WO2008031318A1 - A liquid cathode fuel cell - Google Patents

A liquid cathode fuel cell Download PDF

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Publication number
WO2008031318A1
WO2008031318A1 PCT/CN2007/002238 CN2007002238W WO2008031318A1 WO 2008031318 A1 WO2008031318 A1 WO 2008031318A1 CN 2007002238 W CN2007002238 W CN 2007002238W WO 2008031318 A1 WO2008031318 A1 WO 2008031318A1
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WIPO (PCT)
Prior art keywords
acid
cathode
salt
anode
fuel cell
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PCT/CN2007/002238
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French (fr)
Chinese (zh)
Inventor
Ji Cui
Nie Luo
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Ji Cui
Nie Luo
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Publication of WO2008031318A1 publication Critical patent/WO2008031318A1/en

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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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 chemical energy-electric energy conversion device, a fuel cell based on a liquid oxidant and a liquid reducing agent.
  • the hydrogen-oxygen fuel is carried as a gas.
  • the need for a high-pressure gas cylinder or liquefaction unit increases the weight and risk of the system.
  • the adiabatic liquefaction device only has the ability to temporarily store liquid oxygen and liquid hydrogen.
  • the catalytic reduction process of the oxyhydrogen fuel on the catalyst-carbon powder-proton exchange membrane is a reaction occurring on the gas-solid liquid three-phase, and the volumetric energy density of the gas is low, and the water generated by the reaction is difficult to control. Too much water will flood the catalyst making it difficult to reduce the gaseous fuel, too little water will increase the transmembrane resistance and electrode polarization. Often the cathode is too wet and the anode is too dry resulting in a decrease in battery efficiency and power.
  • Methanol-air fuel cells overcome the problem of gas fuel storage.
  • the specific operation is that liquid methanol replaces hydrogen as the anode fuel, thus changing the gas-solid liquid three-phase reaction of the anode into a solid-liquid two-phase reaction, which greatly increases the contact between the fuel and the catalyst.
  • the catalytic reduction of methanol has a low catalytic efficiency and a large overpotential, and the generated carbon monoxide causes poisoning of the platinum catalyst, although it is compensated by a large dose of precious metal catalyst, but it is improved. cost.
  • the cathode of the air electrode is still gas-solid liquid three-phase catalysis, and there is still a disadvantage of difficulty in water management.
  • the vanadium redox battery is a redox battery with V5+/V4+ as the cathode material and V3+/V2+ as the anode material. All valence vanadium exists in the form of liquid ions, completely eliminating the gas medium, eliminating the solid precipitation caused by charge and discharge in a general battery, and is a complete liquid battery. However, due to the solubility of vanadium ions, its volumetric energy density is not suitable for long-term discharge of large currents.
  • the invention provides a fuel cell based on liquid oxidant, which not only overcomes oxygen in the oxyhydrogen fuel cell Gas carrying and storage problems, and overcome the disadvantages of low energy density of vanadium oxide and methanol-air fuel cells.
  • a liquid cathode fuel cell is structurally composed of a cathode fuel, a cathode, a diaphragm, an anode, and an anode fuel, and is characterized in that the fuel cell comprises a halogen oxyacid or a halogen oxyacid having a concentration by weight of 1% to 100% by weight.
  • the acidic liquid solution of the salt is a cathode fuel and is directly or indirectly discharged on the cathode to obtain electrical energy.
  • a halogen oxyacid or a halogen oxyacid salt selected from one or more of the following acids or acid salts thereof: hypochlorous acid, chlorous acid, chloric acid, And perchloric acid, hypobromous acid, bromic acid, bromic acid, and perbromic acid, hypoiodous acid, iodic acid, iodic acid, and periodic acid.
  • the concentration of the halogen oxyacid or the halogen oxyacid salt in the solution of the halogen oxyacid or the halogen oxyacid salt is from 1% to 100% by weight.
  • the cathode is made of an electrically conductive acid-resistant material selected from one or more of the following materials: carbon powder, carbon felt, carbon cloth, glassy carbon, active Carbon, carbon fiber, lead oxide, antimony oxide, porous nickel, Raney ni ckel, and titanium alloy.
  • the cathode is provided with a catalyst for catalytically reducing a halogen oxyacid, which is selected from one or more of the following compounds or elements: nickel, palladium, platinum, copper, silver, gold , lead, cadmium, mercury, antimony, antimony, vanadium, molybdenum and their alloys or compounds.
  • a catalyst for catalytically reducing a halogen oxyacid which is selected from one or more of the following compounds or elements: nickel, palladium, platinum, copper, silver, gold , lead, cadmium, mercury, antimony, antimony, vanadium, molybdenum and their alloys or compounds.
  • the acidic liquid solution may contain one or more of the following adjuvants in addition to the halogen oxyacid: bromine elemental substance and soluble bromide, hydrogen peroxide, soluble barium salt , soluble chromium salts, soluble cobalt salts, soluble iron salts, soluble manganese salts, soluble molybdenum salts, soluble barium salts, soluble barium salts, soluble tin salts, soluble vanadium salts.
  • the separator comprises an ion exchange membrane having a thickness of 0.1 to 200 ⁇ m.
  • the cathode and the anode can be spatially connected in the form of a bipolar plate.
  • the acidic liquid solution may contain, in addition to the halogen oxyacid, one or more of the following concentrations of the catholyte: 0.1% to 95% of the inorganic or organic acid: hydrochloric acid , sulfuric acid, nitric acid, phosphoric acid, tri fluoroacetic acid aci d , benzenesulfonic acid, naphthalenesulfonic acid, polymer acid.
  • the present invention contemplates the technical problem of using a liquid solution of halogen aci d or halogen ac id salts instead of air, pure oxygen or high pressure oxygen as a cathode fuel.
  • Halogen oxyacids include hypohalous acids, halous acids, halogen acids, and perhalogen acids.
  • the halogen in the present invention means chlorine, bromine, iodine, and does not contain fluorine.
  • Halogen oxyacids, especially halogen acids and perhalogen acids are high energy oxygenates. For example, ammonium perchlorate as an oxidant has been widely used in various rocket propellants.
  • halogen oxyacid can be regarded as a solid oxygen and thus has a higher volume energy density than gaseous oxygen.
  • the salt solution of the halogen oxyacid has a strong dissociation degree and solubility, and is more favorable for the increase of the volume energy density.
  • the meaning of "halogen oxyacid" includes halogen oxyacids and salts thereof.
  • the proton required for the reaction may be contained in the catholyte (e.g., sulfuric acid or hydrochloric acid is added to the catholyte), or the protons in the oxyhydrogen gas fuel cell like the proton exchange membrane electrolyte may be diffused from the anode. Electrons are transferred from the external circuit (from the electrons lost by the anolyte fuel).
  • the above reaction is greatly simplified, omitting possible intermediate steps -
  • Catalysts suitable for use include nickel palladium platinum, copper silver gold, and alloys or compounds thereof.
  • some oxides, such as lead oxide, antimony oxide, titanium oxide, antimony oxide, and the like have been widely used in the industrial electrolysis of perchlorate and chlorate. It is worth noting, however, that they are used to catalyze the oxidation of low-cost halogen oxyacids to high-valence halogen oxyacids, rather than the opposite.
