WO2015143954A1 - Oxygen sensor - Google Patents

Oxygen sensor Download PDF

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WO2015143954A1
WO2015143954A1 PCT/CN2015/072094 CN2015072094W WO2015143954A1 WO 2015143954 A1 WO2015143954 A1 WO 2015143954A1 CN 2015072094 W CN2015072094 W CN 2015072094W WO 2015143954 A1 WO2015143954 A1 WO 2015143954A1
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oxygen sensor
fuel cell
cell oxygen
sensor according
fuel
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PCT/CN2015/072094
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French (fr)
Chinese (zh)
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金·沃尔特·约翰
岳兰
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达特传感器（深圳）有限公司
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/409—Oxygen concentration cells

Definitions

  • This invention relates to electrochemical sensors, and more particularly to oxygen sensors.
  • One of the simplest types of oxygen sensors operating on the basis of electrochemical principles is the two-electrode system.
  • the most common modes include lead anodes and oxygen cathodes.
  • the working and counter electrodes are separated by a thin layer of electrolyte and communicate with the external circuit via a small resistor. After the gas diffuses into the sensor, an oxidation or reduction reaction is performed on the surface of the sensitive electrode to generate a current and flow through the two electrodes through the external circuit. The magnitude of this current is proportional to the concentration of the gas and can be measured by the load resistance of the external circuit.
  • the potential of the sensitive electrode In order for the reaction to occur, the potential of the sensitive electrode must be maintained within a specific range. However, as the concentration of the gas increases, the reaction current also increases, thus causing a change in the potential of the counter electrode (polarization). Since the two electrodes are connected by a simple load resistor, the potential of the sensitive electrode also varies with the potential of the counter electrode. If the concentration of the gas continues to rise, the potential of the sensitive electrode may eventually move out of its allowable range. At this point, the sensor will not be linear, so the upper limit concentration detected by the two-electrode gas sensor is limited.
  • the limitation on the polarization of the electrodes can be avoided by introducing a three-electrode system (i.e., a third electrode, a reference electrode, and an external potentiostatic operating circuit).
  • a three-electrode system i.e., a third electrode, a reference electrode, and an external potentiostatic operating circuit.
  • the sensitive electrode profile maintains a fixed value relative to the reference electrode. No current flows through the reference electrode, so both electrodes are maintained at a constant potential.
  • the counter electrode can still be polarized, but it does not have any limiting effect on the sensor.
  • Such an oxygen sensor has many advantages. They are compact, reliable, power-free, and operate across an acceptable temperature range without the need for heating. Despite their ability to provide satisfactory performance, the fact that they contain lead has caught the attention of today, and people are now actively looking for new lead-free formulations. The choice of available metals is limited to the contents of the periodic table and their alloys, and the success of such routes is judged by the success of electrochemical oxygen sensors that replace lead.
  • the lead-free oxygen sensor that has entered the market uses the three-electrode system described above, and thus is more complicated in structure and has a problem of pin incompatibility with the existing type of oxygen sensor.
  • the fuel cell oxygen sensor set forth in the present invention comprises: an oxygen cathode, a diffusion control device for controlling the rate of diffusion of oxygen to the cathode, and a fuel capable of obtaining an electric current by electrochemical oxidation of the fuel.
  • the cathode contains platinum.
  • the cathode contains gold.
  • the cathode contains silver.
  • the cathode contains carbon
  • the diffusion control device is a bore.
  • the diffusion control device is a microporous membrane.
  • the diffusion control device is a non-porous membrane.
  • the anode contains platinum.
  • the fuel is an alcohol
  • the electrolyte is acidic.
  • the electrolyte is alkaline.
  • the generated current is discharged through a resistor.
  • the fuel is 1,2-ethanediol (ethylene glycol).
  • the fuel is 1,2,3-propanetriol (glycerol).
  • the electrolyte contains sulfuric acid.
  • the electrolyte contains potassium hydroxide.
  • FIG. 1 is a schematic diagram of a fuel cell oxygen sensor in accordance with an embodiment of the present invention.
  • oxygen entering the sensor from the air can generally be strictly controlled in the following three ways:
  • the first two methods provide a value that is proportional to the percentage of oxygen and is linear over the effective range and is therefore unaffected by changes in atmospheric pressure. These methods are more commonly used and are widely used in the industrial and pharmaceutical industries.
