量密度高。 由于这类电池可 由海水直接提供电解质， 因此其理论质量比能量高达数百瓦时每千克。 二、 原料来源丰富。 镁、铝均为地球储量大的金属元素， 且价格低廉。 三、 储存性能好。 该类电池在不接触电解 质 （如海水） 时处于不激活状态， 其储存性能好， 储存时间长达数年。 由于单体金属 /氧电 池的工作电压只有 1-1.5V, 无法满足用电设备的较高额定电压的需求， 而使用 DC-DC升压 电路则会大大降低电池的效率。 因此， 需要将若干金属 /氧电池串联起来， 以获得更高的输 出电压。 但是， 金属 /氧电池工作时阳极会发生析氢反应， 在水下特别是海水中使用时， 需 同时解决氢气排出和串联过程中由于离子导通引起的漏电流问题。 此外， 金属 /氧电池堆在 工作时会排出大量的热量， 电池堆的散热也是影响系统可靠运行的关键因素。 发明内容
本发明针对现有技术的不足，提供一种金属 /氧电池堆结构， 该电池堆结构通过对单体电 池的封闭设计并在单体电池外壳侧面上方设置注液孔， 使电池可使用较高浓度的电解液（氯 化钠或氢氧化钾）， 同时也解决了由于离子导通而引起的漏电流的问题； 在顶部设置用于分 割外界海水的疏水透气层， 解决了金属 /氧电池在海水或淡水中的排气问题； 将金属 /氧电池 单体间进行分割， 在单体间留出海水可自由进出的空间， 利用海水在单池表面的流动降低电 堆温度， 保证电池堆的可靠运行。
为实现上述目的， 本发明采用的技术方案为：
一种用于水下的串联型金属 /氧气电池堆， 包括氧气传输腔、 n个结构和尺寸相同的单体 金属 /氧气电池； n为 5=2的正整数；
氧气传输腔为中空的密闭腔体结构， n个结构和尺寸相同的单体电池依次平行并列设置， 单体电池均与氧气传输腔相固接； 单体电池包括中空的长方体壳体、 板状金属阳极和板状惰性阴极；
一板状金属阳极四周周边固定于长方体壳体内部， 并与壳体的一侧表面相平行， 两片板 状惰性阴极平行置于板状金属阳极的两侧、并其四周周边固定于长方体壳体内部， 两片板状 惰性阴极与板状金属阳极之间、 以及与阴极板体平行的长方体壳体侧壁面之间均留有空隙； 由两片板状惰性阴极分别与板状金属阳极、以及垂直于阴极板面的长方体壳体壁面分别构成 两个独立的电解液腔； 于两个独立的电解液腔的长方体壳体上壁面上分别设有开口， 长方体 壳体的上端开口位于两个独立的电解液腔的正上方， 且开口处覆盖有疏水透气层； 两片板状 惰性阴极分别与其远离金属阳极侧且与其相平行的长方体壳体壁面、以及垂直于阴极板面的 长方体壳体壁面分别构成两个独立的氧气腔； 两片板状惰性阴极通过导线电连接； 氧气传输腔的腔体与 n个单体电池的 2η个氧气腔相连通， 用于为电堆传输氧气； n个单 体电池的阳极和阴极通过电流导线电路串联连接。
所述 n个结构相同的单体电池依次平行地垂直固接于氧气传输腔的一侧壁面上。 所述两片板状惰性阴极以对称的方式平行置于板状金属阳极的两侧。
所述电解液腔的长方体壳体壁面上方设置有一配有塞体的注液孔， 用于注入电解液。 所述 n个结构相同的单体电池氧气传输腔上组装时， 相邻单体电池之间留有空隙， 作为 海水流动空间。
所述氧气传输腔的腔体与外界的氧气瓶管路连接、 或与氧气泵的出气口管路连接； n个 单体电池串联连接时采用的电流导线置于一保护罩内。
所述金属阳极是由 Al、 Mg、 Li或 Zn之一、 或它们中二种或二种以上的合金制备而成 板体， 惰性阴极采用碳毡、碳板、铜合金、 碳钢或以它们中的一种为基底的复合材料制成的 板体。
本发明与传统技术相比， 具有以下优点：
1.通过在金属 /氧电池顶部设置疏水透气层， 使阳极析出氢气顺利排出， 并阻隔海水， 实 现电池在水下的串联使用。
2.封闭式的单池结构使电池可以使用较高浓度的盐水或碱液， 提高电池的性能， 避免漏 电流的产生。
3.单池间分割设计， 海水可进入每个电池两侧表面， 利用海水的流动， 及时排走电池热 量， 解决电池的散热问题。 國翻
图 1用于水下的串联型金属 /氧气电池堆整体结构图。
图 2用于水下的串联型金属 /氧气电池堆俯视图。
图 3用于水下的串联型金属 /氧气电池堆侧视图。
图 4用于水下的串联型金属 /氧气电池堆串联连接示意图。
图 5用于水下的串联型金属 /氧气电池堆内部结构示意图。 图 6镁 /氧气电池堆恒流工作时的温度变化曲线。
图 7镁 /氧气电池堆工作时的极化曲线和功率曲线。
图中， 1为氧气传输腔； 2为单体电池； 3为单体电池间用于海水流动的栅格； 4为疏水 透气层； 5为注液孔； 6为板状金属阳极； 7为板状惰性阴极； 8为电解液腔； 9为氧气腔； 10为电流导线。 具体实施方式
图中 1-3为本发明所述用于水下的金属 /氧气电池堆的一种， 包括由 ABS塑料版制成的 氧气传输腔 1和 11个结构相同的单体电池 2。 氧气传输腔 1为中空的密闭腔体结构， 11个 结构相同的单体电池 2依次平行地于单体电池 2中垂直于极板的两个侧壁面上对称的与两个 相同的氧气传输腔 1固接； 11个结构相同的单体电池在氧气传输腔上组装时，单体电池之间 留有空隙， 作为海水流动栅格 3;
图 5为用于水下的串联型金属 /氧气电池堆内部结构示意图。板状金属阳极 6固定于长方 体壳体内部， 两片板状惰性阴极 7以对称的方式平行置于板状金属阳极 6的两侧、并固定于 长方体壳体内部， 两片板状惰性阴极 7与板状金属阳极 6之间、 以及与阴极板体垂直方向的 长方体壳体侧壁面之间均留有空隙； 由板状金属阳极 6、 两片板状惰性阴极 7、 以及垂直于 阴极板面的长方体壳体壁面分别构成两个独立的电解液腔 8, 于两个独立的电解液腔的长方 体壳体上壁面上设有开口， 长方体壳体的上端开口位于两个独立的电解液腔的正上方， 且开 口处覆盖有疏水透气层 4; 电解液腔 8的长方体壳体壁面上方设置有配有塞体的注液孔 5, 用于注入电解液。两片板状惰性阴极 7与长方体壳体间的空隙分别构成两个独立的氧气腔 9; 两片板状惰性阴极 7通过电流导线 W电路串联连接， 且电流导线 10置于一保护罩内； 氧 气传输腔 1的腔体与氧气瓶管路连接。
本实施例中电堆的金属阳极采用镁铝合金板， 惰性阴极采用碳毡。 电堆在 30 mA/cm2恒 流放电下， 电池内的温度变化曲线如图 6所示， 从图中可以看出， 在电堆运行 2小时内， 电 堆温度可控制在 4(TC ,表明单体电池串联连接时之间留有利于海水流动的栅格，可以有效的 帮助电堆排热， 控制电堆工作过程中的温度保持在合适区间。
图 7为串联的镁 /氧气电池堆工作时的极化曲线和功率曲线。 由图可见， 电堆开路电压为 17.7V,单体电池平均开路电压为 1.61V。表明封闭的单体电池结构的设计完全可以避免漏电 流引起的电压损失。