  • the battery of the present invention is similar in overall structure to a conventional bipolar plate type proton exchange membrane oxyhydrogen fuel cell.
  • the gas cylinder of a conventional oxyhydrogen fuel cell is replaced by a liquid fuel storage tank, and the catholyte and the anode liquid are transported by the infusion pump.
  • the catholyte therein contains a halogen oxyacid or a salt solution thereof.
  • the anode can be a variety of gas or liquid reducible substances, such as gas hydrogen, liquid sodium borohydride solution, hydrazine, ammonia solution.
  • the catholyte and the cathode catalytic layer may contain a redox catalyst.
  • the catholyte is pumped from the catholyte storage tank to the cathode inlet, passed through the cathode catalytic layer, and exits the cathode outlet.
  • the configuration of the battery pack can be a bipolar plate type, similar to the bipolar plate venting type in the oxyhydrogen fuel cell stack cited in the literature. In order to reduce the pressure loss in the through-liquid, the flow path of the bipolar plate can be changed to a straight-through type.
  • the carbon used in the carbon electrode of the present invention includes carbon powder, carbon felt, carbon cloth, glassy carbon, activated carbon and carbon fibers (including nano carbon fibers).
  • the carbon electrode can be formed by a calendering method or a hot pressing method.
  • the catholyte and the carbon electrode layer may optionally contain a cathode catalyst.
  • a cathode catalyst include nickel Palladium uranium, copper silver, and their alloys or compounds, lead oxide, cerium oxide, cerium oxide, titanium oxide, and the like.
  • the dispersion of the cathode catalyst in the carbon electrode layer can be achieved in various ways, such as grinding and mixing, chemical or electrochemical reduction of catalyst precursors, electroplating, and the like.
  • the most preferred catalyst is lead oxide.
  • conductive acid-resistant materials can also serve as the cathode.
  • the halogen oxyacid cathode fuel most preferred for use is an aqueous solution of a halogen acid and a perhalogen acid, i.e., perchloric acid, perbromic acid, periodic acid, i.e., chloric acid, bromic acid, iodic acid, and salts thereof.
  • a single halogen acid and a perhalogen acid may be used in the case of use, and a mixture of different halogen acids and perhalogen acids may also be used.
  • the pH of the aqueous solution of the cathode fuel should be acidic, ie pH ⁇ 7. 0. The acidic conditions facilitate the catalytic reduction of halogen oxyacids.
  • an acid may be additionally added to the catholyte in addition to the acidity of the halogen acid and the perhalogen acid.
  • the most preferred inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
  • Organic acids include fluorosulfonic acid (e.g., trifluoroacetic acid), benzenesulfonic acid, aromatic ring-containing sulfonic acid, and the like.
  • the concentration of the aqueous solution of the halogen oxyacid catholyte is between 0.1% and 100%, and the concentration most likely to be used for energy density is between 0.5% and 70%.
  • industrial concentrated perchloric acid is present in 70% form and can be used directly as fuel.
  • the battery separator used in the halogen oxyacid cathode fuel cell of the present invention is a separator having a thickness of 0.1 to 200 ⁇ m.
  • the most preferred membrane to be used is the cation exchange membrane - Nafion 117.
  • an anion exchange membrane which is stable under acid hydrazine conditions can also be used.
  • auxiliary agent In addition to the halogen oxyacid fuel, other adjuvants may be added to the cathode.
  • the function of the auxiliary agent is to improve the dissociation degree of the halogen oxyacid salt, reduce the side reaction, especially the occurrence of oxygen and chlorine, reduce the chlorine generated by the side reaction, the vapor pressure of bromine, and increase the chlorine and bromine generated by the side reaction. Solubility.
  • the optional inorganic adjuvant includes a plurality of standard or redox potentials of 1. 5V-0. 5V of a compound or element, or a reduced precursor of a compound or element, such as sodium bromide, potassium bromide, and other metal bromides. .
  • auxiliary Qi 1 J is an organic ammonium salt, including pyrrol idinium bromide, morphol inium bromide.
  • the halogen oxyacid catholyte may be suitable for temperatures ranging from -10 ° C to 90 ° C, and most preferably at room temperatures between 15 and 35 ° C.
  • the anode fuel that can be selected can be gaseous hydrogen or a solution of molecules that can carry hydrogen. These hydrogen-carrying molecules include small molecule alcohols, metal hydrides.
  • the most preferred anode fuel for use is a strongly alkaline aqueous solution of a boron hydride such as sodium borohydride, potassium borohydride or ammonium borohydride.
  • Liquid anode fuel is more preferred than gas anode fuel in terms of fuel carrying convenience, energy density, and heat dissipation.
  • the fuel is stored in a liquid form at atmospheric pressure, is convenient to carry, has no gas cylinders, or other high pressure devices or cooling devices, which greatly increases the volumetric energy density of the battery.
  • the fuel reacts on the electrode in liquid form, and the gas-solid-liquid three-phase catalytic reaction is a solid-liquid two-phase catalytic reaction, which greatly improves the redox kineti cs of the fuel, thereby increasing the power density of the battery. .
  • halogen oxyacids are high-energy oxygenates, and many oxyacids have an oxygen content of more than 30%, which has the advantage of high energy density as a cathode fuel.
  • the aqueous solution of liquid fuel has a better heat dissipation function than gas circulation.
  • Figure 1 is a schematic view showing the structure of a battery of the present invention
  • Figure 3 is a second diagram of the current and voltage curves of the battery of the present invention.
  • Figure 4 is a graph of current and voltage curves of the battery of the present invention.
  • Fig. 5 is a schematic view showing the structure of a battery according to another embodiment of the present invention.
  • the construction of a single battery is as described in Fig. 1, and the basic structure includes a cathode, an anode, and a diaphragm 1.
  • the cathode includes a cathode flow fi eld plate (6), a catholyte 8, a cathode catalytic layer 2, and a cathode liquid diffusion layer 4.
  • the anode includes an anode flow field plate (anode fl ow fi el d plate, 7), an anolyte 9, an anode catalytic layer 3, and an anode liquid diffusion layer 5.
  • the separator 1 may be a cation exchange membrane, an anion exchange membrane, or a porous membrane (a pore size of 0.1 to 1000 nm).
  • Cathode flow field plates and anode flow field plates are typically machined from graphite or stainless steel.
  • the surface has grooves for the auxiliary reaction liquids (i.e., catholyte and anolyte) to flow. Further, in order to ensure that the liquid does not leak, the periphery of the cathode plate and the anode plate are sealed by a sealing gasket 10.
  • the battery adopts the structure of Fig. 1.
  • the cathode fuel 8 is a mixture of 20% ammonium perchlorate and 5% sulfuric acid (weight ratio, the same below), and the anode fuel 9 is composed of 10% sodium borohydride and 10% hydrogen peroxide. a mixture of sodium.