  • the third way gives a partial pressure value and can be used for specialized applications such as the underwater breathing system, typically linear to 100%.
  • the inventors attempted to replace the lead electrode with other materials to obtain a new lead-free oxygen sensor.
  • These alternative materials may include some metals in the periodic table and their alloys, but in reality the metal is not the only one that can be used as an anode.
  • the material, the oxidizable molecule-fuel can also be used as the material for the anode.
  • the fuel can be in the form of a gas, a solid or a liquid. The gas is too large to be stored, so it cannot be used in actual operation.
  • Alkaline electrolytes may be preferred because non-precious metal materials can be used for current carrying, but they are susceptible to carbonation, and the selection of alkaline electrolytes is advantageous in suppressing this phenomenon, which must be taken into account when selecting materials.
  • the carbonation is caused by the oxidation product of the carbonaceous fuel rather than by carbon dioxide in the air. Specifically, because the proportion of carbon dioxide in the air is originally low, even if it is compared with the oxygen content introduced into the oxygen sensor from air in a strictly restricted manner, the carbon dioxide content is several orders of magnitude lower, so carbon dioxide in the air It is not the cause of carbonation of non-precious metal materials.
  • High energy density that is, not only has a low molecular weight, but also releases a plurality of electrons per molecule upon oxidation
  • the oxidation product at the anode should preferably not be insoluble and must never cause poisoning of the electrode catalyst.
  • liquid fuel that best meets these requirements appears to be a liquid polyol, specifically ethylene glycol (1,2-ethanediol).
  • Ethylene glycol is low in toxicity, and in a preferred design, its liquid temperature ranges from about -50 ° C to over 100 ° C, and no solid reaction product is observed during development and prototype testing.
  • the constituent parts of the fuel cell include: a cathode (oxygen electrode), typically containing platinum, gold or silver; a diffusion control device that controls the rate at which oxygen diffuses toward the cathode; an electrocatalytic anode, preferably comprising a platinum black catalyst; and an electrolyte/fuel mixture .
  • the fuel cell is operated continuously and the generated current is discharged through a parallel resistor, typically 100 ohms, to produce a potential of 1 to 15 millivolts, depending on the diameter of the pores or the properties of other diffusion control mechanisms previously mentioned.
  • the current generating such a potential is thus typically in the range of 10 to 150 mA.
  • FIG. 1 is a schematic diagram of a fuel cell oxygen sensor in accordance with an embodiment of the present invention.
  • the process of oxygen entering the sensor from the air is controlled by a hole in the disc 3, which is protected by the porous PTFE membranes 1 and 4.
  • oxygen molecules are reduced to hydroxide ions.
  • the reaction requires supply of electrons from the contact line 8 through an external circuit (usually a load resistor) at the contact line 5, which is catalyzed by a fuel such as ethylene glycol (1,2-ethanediol) dissolved in the electrolyte.
  • Oxidation at the active anode 7 is supplied.
  • the fuel/electrolyte mixture is stored in the vessel 9 to supplement the fuel consumed at the anode 7.
  • the hydroxide ions move from the cathode to the anode through the electrolyte to complete the internal circuit, thereby balancing the charge imbalance.
  • the entire assembly is housed within the outer casing 9. The amount of current generated depends on the percentage of oxygen in the air adjacent to the sensor inlet.
  • oxygen in the air passes through the PTFE membrane 1 and passes through a hole in the disc 3 in a controlled manner through the PTFE membrane 4 to the cathode 6 .
  • the fuel undergoes an oxidation reaction at the catalytically active anode 7, and the released electrons are led out through the contact line 8 and reach the contact line 5 through an external circuit (including a load resistor), and then these electrons are in contact with the above-mentioned oxygen from the air on the cathode 6, Reduction forms hydroxide ions.
  • the formed hydroxide ions move from the cathode 6 to the anode 7 under the action of a potential.
  • the electrons are passed from the contact line 8 through an external circuit During the movement to the contact line 5, corresponding currents and potentials are generated in the external circuit, and by measuring the current and potential, the percentage of oxygen in the air entering the sensor can be accurately determined.
  • An alkaline fuel cell oxygen sensor consisting of a gold cathode, a platinum black anode, a diffusion pore having a size of 10 to 100 ⁇ m, and an electrolyte composed of 25% by weight of ethylene glycol and 75% by weight of 4 M potassium hydroxide.