Claims

1. 一种用于水下的串联型金属 /氧气电池堆， 其特征在于： 包括氧气传输腔、 n个结构 和尺寸相同的单体金属 /氧气电池； n为 5=2的正整数；
氧气传输腔为中空的密闭腔体结构， n个结构和尺寸相同的单体电池依次平行并列设 置， 单体电池均与氧气传输腔相固接；
单体电池包括中空的长方体壳体、 板状金属阳极和板状惰性阴极；
一板状金属阳极四周周边固定于长方体壳体内部，并与壳体的一侧表面相平行，两片板 状惰性阴极平行置于板状金属阳极的两侧、并其四周周边固定于长方体壳体内部， 两片板状 惰性阴极与板状金属阳极之间、 以及与阴极板体平行的长方体壳体侧壁面之间均留有空隙； 由两片板状惰性阴极分别与板状金属阳极、以及垂直于阴极板面的长方体壳体壁面分别构成 两个独立的电解液腔； 于两个独立的电解液腔的长方体壳体上壁面上分别设有开口， 长方体 壳体的上端开口位于两个独立的电解液腔的正上方， 且开口处覆盖有疏水透气层； 两片板状 惰性阴极分别与其远离金属阳极侧且与其相平行的长方体壳体壁面、以及垂直于阴极板面的 长方体壳体壁面分别构成两个独立的氧气腔； 两片板状惰性阴极通过导线电连接；
氧气传输腔的腔体与 n个单体电池的 2η个氧气腔相连通， 用于为电堆传输氧气； n个 单体电池的阳极和阴极通过电流导线电路串联连接。
2. 按照权利要求 1所述电池堆， 其特征在于： n个结构相同的单体电池依次平行地垂 直固接于氧气传输腔的一侧壁面上。
3. 按照权利要求 1或 3所述电池堆， 其特征在于：
两片板状惰性阴极以对称的方式平行置于板状金属阳极的两侧。
4. 按照权利要求 1所述电池堆， 其特征在于： 电解液腔的长方体壳体壁面上方设置有 一配有塞体的注液孔， 用于注入电解液。
5. 按照权利要求 1所述电池堆， 其特征在于：
n个结构相同的单体电池在氧气传输腔上组装时， 相邻单体电池之间留有空隙， 作为海 水流动空间。
6. 按照权利要求 1所述电池堆， 其特征在于：
氧气传输腔的腔体与外界的氧气瓶管路连接、或与氧气泵的出气口管路连接； n个单体 电池串联连接时采用的电流导线置于一保护罩内。
7. 按照权利要求 1所述电池堆， 其特征在于：
金属阳极是由 Al、 Mg、 Li或 Zn之一、 或它们中二种或二种以上的合金制备而成的板 体， 惰性阴极采用碳毡、碳板、铜合金、碳钢或以它们中的一种为基底的复合材料制成的板 体。
PCT/CN2011/084482 2011-12-15 2011-12-22 一种用于水下的串联型金属/氧气电池堆 Ceased WO2013086752A1 (zh)

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