  • the diaphragm 1 is composed of Nafion 1 12, and the cathode plate 6 and the anode plate 7 are made of a highly conductive graphite material, and the apparent area of the electrode plate
  • the cathode catalyst layer 2 is composed of a conductive carbon cloth loaded with a noble metal catalyst
  • the anode catalyst layer 3 is also composed of a catalyst-conductive carbon cloth.
  • the carbon cloth is coated with only one side of the catalyst (ie, the catalytic layer, in direct contact with Nafion), and the other side of the diffusion layer (cathode diffusion layer 4, anode diffusion layer 5).
  • the use of the gasket 10 prevents fuel leakage.
  • the anodes are respectively led out by wires and connected to a variable resistance load. The current voltage curve of the entire battery is shown in Figure 2.
  • Embodiment 2 to Embodiment 8 employ a salt bridge battery structure.
  • the two beakers contain a catholyte and an anolyte, respectively, and the catholyte and anolyte are connected by a salt bridge of 1 cm in diameter containing 20% sodium sulphate and 3% clay.
  • the anolyte used was a mixed solution of 30% ferric sulfate and ferrous sulfate (the molar ratio of ferric iron to divalent iron was 1:1).
  • the catholyte is a mixed solution of different halogen oxyacids and different adjuvants.
  • Two graphite rods are respectively contacted with the catholyte and the anolyte as the cathode and anode of the battery.
  • the discharge performance of the battery is characterized by a circuit voltage (relative to ferric and divalent ferroelectric pairs) and short-circuit current measured by a universal meter.
  • the following examples are provided to illustrate the utility of the catholyte adjuvant.
  • the catholyte consists of 10% magnesium perchlorate and 10% sulfuric acid and contains no adjuvant.
  • the graphite rod does not contain a catalyst.
  • the resulting open circuit voltage and short circuit current are 0.56 V and 35 A/cm 2 , respectively .
  • the catholyte consists of 10% magnesium perchlorate and 10% sulfuric acid and contains 3% sodium molybdate as an adjuvant.
  • the graphite rod does not contain a catalyst.
  • the resulting open circuit voltage and short circuit current are 0.58 V and 43 ⁇ ⁇ 2 , respectively .
  • the catholyte consists of 10% magnesium perchlorate and 10% sulfuric acid and contains 3% sodium molybdate (Na2Mo04) as an adjuvant.
  • the graphite rod carries molybdenum oxide and molybdic acid as catalysts.
  • the resulting open circuit voltage and short circuit current are 0.65 V and 265 A/cm 2 , respectively .
  • the catholyte consists of 10% sodium chlorate and 10% sulfuric acid and contains no adjuvant.
  • the graphite rod does not contain a catalyst.
  • the resulting open circuit voltage and short circuit current are 0.44 V and 10 ⁇ : i ⁇ 2 .
  • the catholyte consists of 10% sodium chlorate and 10% sulfuric acid, and contains 3% sodium bromide as an adjuvant.
  • the graphite rod does not contain a catalyst.
  • the resulting open circuit voltage and short circuit current are 0.55 V and 20 ⁇ /( ⁇ 2 , respectively .
  • the catholyte consists of 10% sodium chlorate and 10% sulfuric acid, and contains 3% sodium bromide and 2% sodium vanadate (NaV03) as an adjuvant.
  • the graphite rod contains no catalyst.
  • the resulting open circuit voltage and short circuit current are 0.50 V and 100 ⁇ / ⁇ : ⁇ 2 , respectively .
  • the catholyte consists of 10% magnesium perchlorate, contains no sulfuric acid and adjuvant, and has a neutral pH.
  • the graphite rod does not contain a catalyst.
  • the resulting open circuit voltage and short circuit current are 0.56 V and 2 A/ C m 2 , respectively .
  • This example illustrates the effect of acid on catalytic reduction compared to Example 2.
  • This example uses the cell structure of Example 1, except that the cathode fuel 8 uses an additional reaction aid in addition to 20% ammonium perchlorate and 5% sulfuric acid mixture: 5% sodium bromide.
  • the anode fuel 9 is still a mixture of 10% sodium borohydride and 10% sodium hydroxide.
  • Other conditions of the fuel cell are the same as in the first embodiment.
  • the addition of sodium bromide increases the rate of reduction of ammonium perchlorate, which in turn increases the discharge current.
  • Figure 3 shows the increase in the current voltage curve of the entire battery. Compared with the embodiment 1, the output power per unit area is nearly doubled.
  • Example 2 uses the battery structure of Example 1, but the cathode fuel 8 employs a mixture of 20% potassium perchlorate and 5% sulfuric acid.
  • the difference from Example 1 is that potassium perchlorate is used here instead of ammonium perchlorate.
  • the anode fuel 9 is still a mixture of 10% sodium borohydride and 10% sodium hydroxide.
  • Other conditions of the fuel cell were the same as in the first embodiment.
  • the use of potassium perchlorate results in a slightly higher open circuit voltage than ammonium perchlorate.
  • Figure 4 shows the current curve of the entire battery. Compared with Example 1, the output power per unit area was increased by a slight 5%.
  • halogen oxyacids can also be mixed with other adjuvants as cathode materials for ordinary dry batteries.
  • it can replace manganese dioxide in zinc-manganese batteries as an oxidant for dry battery cathodes.
  • Figure 5 1-carbon rod (positive), 2-nickel steel shell (anode), colloidal mixture of sodium 3-borohydride and porous carbon (cathode), 4-halogen oxygen A colloidal mixture of acid and porous carbon (anode material), 5- septum.
  • Examples 1 1 to 14 are examples of the use of halogen oxyacids as cathode materials for dry cells:
  • the Nafion membrane Nafion 111 to 117 can be used as a membrane
  • the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder
  • the carbon rod is used as the cathode current collector
  • the stainless steel shell is used as the anode.
  • the collector of the current The final battery structure is shown in Figure 5.
  • the open circuit voltage of the obtained battery was 0.9 V
  • the short-circuit current density was 20 mA/cm 2 (calculated as the outer surface of the stainless steel).
  • the anode colloidal mixture is prepared by mixing sodium borohydride, carbon powder, sodium carboxymethylcellulose, and water in a beaker at a weight ratio of 2:3:1:4. The resulting viscous paste was used as the anode colloidal mixture 3 in FIG.
  • the Nafion membrane Nafion 111 to 117 can be used as a membrane
  • the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder
  • the carbon rod is used as the cathode current collector
  • the stainless steel shell is used as the anode.
  • the collector of the current The final battery structure is shown in Figure 5.
  • the open circuit voltage of the obtained battery was 1. 9 V
  • the short circuit current density was 100 mA/cm 2 (calculated as the outer surface of the stainless steel).
  • the Nafion membrane Nafion 111 to 117 can be used as a membrane
  • the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder
  • the carbon rod is used as the cathode current collector
  • the stainless steel shell is used as the anode.
  • the collector of the current The final battery structure is shown in Figure 5.
  • the obtained battery had an open circuit voltage of 0.95 V and a short-circuit current density of 20 mA/cm 2 (calculated on the outer surface of the stainless steel).
  • the anode colloidal mixture is prepared by mixing ferrous sulfate, carbon powder, sodium carboxymethylcellulose, and water in a beaker at a weight ratio of 2 : 3:1:4. The resulting viscous paste was used as the anode colloidal mixture 3 in FIG.