  • An acidic fuel cell oxygen sensor consists of a platinum cathode, a platinum black anode, a diffusion pore having a size of 10 to 100 ⁇ m, and an electrolyte composed of 75% by weight of ethylene glycol and 25% by weight of 4M sulfuric acid.
  • the lead-free oxygen sensor described herein using a two-electrode system is not only compact, reliable, non-electric, and can operate across an acceptable temperature range without heating, and is environmentally friendly.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A fuel cell oxygen sensor, comprising: an oxygen cathode (6); a diffusion control device used for controlling the rate of diffusion of oxygen to the cathode; fuel; an electro-catalysis anode (7) capable of obtaining a current through the electrochemical oxidation of the fuel; and an electrolyte, wherein some or all of the fuel is dissolved in the electrolyte.

Description

氧传感器Oxygen Sensor 技术领域Technical field
本发明涉及电化学传感器，尤其涉及氧传感器。This invention relates to electrochemical sensors, and more particularly to oxygen sensors.
背景技术Background technique
从20世纪七十年代起，电化学氧传感器(galvanic oxygen sensor)是被开发和市场化的第一批电化学传感器。Since the 1970s, galvanic oxygen sensors have been the first electrochemical sensors to be developed and marketed.
基于电化学原理工作的氧传感器其最简单的一种型式就是两电极系统。最常见的模式包括铅阳极和氧阴极。其工作电极和对电极由一薄层电解液隔开并经由一个很小的电阻联通外电路。当气体扩散进入传感器后，在敏感电极表面进行氧化或还原反应，产生电流并通过外电路流经两个电极。该电流的大小与气体的浓度成比例，可通过外电路的负荷电阻予以测量。One of the simplest types of oxygen sensors operating on the basis of electrochemical principles is the two-electrode system. The most common modes include lead anodes and oxygen cathodes. The working and counter electrodes are separated by a thin layer of electrolyte and communicate with the external circuit via a small resistor. After the gas diffuses into the sensor, an oxidation or reduction reaction is performed on the surface of the sensitive electrode to generate a current and flow through the two electrodes through the external circuit. The magnitude of this current is proportional to the concentration of the gas and can be measured by the load resistance of the external circuit.
为了使反应能够发生，敏感电极的电位必须保持在一个特定的范围内。但气体的浓度增加时，反应电流也增加，于是导致对电极电位改变(极化)。由于两电极是通过一个简单的负荷电阻连接起来的，虽然敏感电极的电位也会随着对电极的电位一起变化。如果气体的浓度不断地升高，敏感电极的电位最终有可能移出其允许范围。至此传感器将不成线性，因此两电极气体传感器检测的上限浓度受到一定限制。In order for the reaction to occur, the potential of the sensitive electrode must be maintained within a specific range. However, as the concentration of the gas increases, the reaction current also increases, thus causing a change in the potential of the counter electrode (polarization). Since the two electrodes are connected by a simple load resistor, the potential of the sensitive electrode also varies with the potential of the counter electrode. If the concentration of the gas continues to rise, the potential of the sensitive electrode may eventually move out of its allowable range. At this point, the sensor will not be linear, so the upper limit concentration detected by the two-electrode gas sensor is limited.
对电极的极化所受的限制可以引进三电极系统(即第三电极、参考电极、和利用一外部的恒电位工作电路)来予以避免。在这样一种装置中，敏感电极曲线相对于参考电极保持一固定值。在参考电极中无电流流过，因此这两个电极均维持在一恒定的电位。对电极则仍然可以进行极化，但对传感器而言已不产生任何限制作用。The limitation on the polarization of the electrodes can be avoided by introducing a three-electrode system (i.e., a third electrode, a reference electrode, and an external potentiostatic operating circuit). In such a device, the sensitive electrode profile maintains a fixed value relative to the reference electrode. No current flows through the reference electrode, so both electrodes are maintained at a constant potential. The counter electrode can still be polarized, but it does not have any limiting effect on the sensor.
这样的氧传感器具有很多优点。它们紧凑、可靠、不用电、且可跨可接受温度范围操作而无需加热。尽管它们能够提供令人满意的性能，但是其含铅的事实在当今引起了关注，人们如今在积极寻找新的无铅配方。可用金属的选择限于周期表的内容以及它们的合金，此类途径的成功与否通过替代掉铅的电化学氧传感器的成功来判断。Such an oxygen sensor has many advantages. They are compact, reliable, power-free, and operate across an acceptable temperature range without the need for heating. Despite their ability to provide satisfactory performance, the fact that they contain lead has caught the attention of today, and people are now actively looking for new lead-free formulations. The choice of available metals is limited to the contents of the periodic table and their alloys, and the success of such routes is judged by the success of electrochemical oxygen sensors that replace lead.