  • the Nafion membrane Nafion 111 to 117 can be used as a membrane
  • the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder
  • the carbon rod is used as the cathode current collector
  • the stainless steel shell is used as the anode.
  • the collector of the current The final battery structure is shown in Figure 5.
  • the open circuit voltage of the obtained battery was 0.85 V
  • the short-circuit current density was 50 mA/cm 2 (calculated as the outer surface of the stainless steel).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A liquid cathode fuel cell and a primary cell capable of sealed including this such liquid cathode, the cathode includes 1wt.%-100wt.% of halogen oxyacid or halogen oxysalt. This liquid directly or indirectly discharges on the cathode so as to generate power.

Description

液体阴极燃料电池 技术领域  Liquid cathode fuel cell
本发明涉及一种化学能-电能转换装置， 一种基于液体氧化剂和液体还原剂的燃料 电池。  The present invention relates to a chemical energy-electric energy conversion device, a fuel cell based on a liquid oxidant and a liquid reducing agent.
背景技术 Background technique
目前， 基于质子交换膜电解质的氢氧气体燃料电池经过半个世纪的发展， 逐渐开 始被运用与各个工业， 民用， 及军用领域。 该型电池利用氢氧在电极上的催化还原以 产生电能， 是最为人们所熟悉掌握的燃料电池技术。 近年来在无污染型燃料电池公共 汽车和潜艇不依赖氧的推进***中应用体现了这种技术的成熟。 然而， 它在以下几方 面的局限性限制了广泛应用。  At present, hydrogen-oxygen gas fuel cells based on proton exchange membrane electrolytes have gradually been used in various industrial, civil, and military fields after half a century of development. This type of battery utilizes the catalytic reduction of hydrogen and oxygen on the electrode to generate electrical energy, and is the most familiar fuel cell technology. In recent years, the application of this technology has matured in the application of pollution-free fuel cell public vehicles and submarines that do not rely on oxygen. However, its limitations in the following areas limit its wide range of applications.
第一， 氢氧燃料以气体形式携带需要高压气瓶或液化装置增加了体系的重量及危 险性。  First, the hydrogen-oxygen fuel is carried as a gas. The need for a high-pressure gas cylinder or liquefaction unit increases the weight and risk of the system.
此外， 绝热型液化装置只有暂时储存液氧液氢能力。  In addition, the adiabatic liquefaction device only has the ability to temporarily store liquid oxygen and liquid hydrogen.
再次， 高压输气对电池组体系耐压性提出更高的要求。  Again, high pressure gas delivery places higher demands on the pressure resistance of the battery system.
第二， 氢氧燃料在催化剂-碳粉-质子交换膜上催化还原过程是一种在气固液三相 上发生的反应， 气体的体积能量密度底， 而其中反应生成的水难以控制。 太多的水会 淹没催化剂使气体燃料难以还原， 太少的水会增加跨膜电阻和电极极化。 往往阴极会 过湿而阳极过干导致电池效率及功率的降低。  Second, the catalytic reduction process of the oxyhydrogen fuel on the catalyst-carbon powder-proton exchange membrane is a reaction occurring on the gas-solid liquid three-phase, and the volumetric energy density of the gas is low, and the water generated by the reaction is difficult to control. Too much water will flood the catalyst making it difficult to reduce the gaseous fuel, too little water will increase the transmembrane resistance and electrode polarization. Often the cathode is too wet and the anode is too dry resulting in a decrease in battery efficiency and power.
甲醇-空气燃料电池克服了气体燃料储存的问体。 具体操作是液体甲醇取代了氢气 做为阳极燃料， 这样一来把阳极的气固液三相反应变为固液两相'反应， 大大增加了燃 料与催化剂的接触。 然而， 两个缺点依然存在： 第一， 甲醇的催化还原催化效率低具 有很大的过电势， 而且生成的一氧化碳会导致铂催化剂中毒， 虽然人们用大剂量的贵 金属催化剂以补偿， 但却提高了成本。第二， 空气电极的阴极依然是气固液三相催化， 依然存在水管理（water management)难的缺点。  Methanol-air fuel cells overcome the problem of gas fuel storage. The specific operation is that liquid methanol replaces hydrogen as the anode fuel, thus changing the gas-solid liquid three-phase reaction of the anode into a solid-liquid two-phase reaction, which greatly increases the contact between the fuel and the catalyst. However, two shortcomings still exist: First, the catalytic reduction of methanol has a low catalytic efficiency and a large overpotential, and the generated carbon monoxide causes poisoning of the platinum catalyst, although it is compensated by a large dose of precious metal catalyst, but it is improved. cost. Second, the cathode of the air electrode is still gas-solid liquid three-phase catalysis, and there is still a disadvantage of difficulty in water management.
钒氧还电池（vanadium redox battery)是一种以 V5+/V4+为阴极物质， 以 V3+/V2+ 为阳极物质的氧化还原电池。 所有价态的钒都是以液态离子形式存在， 全面消除了气 体介质， 消除了一般电池中充放电产生的固体沉淀， 是一种彻底的液体电池。 然而， 受钒离子的溶解度限制， 它的体积能量密度底， 不适于大电流长时间放电。  The vanadium redox battery is a redox battery with V5+/V4+ as the cathode material and V3+/V2+ as the anode material. All valence vanadium exists in the form of liquid ions, completely eliminating the gas medium, eliminating the solid precipitation caused by charge and discharge in a general battery, and is a complete liquid battery. However, due to the solubility of vanadium ions, its volumetric energy density is not suitable for long-term discharge of large currents.
发明内容 Summary of the invention
本发明提供一种基于液体氧化剂的燃料电池， 不仅克服了氢氧燃料电池中的氧气 气体携带及储存问题， 而且克服了钒氧还电池和甲醇-空气燃料电池能量密度低的缺 点。 The invention provides a fuel cell based on liquid oxidant, which not only overcomes oxygen in the oxyhydrogen fuel cell Gas carrying and storage problems, and overcome the disadvantages of low energy density of vanadium oxide and methanol-air fuel cells.
为了达到解决上述技术问题的目的， 本发明的技术方案是，  In order to achieve the object of solving the above technical problems, the technical solution of the present invention is
一种液体阴极燃料电池， 结构上由阴极燃料， 阴极， 隔膜， 阳极， 阳极燃料构成， 其特征是：该燃料电池包含有重量百分比浓度 1%— 100%的卤素含氧酸或卤素含氧酸盐 的酸性液体溶液为阴极燃料， 并使其在阴极上直接或间接放电以获得电能。  A liquid cathode fuel cell is structurally composed of a cathode fuel, a cathode, a diaphragm, an anode, and an anode fuel, and is characterized in that the fuel cell comprises a halogen oxyacid or a halogen oxyacid having a concentration by weight of 1% to 100% by weight. The acidic liquid solution of the salt is a cathode fuel and is directly or indirectly discharged on the cathode to obtain electrical energy.
在本发明中， 还具有以下技术特征： 卤素含氧酸或卤素含氧酸盐， 由以下酸或其 酸盐中的一个或几个中选出： 次氯酸， 亚氯酸， 氯酸， 及高氯酸， 次溴酸， 亚溴酸， 溴酸， 及高溴酸， 次碘酸， 亚碘酸， 碘酸， 及高碘酸。  In the present invention, it also has the following technical features: a halogen oxyacid or a halogen oxyacid salt, selected from one or more of the following acids or acid salts thereof: hypochlorous acid, chlorous acid, chloric acid, And perchloric acid, hypobromous acid, bromic acid, bromic acid, and perbromic acid, hypoiodous acid, iodic acid, iodic acid, and periodic acid.
在本发明中， 还具有以下技术特征： 卤素含氧酸或卤素含氧酸盐的溶液中卤素含 氧酸或卤素含氧酸盐所占的重量百分比浓度为 1%— 100%。  In the present invention, it is also characterized by the following technical characteristics: The concentration of the halogen oxyacid or the halogen oxyacid salt in the solution of the halogen oxyacid or the halogen oxyacid salt is from 1% to 100% by weight.
在本发明中， 还具有以下技术特征： 阴极由导电耐酸材料制成， 该阴极材料由以 下几种材料中的一个或几个中选出： 碳粉， 碳毡， 碳布， 玻璃碳， 活性碳， 碳纤维， 氧化铅， 氧化铋， 多孔镍， Raney ni ckel, 以及钛合金。  In the present invention, the following technical features are also present: The cathode is made of an electrically conductive acid-resistant material selected from one or more of the following materials: carbon powder, carbon felt, carbon cloth, glassy carbon, active Carbon, carbon fiber, lead oxide, antimony oxide, porous nickel, Raney ni ckel, and titanium alloy.
在本发明中， 还具有以下技术特征： 阴极上载有催化还原卤素含氧酸的催化剂， 该催化剂由以下一种或几种化合物或单质中选出： 镍， 钯， 铂， 铜， 银， 金， 铅， 镉， 汞， 铋， 钌， 钒， 钼以及它们的合金或化合物。  In the present invention, the following technical features are also present: The cathode is provided with a catalyst for catalytically reducing a halogen oxyacid, which is selected from one or more of the following compounds or elements: nickel, palladium, platinum, copper, silver, gold , lead, cadmium, mercury, antimony, antimony, vanadium, molybdenum and their alloys or compounds.
在本发明中， 还具有以下技术特征： 酸性液体溶液除含有卤素含氧酸外， 还可以 包含有以下一种或几种辅助剂： 溴单质及可溶性溴化物， 过氧化氢，可溶性铈的盐， 可 溶性铬的盐， 可溶性钴的盐， 可溶性铁的盐， 可溶性锰的盐， 可溶性钼的盐， 可溶性 铑的盐， 可溶性钌的盐， 可溶性锡的盐， 可溶性钒的盐。  In the present invention, it also has the following technical features: The acidic liquid solution may contain one or more of the following adjuvants in addition to the halogen oxyacid: bromine elemental substance and soluble bromide, hydrogen peroxide, soluble barium salt , soluble chromium salts, soluble cobalt salts, soluble iron salts, soluble manganese salts, soluble molybdenum salts, soluble barium salts, soluble barium salts, soluble tin salts, soluble vanadium salts.
在本发明中， 还具有以下技术特征： 所述的隔膜包括厚度在 0. 1-200 μ πι的离子交 换膜。  In the present invention, the following technical features are also provided: The separator comprises an ion exchange membrane having a thickness of 0.1 to 200 μm.
在本发明中，还具有以下技术特征： 阴极和阳极可以在空间上以双极板形式连接。 在本发明中， 还具有以下技术特征： 酸性液体溶液除含有卤素含氧酸外， 可以含 有以下一种或几种占阴极液重量百分比浓度 0. 1%- 95%的无机或有机酸： 盐酸， 硫酸， 硝酸， 磷酸， tri fluoroacet i c aci d , 苯磺酸， 萘磺酸， 聚合物的酸。  In the present invention, there are also the following technical features: The cathode and the anode can be spatially connected in the form of a bipolar plate. In the present invention, it has the following technical features: The acidic liquid solution may contain, in addition to the halogen oxyacid, one or more of the following concentrations of the catholyte: 0.1% to 95% of the inorganic or organic acid: hydrochloric acid , sulfuric acid, nitric acid, phosphoric acid, tri fluoroacetic acid aci d , benzenesulfonic acid, naphthalenesulfonic acid, polymer acid.
本发明 决其技术问题所采用的构思是： 以卤素含氧酸（halogen aci d)或卤素含 氧酸盐（halogen ac i d salts)的液体溶液， 取代空气， 纯氧气或高压氧气作为阴极燃 料。 卤素含氧酸包括次卤酸， 亚卤酸， 卤酸， 及高卤酸。 本发明专利中的卤是指氯， 溴， 碘， 不包含氟。 卤素含氧酸， 尤其是卤酸及高卤酸， 是高能含氧化合物。 例如， 高氯酸铵做为氧化剂己被广泛应用于各种火箭推进剂中。 高氯酸铵中氧的含量高达 54%， 高氯酸中高达 64%， 氯酸中 56%， 氯酸钠中也有 42%。 因此可以把卤素含氧酸看成 是一种固态的氧， 因而比气体氧具有更高的体积能量密度。 不仅如此， 卤素含氧酸的 盐溶液具有很强的解离度和溶解度，更有利于体积能量密度的增加。在本发明中， "卤 素含氧酸" 的涵义包括了卤素含氧酸及其盐。 The present invention contemplates the technical problem of using a liquid solution of halogen aci d or halogen ac id salts instead of air, pure oxygen or high pressure oxygen as a cathode fuel. Halogen oxyacids include hypohalous acids, halous acids, halogen acids, and perhalogen acids. The halogen in the present invention means chlorine, bromine, iodine, and does not contain fluorine. Halogen oxyacids, especially halogen acids and perhalogen acids, are high energy oxygenates. For example, ammonium perchlorate as an oxidant has been widely used in various rocket propellants. High content of oxygen in ammonium perchlorate 54%, up to 64% in perchloric acid, 56% in chloric acid, and 42% in sodium chlorate. Therefore, the halogen oxyacid can be regarded as a solid oxygen and thus has a higher volume energy density than gaseous oxygen. Moreover, the salt solution of the halogen oxyacid has a strong dissociation degree and solubility, and is more favorable for the increase of the volume energy density. In the present invention, the meaning of "halogen oxyacid" includes halogen oxyacids and salts thereof.