已进入市场的无铅氧传感器采用的是以上所述的三电极系统，因此在结构上更加复杂，且与现有类型的氧传感器之间存在管脚不兼容的问题。 The lead-free oxygen sensor that has entered the market uses the three-electrode system described above, and thus is more complicated in structure and has a problem of pin incompatibility with the existing type of oxygen sensor.
因此，人们需要开发一种采用两电极系统的无铅氧传感器，其不仅紧凑、可靠、不用电、可跨可接受温度范围操作而无需加热，而且对环境友好。Therefore, there is a need to develop a lead-free oxygen sensor that employs a two-electrode system that is not only compact, reliable, non-electric, can operate across an acceptable temperature range without heating, and is environmentally friendly.
发明内容Summary of the invention
鉴于上述提到的主要问题，本发明中阐述的燃料电池氧传感器，包括：氧阴极，用于控制氧向阴极扩散的速率的扩散控制装置，燃料，能够通过燃料的电化学氧化来得到电流的电催化阳极，以及电解质，所述燃料部分或全部地溶解在所述电解质中。In view of the above-mentioned main problems, the fuel cell oxygen sensor set forth in the present invention comprises: an oxygen cathode, a diffusion control device for controlling the rate of diffusion of oxygen to the cathode, and a fuel capable of obtaining an electric current by electrochemical oxidation of the fuel. An electrocatalytic anode, and an electrolyte, the fuel being partially or completely dissolved in the electrolyte.
在本发明的燃料电池氧传感器的一个实施例中，阴极含铂。In one embodiment of the fuel cell oxygen sensor of the present invention, the cathode contains platinum.
在本发明的燃料电池氧传感器的一个实施例中，阴极含金。In one embodiment of the fuel cell oxygen sensor of the present invention, the cathode contains gold.
在本发明的燃料电池氧传感器的一个实施例中，阴极含银。In one embodiment of the fuel cell oxygen sensor of the present invention, the cathode contains silver.
在本发明的燃料电池氧传感器的一个实施例中，阴极含碳。In one embodiment of the fuel cell oxygen sensor of the present invention, the cathode contains carbon.
在本发明的燃料电池氧传感器的一个实施例中，扩散控制装置是孔。In one embodiment of the fuel cell oxygen sensor of the present invention, the diffusion control device is a bore.
在本发明的燃料电池氧传感器的一个实施例中，扩散控制装置是微孔膜。In one embodiment of the fuel cell oxygen sensor of the present invention, the diffusion control device is a microporous membrane.
在本发明的燃料电池氧传感器的一个实施例中，扩散控制装置是无孔膜。In one embodiment of the fuel cell oxygen sensor of the present invention, the diffusion control device is a non-porous membrane.
在本发明的燃料电池氧传感器的一个实施例中，阳极含铂。In one embodiment of the fuel cell oxygen sensor of the present invention, the anode contains platinum.
在本发明的燃料电池氧传感器的一个实施例中，燃料是醇。In one embodiment of the fuel cell oxygen sensor of the present invention, the fuel is an alcohol.
在本发明的燃料电池氧传感器的一个实施例中，电解质是酸性的。In one embodiment of the fuel cell oxygen sensor of the present invention, the electrolyte is acidic.
在本发明的燃料电池氧传感器的一个实施例中，电解质是碱性的。In one embodiment of the fuel cell oxygen sensor of the present invention, the electrolyte is alkaline.
在本发明的燃料电池氧传感器的一个实施例中，所产生的电流通过电阻器放电。In one embodiment of the fuel cell oxygen sensor of the present invention, the generated current is discharged through a resistor.
在本发明的燃料电池氧传感器的一个实施例中，燃料是1，2-乙二醇(乙二醇)。In one embodiment of the fuel cell oxygen sensor of the present invention, the fuel is 1,2-ethanediol (ethylene glycol).
在本发明的燃料电池氧传感器的一个实施例中，燃料是1，2，3-丙三醇(甘油)。In one embodiment of the fuel cell oxygen sensor of the present invention, the fuel is 1,2,3-propanetriol (glycerol).
在本发明的燃料电池氧传感器的一个实施例中，电解质含硫酸。In one embodiment of the fuel cell oxygen sensor of the present invention, the electrolyte contains sulfuric acid.
在本发明的燃料电池氧传感器的一个实施例中，电解质含氢氧化钾。In one embodiment of the fuel cell oxygen sensor of the present invention, the electrolyte contains potassium hydroxide.
附图说明DRAWINGS
图1是根据本发明一实施例的燃料电池氧传感器的示意图。 1 is a schematic diagram of a fuel cell oxygen sensor in accordance with an embodiment of the present invention.
具体实施方式detailed description
为了更好地理解本发明，下面结合附图对本发明的实施例作详细说明。但本发明的保护范围不仅仅局限于下面的实施例。本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样在所附权利要求书限定的范围之内。In order to better understand the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, the scope of protection of the present invention is not limited only to the following embodiments. A person skilled in the art can make various modifications or changes to the invention, and such equivalents are also within the scope of the appended claims.
在本发明的氧传感器中，从空气进入传感器的氧通常可通过以下三种方式被严格控制：In the oxygen sensor of the present invention, oxygen entering the sensor from the air can generally be strictly controlled in the following three ways:
1.小毛细孔；1. small pores;
2.低渗透率的微孔膜；2. a low permeability microporous membrane;
3.无孔膜。3. No pore film.
前两种方式提供与氧百分比成正比并在有效范围内呈线性的值，因此不受大气压变化的影响。这些方式较为常用，广泛应用于工业和制药业。第三种方式给出分压值，并且可被用于诸如水下呼吸系统的专门应用，通常线性至100％。The first two methods provide a value that is proportional to the percentage of oxygen and is linear over the effective range and is therefore unaffected by changes in atmospheric pressure. These methods are more commonly used and are widely used in the industrial and pharmaceutical industries. The third way gives a partial pressure value and can be used for specialized applications such as the underwater breathing system, typically linear to 100%.
另一方面，发明人试图使用其他材料替代铅电极以获得的新的无铅氧传感器，这些替代材料可以包括周期表中的一些金属及其合金，但是实际上金属并不是唯一可用作阳极的材料，可被氧化的分子-燃料-也可用作阳极的材料。原则上来说，燃料可以是气体、固体或液体的形式。气体体积过大，不便于储存，因此在实际操作中是不能采用的。On the other hand, the inventors attempted to replace the lead electrode with other materials to obtain a new lead-free oxygen sensor. These alternative materials may include some metals in the periodic table and their alloys, but in reality the metal is not the only one that can be used as an anode. The material, the oxidizable molecule-fuel, can also be used as the material for the anode. In principle, the fuel can be in the form of a gas, a solid or a liquid. The gas is too large to be stored, so it cannot be used in actual operation.
我们考虑使用可溶于所选择的酸性或碱性的电解质中的固体和液体形式的燃料。碱性电解质可能是优选的，因为非贵金属材料可用于载流，但是它们易于被碳酸化，选择碱性电解质有利于抑制此种现象的发生，在选择材料的时候必须将此因素考虑在内。所述碳酸化是由于含碳燃料的氧化产物造成的，而不是由空气中的二氧化碳造成的。具体来说，因为空气中二氧化碳的比例原本就很低，即使是与以严格限制的方式从空气引入该氧传感器的氧气含量相比，二氧化碳的含量也要低好几个数量级，因此空气中的二氧化碳并不是导致非贵金属材料碳酸化的原因。We consider the use of fuels in solid and liquid form that are soluble in the selected acidic or basic electrolyte. Alkaline electrolytes may be preferred because non-precious metal materials can be used for current carrying, but they are susceptible to carbonation, and the selection of alkaline electrolytes is advantageous in suppressing this phenomenon, which must be taken into account when selecting materials. The carbonation is caused by the oxidation product of the carbonaceous fuel rather than by carbon dioxide in the air. Specifically, because the proportion of carbon dioxide in the air is originally low, even if it is compared with the oxygen content introduced into the oxygen sensor from air in a strictly restricted manner, the carbon dioxide content is several orders of magnitude lower, so carbon dioxide in the air It is not the cause of carbonation of non-precious metal materials.