卤素含氧酸的还原机理（以高氯酸为例）如下：  The reduction mechanism of halogen oxyacid (taking perchloric acid as an example) is as follows:
CIO + 8H+ + 8e" C1" + 4H20 E = 1. 39 V CIO + 8H+ + 8e"C1" + 4H 2 0 E = 1. 39 V
反应所需的质子可以是阴极液中所含有的（如在阴极液中添加硫酸， 盐酸）， 也可 以象质子交换膜电解质的氢氧气体燃料电池中的质子是从阳极扩散来的。 电子是从外 部电路中导电传递过来的（起源于阳极液燃料失去的电子）。 当然， 以上反应是极大简 化了的， 省略其间可能的中间步骤- The proton required for the reaction may be contained in the catholyte (e.g., sulfuric acid or hydrochloric acid is added to the catholyte), or the protons in the oxyhydrogen gas fuel cell like the proton exchange membrane electrolyte may be diffused from the anode. Electrons are transferred from the external circuit (from the electrons lost by the anolyte fuel). Of course, the above reaction is greatly simplified, omitting possible intermediate steps -
C104— + 2H+ + 2e— C103" + H20 E = 1. 20 V C10 4 — + 2H+ + 2e— C10 3 " + H 2 0 E = 1. 20 V
C103" + 3H+ + 2e" HC102+ H20 E = 1 · 18 V C10 3 " + 3H+ + 2e" HC10 2 + H 2 0 E = 1 · 18 V
C103" + 6H+ + 6e" C1— + 3H20 E = 1. 45 V C10 3 " + 6H+ + 6e" C1— + 3H 2 0 E = 1. 45 V
HC102 + 2H+ + 2e" HC10 + H20 E = 1. 64 V HC10 2 + 2H+ + 2e" HC10 + H 2 0 E = 1. 64 V
HC102 + 3H+ + 4e" C1— + 2H20 E = 1. 58 V HC10 2 + 3H+ + 4e" C1— + 2H 2 0 E = 1. 58 V
以上反应由阴极液或阴极催化层中的催化剂所催化。 适于使用的催化剂包括镍钯 铂， 铜银金， 以及它们的合金或化合物。 此外一些氧化物， 比如氧化铅， 氧化钌， 氧 化钛， 氧化铋等。 这些元素及它们的化合物在工业上电解制备高氯酸盐， 氯酸盐中已 得到广泛应用。 但是值得指出的是， 它们是用于阳极催化低价卤素含氧酸氧化成高价 价卤素含氧酸， 而不是相反。  The above reaction is catalyzed by a catalyst in the catholyte or cathode catalytic layer. Catalysts suitable for use include nickel palladium platinum, copper silver gold, and alloys or compounds thereof. In addition, some oxides, such as lead oxide, antimony oxide, titanium oxide, antimony oxide, and the like. These elements and their compounds have been widely used in the industrial electrolysis of perchlorate and chlorate. It is worth noting, however, that they are used to catalyze the oxidation of low-cost halogen oxyacids to high-valence halogen oxyacids, rather than the opposite.
本发明电池在总体结构上与普通双极板型质子交换膜氢氧燃料电池相似。 不过， 普通氢氧燃料电池的气体钢瓶被液体燃料储存罐所替代， 并由输液泵传输阴极液和阳 极液。 其中的阴极液即含有卤素含氧酸或其盐溶液。 阳极可以采用多种气体或液体的 可还原性物质， 如气体氢， 液体硼氢化钠溶液，肼， 氨溶液。 阴极液和阴极催化层中 可以含有氧化还原催化剂。 阴极液被泵从阴极液储存罐输入到阴极入口， 经过阴极催 化层还原后从阴极出口出来。 电池组的构造可以采用双极板通液型， 类似文献中所引 用的氢氧气体燃料电池组中的双极板通气型。 为了减少通液中的压力损失， 双极板的 通液道可改迂回型为直通型。  The battery of the present invention is similar in overall structure to a conventional bipolar plate type proton exchange membrane oxyhydrogen fuel cell. However, the gas cylinder of a conventional oxyhydrogen fuel cell is replaced by a liquid fuel storage tank, and the catholyte and the anode liquid are transported by the infusion pump. The catholyte therein contains a halogen oxyacid or a salt solution thereof. The anode can be a variety of gas or liquid reducible substances, such as gas hydrogen, liquid sodium borohydride solution, hydrazine, ammonia solution. The catholyte and the cathode catalytic layer may contain a redox catalyst. The catholyte is pumped from the catholyte storage tank to the cathode inlet, passed through the cathode catalytic layer, and exits the cathode outlet. The configuration of the battery pack can be a bipolar plate type, similar to the bipolar plate venting type in the oxyhydrogen fuel cell stack cited in the literature. In order to reduce the pressure loss in the through-liquid, the flow path of the bipolar plate can be changed to a straight-through type.
本发明的碳电极使用的碳包括碳粉， 碳毡， 碳布， 玻璃碳， 活性碳和碳纤维（包括 纳米碳纤维）。 对于粉末状或纤维状碳来说碳电极的成型可以用压扎法或热压法。  The carbon used in the carbon electrode of the present invention includes carbon powder, carbon felt, carbon cloth, glassy carbon, activated carbon and carbon fibers (including nano carbon fibers). For powdered or fibrous carbon, the carbon electrode can be formed by a calendering method or a hot pressing method.
本发明所提出的卤素含氧酸阴极燃料电池中阴极液以及碳电极层里可以选择性 (optional ly)的包含有阴极催化剂。 最倾向于使用的（most preferred)催化剂包括镍 钯铀， 铜银金， 以及它们的合金或化合物， 氧化铅， 氧化铋， 氧化钌， 氧化钛等。 阴 极催化剂在碳电极层里的分散可以以多种方式实现， 如研磨混合， 化学或电化学还原 氧化剂前体（reduction of catalyst precursor) , 电镀法等。 当以高氯酸以及氯酸 作为燃料时， 最倾向于使用的催化剂是氧化铅。 In the halogen oxyacid cathode fuel cell of the present invention, the catholyte and the carbon electrode layer may optionally contain a cathode catalyst. Most preferred catalysts include nickel Palladium uranium, copper silver, and their alloys or compounds, lead oxide, cerium oxide, cerium oxide, titanium oxide, and the like. The dispersion of the cathode catalyst in the carbon electrode layer can be achieved in various ways, such as grinding and mixing, chemical or electrochemical reduction of catalyst precursors, electroplating, and the like. When perchloric acid and chloric acid are used as fuels, the most preferred catalyst is lead oxide.
除了碳电极外， 其它导电耐酸材料也可以作为阴极。 例如氧化铅， 氧化铋， 多孔 镍， Raney ni ckel, 以及表明涂有氧化钌 -氧化钕的钛合金。  In addition to the carbon electrode, other conductive acid-resistant materials can also serve as the cathode. For example, lead oxide, cerium oxide, porous nickel, Raney ni ckel, and a titanium alloy coated with yttria-yttria.