所选择燃料的期望特性包括：The desired characteristics of the selected fuel include:
1.低毒性，因为用一种有毒成分替代另一种有毒成分并无益处；1. Low toxicity, because it is not beneficial to replace one toxic component with another toxic component;
2.低挥发性，否则燃料会因为蒸发而损耗；2. Low volatility, otherwise the fuel will be lost due to evaporation;
3.在电解质中的溶解性，否则燃料在阳极处无法以令人满意的程度发生反应； 3. Solubility in the electrolyte, otherwise the fuel cannot react at a satisfactory level at the anode;
4.低凝固点，由此使得燃料/电解质混合物可以在尽可能宽的范围内用来进行操作；4. a low freezing point, thereby allowing the fuel/electrolyte mixture to be used in the widest possible range;
5.高能密度，即不但具有低的分子量，而且在氧化时每个分子释放多个电子；5. High energy density, that is, not only has a low molecular weight, but also releases a plurality of electrons per molecule upon oxidation;
6.阳极处的氧化产物优选地应当不是不溶性的，并且绝不能造成电极催化剂中毒。6. The oxidation product at the anode should preferably not be insoluble and must never cause poisoning of the electrode catalyst.
最符合这些要求的一类液态燃料似乎是液态多元醇，具体而言是乙二醇(1，2-乙二醇)。乙二醇毒性低，在优选的设计中，其液态温度范围为约-50℃至100℃以上，且在开发和原型测试时没有观察到有固态反应产物。One type of liquid fuel that best meets these requirements appears to be a liquid polyol, specifically ethylene glycol (1,2-ethanediol). Ethylene glycol is low in toxicity, and in a preferred design, its liquid temperature ranges from about -50 ° C to over 100 ° C, and no solid reaction product is observed during development and prototype testing.
因此，燃料电池的构成部分包括：阴极(氧电极)，通常含有铂、金或银；控制氧向阴极扩散的速率的扩散控制装置；电催化阳极，优选包含铂黑催化剂；以及电解质/燃料混合物。该燃料电池连续操作，所产生的电流通过通常为100Ω的并联电阻器放电以产生1至15毫伏的电位，这取决于孔隙的直径或前面提及的其他扩散控制机制的性质。产生这样的电位的电流由此通常在10至150毫安的范围内。Thus, the constituent parts of the fuel cell include: a cathode (oxygen electrode), typically containing platinum, gold or silver; a diffusion control device that controls the rate at which oxygen diffuses toward the cathode; an electrocatalytic anode, preferably comprising a platinum black catalyst; and an electrolyte/fuel mixture . The fuel cell is operated continuously and the generated current is discharged through a parallel resistor, typically 100 ohms, to produce a potential of 1 to 15 millivolts, depending on the diameter of the pores or the properties of other diffusion control mechanisms previously mentioned. The current generating such a potential is thus typically in the range of 10 to 150 mA.
图1是根据本发明一实施例的燃料电池氧传感器的示意图。1 is a schematic diagram of a fuel cell oxygen sensor in accordance with an embodiment of the present invention.
通过圆盘3中的孔控制氧从空气中进入传感器的过程，该孔由多孔PTFE膜1和4保护。在阴极6处，氧分子还原成氢氧根离子。该反应需要从接触线8通过外部电路(通常是负载电阻)在接触线5处供应电子，该电子是通过溶解在电解质中的诸如乙二醇(1，2-乙二醇)的燃料在催化活性阳极7处的氧化来供应的。燃料/电解质混合物保存在容器9中，从而对阳极7处消耗的燃料进行补充。氢氧根离子通过电解质从阴极移向阳极以完成内部电路，由此使电荷的不平衡得以平衡。整个组件被容纳在外壳9内。所产生的电流的量取决于与传感器入口相邻的空气中氧的百分比。The process of oxygen entering the sensor from the air is controlled by a hole in the disc 3, which is protected by the porous PTFE membranes 1 and 4. At the cathode 6, oxygen molecules are reduced to hydroxide ions. The reaction requires supply of electrons from the contact line 8 through an external circuit (usually a load resistor) at the contact line 5, which is catalyzed by a fuel such as ethylene glycol (1,2-ethanediol) dissolved in the electrolyte. Oxidation at the active anode 7 is supplied. The fuel/electrolyte mixture is stored in the vessel 9 to supplement the fuel consumed at the anode 7. The hydroxide ions move from the cathode to the anode through the electrolyte to complete the internal circuit, thereby balancing the charge imbalance. The entire assembly is housed within the outer casing 9. The amount of current generated depends on the percentage of oxygen in the air adjacent to the sensor inlet.
在图1所示的燃料电池氧传感器的实际操作的一个实施方式中，空气中的氧气透过PTFE膜1，以受控的方式通过圆盘3中的孔，通过PTFE膜4，到达阴极6。燃料在催化活性阳极7处发生氧化反应，释放出的电子通过接触线8导出，通过外部电路(包括负载电阻)到达接触线5，然后这些电子在阴极6上与上述来自空气中的氧气接触，还原形成氢氧根离子。该形成的氢氧根离子在电势作用下从阴极6移动到阳极7处。所述电子在通过外部电路从接触线8 移动到接触线5的过程中，在外部电路中产生相应的电流和电势，通过测量该电流和电势，可以准确地确定进入该传感器的空气中氧气的百分比。In one embodiment of the actual operation of the fuel cell oxygen sensor shown in Figure 1, oxygen in the air passes through the PTFE membrane 1 and passes through a hole in the disc 3 in a controlled manner through the PTFE membrane 4 to the cathode 6 . The fuel undergoes an oxidation reaction at the catalytically active anode 7, and the released electrons are led out through the contact line 8 and reach the contact line 5 through an external circuit (including a load resistor), and then these electrons are in contact with the above-mentioned oxygen from the air on the cathode 6, Reduction forms hydroxide ions. The formed hydroxide ions move from the cathode 6 to the anode 7 under the action of a potential. The electrons are passed from the contact line 8 through an external circuit During the movement to the contact line 5, corresponding currents and potentials are generated in the external circuit, and by measuring the current and potential, the percentage of oxygen in the air entering the sensor can be accurately determined.
以下描述本发明的燃料电池氧传感器的两个示例。Two examples of the fuel cell oxygen sensor of the present invention are described below.
示例1Example 1
碱性燃料电池氧传感器，由金阴极、铂黑阳极、尺寸为10至100微米的扩散孔、以及由重量百分比25％的乙二醇和重量百分比75％的4M氢氧化钾构成的电解质。An alkaline fuel cell oxygen sensor consisting of a gold cathode, a platinum black anode, a diffusion pore having a size of 10 to 100 μm, and an electrolyte composed of 25% by weight of ethylene glycol and 75% by weight of 4 M potassium hydroxide.
示例2Example 2
酸性燃料电池氧传感器，由铂阴极、铂黑阳极、尺寸为10至100微米的扩散孔、以及由重量百分比75％的乙二醇和重量百分比25％的4M硫酸构成的电解质。An acidic fuel cell oxygen sensor consists of a platinum cathode, a platinum black anode, a diffusion pore having a size of 10 to 100 μm, and an electrolyte composed of 75% by weight of ethylene glycol and 25% by weight of 4M sulfuric acid.
本领域技术人员可以理解，以上示例仅仅是本发明的燃料电池氧传感器的两个示例。Those skilled in the art will appreciate that the above examples are merely two examples of fuel cell oxygen sensors of the present invention.
本文在所述的采用两电极系统的无铅氧传感器不仅紧凑、可靠、不用电、且可跨可接受温度范围操作而无需加热，而且对环境友好。 The lead-free oxygen sensor described herein using a two-electrode system is not only compact, reliable, non-electric, and can operate across an acceptable temperature range without heating, and is environmentally friendly.

Claims (17)

  1. 一种燃料电池氧传感器，包括：A fuel cell oxygen sensor comprising:
    氧阴极，Oxygen cathode,
    用于控制氧向阴极扩散的速率的扩散控制装置，a diffusion control device for controlling the rate of diffusion of oxygen to the cathode,
    燃料，fuel,
    能够通过所述燃料的电化学氧化来得到电流的电催化阳极，以及An electrocatalytic anode capable of obtaining a current by electrochemical oxidation of the fuel, and
    电解质，所述燃料部分或全部地溶解在所述电解质中。An electrolyte that is partially or wholly dissolved in the electrolyte.
  2. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述阴极含铂。A fuel cell oxygen sensor according to claim 1 wherein said cathode contains platinum.
  3. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述阴极含金。A fuel cell oxygen sensor according to claim 1 wherein said cathode contains gold.