最倾向于使用的卤素含氧酸阴极燃料是卤酸及高卤酸， 即高氯酸， 高溴酸， 高碘 酸， 即氯酸， 溴酸， 碘酸， 以及它们的盐的水溶液。 在使用中可以用单一的卤酸及高 卤酸， 也可以用不同卤酸及高卤酸的混合物。 阴极燃料的水溶液 pH 值应为酸性， 即 pH < 7. 0。 酸性条件利於卤素含氧酸的催化还原。 为了达到酸性 pH， 除卤酸及高卤酸 自带的酸性外， 阴极液中可以另外加酸。 最倾向于使用的无机酸包括盐酸， 硫酸， 硝 酸， 磷酸， 有机酸包括含碳氟的磺酸（如 trifluoroacet ic acid) , 苯磺酸， 含芳香环 的磺酸等。 卤素含氧酸阴极液的水溶液浓度在 0. 1% — 100%之间， 而出于能量密度考 虑最倾向于使用的浓度在 5. 0%- 70%。 比如工业用浓高氯酸即以 70%形式存在， 可以直 接用来作燃料。  The halogen oxyacid cathode fuel most preferred for use is an aqueous solution of a halogen acid and a perhalogen acid, i.e., perchloric acid, perbromic acid, periodic acid, i.e., chloric acid, bromic acid, iodic acid, and salts thereof. A single halogen acid and a perhalogen acid may be used in the case of use, and a mixture of different halogen acids and perhalogen acids may also be used. The pH of the aqueous solution of the cathode fuel should be acidic, ie pH < 7. 0. The acidic conditions facilitate the catalytic reduction of halogen oxyacids. In order to achieve an acidic pH, an acid may be additionally added to the catholyte in addition to the acidity of the halogen acid and the perhalogen acid. The most preferred inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Organic acids include fluorosulfonic acid (e.g., trifluoroacetic acid), benzenesulfonic acid, aromatic ring-containing sulfonic acid, and the like. The concentration of the aqueous solution of the halogen oxyacid catholyte is between 0.1% and 100%, and the concentration most likely to be used for energy density is between 0.5% and 70%. For example, industrial concentrated perchloric acid is present in 70% form and can be used directly as fuel.
本发明所提出的卤素含氧酸阴极燃料电池所用的电池隔膜为厚度在 0. 1-200 μ πι的 隔膜。 最倾向于使用的隔膜为阳离子交换膜 -Nafion 117。 此外在酸硷条件下稳定的 阴离子交换膜也可以被选用。  The battery separator used in the halogen oxyacid cathode fuel cell of the present invention is a separator having a thickness of 0.1 to 200 μm. The most preferred membrane to be used is the cation exchange membrane - Nafion 117. In addition, an anion exchange membrane which is stable under acid hydrazine conditions can also be used.
除了卤素含氧酸燃料外， 阴极还可以添加其它辅助剂。 辅助剂的功能是用于提高 卤素含氧酸盐的解离度， 减少副反应， 尤其是氧气， 氯气的发生， 减少副反应产生的 氯， 溴的蒸汽压， 提高副反应产生的氯气和溴的溶解度。 可选用的无机物辅助剂包括 许多标准氧化还原电位在 1. 5V-0. 5V的化合物或单质， 或化合物或单质的还原态前体， 如溴化钠， 溴化钾， 和其它金属溴化物。 钒， 铬， 锰， 铁， 钴， 镍， 铜等第五到第十 一副族的化合物。 可选用的有机物辅助剂包括表明阴离子型， 阳离子型， 和中性表面 活性剂。 当所选用的阴极燃料是溴含氧酸或阴极燃料含有溴化合物时， 最倾向于使用 的辅助齐1 J是有机铵盐， 包括 pyrrol idinium bromide, morphol inium bromide. In addition to the halogen oxyacid fuel, other adjuvants may be added to the cathode. The function of the auxiliary agent is to improve the dissociation degree of the halogen oxyacid salt, reduce the side reaction, especially the occurrence of oxygen and chlorine, reduce the chlorine generated by the side reaction, the vapor pressure of bromine, and increase the chlorine and bromine generated by the side reaction. Solubility. The optional inorganic adjuvant includes a plurality of standard or redox potentials of 1. 5V-0. 5V of a compound or element, or a reduced precursor of a compound or element, such as sodium bromide, potassium bromide, and other metal bromides. . Vanadium, chromium, manganese, iron, cobalt, nickel, copper and other compounds of the fifth to eleventh subgroups. Optional organic adjuvants include anionic, cationic, and neutral surfactants. When the selected cathode fuel is a bromine oxyacid or a cathode fuel containing a bromine compound, the most preferred auxiliary Qi 1 J is an organic ammonium salt, including pyrrol idinium bromide, morphol inium bromide.
在实际操作中， 卤素含氧酸阴极液的可适于温度在 -10°C到 90°C， 而最倾向于使用 温度为 15-35°C的室温。  In practice, the halogen oxyacid catholyte may be suitable for temperatures ranging from -10 ° C to 90 ° C, and most preferably at room temperatures between 15 and 35 ° C.
本发明燃料电池在大功率放电时， 不可避免的在电极上会产生大量的热。 因为液 体的体积热容大大于气体的体积热容， 液体燃料的水溶液循环可以把生成的热迅速带 走， 正好有效地克服了气体氢氧电池的散热缺点。 在必要的时候可以再在输液管上串 连一个热交换器， 以便在更大范围内散热。 可以选择的阳极燃料可以是气体氢， 也可以是可携带氢的分子的溶液。 这些可携 带氢的分子包括小分子醇， 金属氢化物。 最倾向于使用的阳极燃料是硼氢化合物的强 碱性水溶液， 如硼氢化钠， 硼氢化钾， 硼氢化铵。 而液体阳极燃料比气体阳极燃料在 燃料携带方便， 能量密度， 散热等方面更加有优势， 是为首选。 When the fuel cell of the present invention discharges at a high power, a large amount of heat is inevitably generated on the electrode. Because the volumetric heat capacity of the liquid is much larger than the volumetric heat capacity of the gas, the aqueous solution of the liquid fuel can quickly take away the generated heat, which effectively overcomes the heat dissipation disadvantage of the gas oxyhydrogen battery. When necessary, a heat exchanger can be connected in series on the infusion tube to dissipate heat over a wider range. The anode fuel that can be selected can be gaseous hydrogen or a solution of molecules that can carry hydrogen. These hydrogen-carrying molecules include small molecule alcohols, metal hydrides. The most preferred anode fuel for use is a strongly alkaline aqueous solution of a boron hydride such as sodium borohydride, potassium borohydride or ammonium borohydride. Liquid anode fuel is more preferred than gas anode fuel in terms of fuel carrying convenience, energy density, and heat dissipation.
本发明的有益效果是以下四个方面. - 第一， 燃料以液体形式常压下储存， 携带方便， 无气体钢瓶， 或其它高压装置或 冷却装置， 大大增加了电池的体积能量密度。  The beneficial effects of the present invention are as follows: - First, the fuel is stored in a liquid form at atmospheric pressure, is convenient to carry, has no gas cylinders, or other high pressure devices or cooling devices, which greatly increases the volumetric energy density of the battery.
第二， 燃料以液体形式在电极上反应， 改气固液三相催化反应为固液两相催化反 应， 大大改善了燃料氧化还原的动力学（redox kineti cs) ， 因而增加了电池的功率 密度 。  Second, the fuel reacts on the electrode in liquid form, and the gas-solid-liquid three-phase catalytic reaction is a solid-liquid two-phase catalytic reaction, which greatly improves the redox kineti cs of the fuel, thereby increasing the power density of the battery. .