  4. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述阴极含银。A fuel cell oxygen sensor according to claim 1 wherein said cathode contains silver.
  5. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述阴极含碳。A fuel cell oxygen sensor according to claim 1 wherein said cathode contains carbon.
  6. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述扩散控制装置是孔。A fuel cell oxygen sensor according to claim 1 wherein said diffusion control means is a bore.
  7. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述扩散控制装置是微孔膜。A fuel cell oxygen sensor according to claim 1 wherein said diffusion control means is a microporous membrane.
  8. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述扩散控制装置是无孔膜。A fuel cell oxygen sensor according to claim 1, wherein said diffusion control means is a non-porous film.
  9. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述阳极含铂。A fuel cell oxygen sensor according to claim 1 wherein said anode contains platinum.
  10. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述燃料是醇。 A fuel cell oxygen sensor according to claim 1 wherein said fuel is an alcohol.
  11. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述电解质是酸性的。The fuel cell oxygen sensor of claim 1 wherein said electrolyte is acidic.
  12. 如权利要求1所述的燃料电池氧传感器，其特征在于，所述电解质是碱性的。The fuel cell oxygen sensor of claim 1 wherein said electrolyte is alkaline.
  13. 如权利要求1所述的燃料电池氧传感器，其特征在于，所产生的电流通过电阻器放电。A fuel cell oxygen sensor according to claim 1, wherein the generated current is discharged through a resistor.
  14. 如权利要求10所述的燃料电池氧传感器，其特征在于，所述燃料是1，2-乙二醇(乙二醇)。A fuel cell oxygen sensor according to claim 10, wherein said fuel is 1,2-ethanediol (ethylene glycol).
  15. 如权利要求10所述的燃料电池氧传感器，其特征在于，所述燃料是1，2，3-丙三醇(甘油)。A fuel cell oxygen sensor according to claim 10, wherein said fuel is 1,2,3-propanetriol (glycerol).
  16. 如权利要求11所述的燃料电池氧传感器，其特征在于，所述电解质含硫酸。A fuel cell oxygen sensor according to claim 11 wherein said electrolyte contains sulfuric acid.
  17. 如权利要求12所述的燃料电池氧传感器，其特征在于，所述电解质含氢氧化钾。 A fuel cell oxygen sensor according to claim 12, wherein said electrolyte contains potassium hydroxide.
PCT/CN2015/072094 2014-03-26 2015-02-02 Oxygen sensor WO2015143954A1 (en)

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CN106383155A (en) * 2016-12-01 2017-02-08 深圳市深安旭传感技术有限公司 New-energy vehicle hydrogen sensor with gas diffusion channel
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0766085A2 (en) * 1995-09-28 1997-04-02 Matsushita Electric Industrial Co., Ltd. Electrochemical device
US6080294A (en) * 1998-07-15 2000-06-27 Atwood Industries, Inc. Gas sensor with dual electrolytes
JP2006153568A (en) * 2004-11-26 2006-06-15 Nissan Motor Co Ltd Gas measuring instrument
CN1867825A (en) * 2003-08-12 2006-11-22 Rae系统股份有限公司 Solid polymer electrolyte oxygen sensor
CN203929706U (en) * 2014-03-26 2014-11-05 达特传感器（深圳）有限公司 Lambda sensor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573648A (en) * 1995-01-31 1996-11-12 Atwood Systems And Controls Gas sensor based on protonic conductive membranes
US7687184B2 (en) * 2004-10-19 2010-03-30 Panasonic Corporation Membrane electrode assembly with a fibrous substrate, method for producing the same and polymer electrolyte fuel cell
CN102183566A (en) * 2011-01-05 2011-09-14 高国强 Oxygen volume percent concentration sensor based on capillary chemical corrosion method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0766085A2 (en) * 1995-09-28 1997-04-02 Matsushita Electric Industrial Co., Ltd. Electrochemical device
US6080294A (en) * 1998-07-15 2000-06-27 Atwood Industries, Inc. Gas sensor with dual electrolytes
CN1867825A (en) * 2003-08-12 2006-11-22 Rae系统股份有限公司 Solid polymer electrolyte oxygen sensor
JP2006153568A (en) * 2004-11-26 2006-06-15 Nissan Motor Co Ltd Gas measuring instrument
CN203929706U (en) * 2014-03-26 2014-11-05 达特传感器（深圳）有限公司 Lambda sensor

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