第三， 卤素含氧酸是一种高能含氧化合物， 许多含氧酸的含氧量在 30%以上， 做 为阴极燃料具有高能量密度的优势。  Third, halogen oxyacids are high-energy oxygenates, and many oxyacids have an oxygen content of more than 30%, which has the advantage of high energy density as a cathode fuel.
第四， 液体燃料的水溶液循环比气体循环有更好的散热功能。  Fourth, the aqueous solution of liquid fuel has a better heat dissipation function than gas circulation.
附图说明 DRAWINGS
下面结合附图和实施例对本发明进行详细地描述。  The invention will now be described in detail in conjunction with the drawings and embodiments.
图 1是本发明电池结构示意图；  Figure 1 is a schematic view showing the structure of a battery of the present invention;
图 2是本发明电池的电流、 电压曲线图之一；  2 is a graph showing current and voltage curves of the battery of the present invention;
图 3是本发明电池的电流、 电压曲线图之二；  Figure 3 is a second diagram of the current and voltage curves of the battery of the present invention;
图 4是本发明电池的电流、 电压曲线图之三；  Figure 4 is a graph of current and voltage curves of the battery of the present invention;
图 5是本发明另一实施例电池结构示意图。  Fig. 5 is a schematic view showing the structure of a battery according to another embodiment of the present invention.
具体实施方式 detailed description
单个电池的构造如图 1中所描述， 基本结构包括阴极， 阳极， 隔膜 1构成。 阴极包 括阴极流场板（cathode flow fi eld plate, 6) , 阴极液 8， 阴极催化层 2， 阴极液体扩 散层 4。 阳极包括阳极流场板（anode fl ow fi el d plate, 7)， 阳极液 9， 阳极催化层 3， 阳极液体扩散层 5。 隔膜 1可以是阳离子交换膜， 阴离子交换膜， 或多孔隔膜（孔径在 0. 1雇到 1000nm)。 阴极流场板和阳极流场板通常由石墨或者不锈钢机械加工而成。 表 面有辅助反应液体 （即阴极液和阳极液） 流动的沟槽。 此外， 为了保证液体***露， 阴极板和阳极板的周边由密封垫圈密封 10。  The construction of a single battery is as described in Fig. 1, and the basic structure includes a cathode, an anode, and a diaphragm 1. The cathode includes a cathode flow fi eld plate (6), a catholyte 8, a cathode catalytic layer 2, and a cathode liquid diffusion layer 4. The anode includes an anode flow field plate (anode fl ow fi el d plate, 7), an anolyte 9, an anode catalytic layer 3, and an anode liquid diffusion layer 5. The separator 1 may be a cation exchange membrane, an anion exchange membrane, or a porous membrane (a pore size of 0.1 to 1000 nm). Cathode flow field plates and anode flow field plates are typically machined from graphite or stainless steel. The surface has grooves for the auxiliary reaction liquids (i.e., catholyte and anolyte) to flow. Further, in order to ensure that the liquid does not leak, the periphery of the cathode plate and the anode plate are sealed by a sealing gasket 10.
实施例 1 :  Example 1
电池采用图 1的结构， 阴极燃料 8是 20%的高氯酸铵和 5%的硫酸混合液（重量比， 以 下同）， 阳极燃料 9是由 10%的硼氢化钠， 10%的氢氧化钠构成的的混合液。 隔膜 1由 Nafion 1 12 构成， 阴极板 6和阳极板 7由高导电的石墨材料制成， 电极板的表观面积  The battery adopts the structure of Fig. 1. The cathode fuel 8 is a mixture of 20% ammonium perchlorate and 5% sulfuric acid (weight ratio, the same below), and the anode fuel 9 is composed of 10% sodium borohydride and 10% hydrogen peroxide. a mixture of sodium. The diaphragm 1 is composed of Nafion 1 12, and the cathode plate 6 and the anode plate 7 are made of a highly conductive graphite material, and the apparent area of the electrode plate
更正页（细则第 91条) 是 25cm2。 阴极催化剂层 2由加载有贵金属催化剂的导电碳布构成， 阳极催化剂层 3也由 载有催化剂导电碳布构成。碳布只有一侧镀有催化剂（即催化层，和 Nafion直接接触）， 其另一侧为扩散层（阴极扩散层 4, 阳极扩散层 5)密封垫 10的使用阻止了燃料的泄露. 阴极和阳极分别用导线引出并接在可变电阻荷载上。 整个电池的电流（current)电压 (voltage)曲线如图 2所示。 Correction page (Article 91) It is 25cm 2 . The cathode catalyst layer 2 is composed of a conductive carbon cloth loaded with a noble metal catalyst, and the anode catalyst layer 3 is also composed of a catalyst-conductive carbon cloth. The carbon cloth is coated with only one side of the catalyst (ie, the catalytic layer, in direct contact with Nafion), and the other side of the diffusion layer (cathode diffusion layer 4, anode diffusion layer 5). The use of the gasket 10 prevents fuel leakage. The anodes are respectively led out by wires and connected to a variable resistance load. The current voltage curve of the entire battery is shown in Figure 2.
与实施例 1不同的是： 实施例 2到实施例 8采用盐桥电池结构。 具体方式是： 两个 烧杯中分别盛有阴极液和阳极液， 阴极液和阳极液用一根直径 l cm的， 含有 20%的硫酸 钠和 3%的粘土的盐桥相连。 其中阳极液用的是 30%硫酸铁和硫酸亚铁混合溶液 （三价 铁和二价铁的摩尔比为 1 : 1 )。 阴极液用的是不同的卤素含氧酸及不同辅助剂的混合溶 液。 两根石墨棒分别与阴极液和阳极液接触做为电池的阴极和阳极。 电池的放电性能 由一个万用电表测得的幵路电压 （相对于三价铁和二价铁电对） 和短路电流来表征。 以下实施例用以说明阴极液辅助剂的功用。  The difference from Embodiment 1 is that Embodiment 2 to Embodiment 8 employ a salt bridge battery structure. Specifically, the two beakers contain a catholyte and an anolyte, respectively, and the catholyte and anolyte are connected by a salt bridge of 1 cm in diameter containing 20% sodium sulphate and 3% clay. The anolyte used was a mixed solution of 30% ferric sulfate and ferrous sulfate (the molar ratio of ferric iron to divalent iron was 1:1). The catholyte is a mixed solution of different halogen oxyacids and different adjuvants. Two graphite rods are respectively contacted with the catholyte and the anolyte as the cathode and anode of the battery. The discharge performance of the battery is characterized by a circuit voltage (relative to ferric and divalent ferroelectric pairs) and short-circuit current measured by a universal meter. The following examples are provided to illustrate the utility of the catholyte adjuvant.
实施例 2:  Example 2:
阴极液由 10%的高氯酸镁和 10%的硫酸构成， 不含辅助剂。 石墨棒上不含催化剂。 所得开路电压和短路电流分别是 0. 56V和 35 A/cm2。 The catholyte consists of 10% magnesium perchlorate and 10% sulfuric acid and contains no adjuvant. The graphite rod does not contain a catalyst. The resulting open circuit voltage and short circuit current are 0.56 V and 35 A/cm 2 , respectively .
实施例 3:  Example 3:
阴极液由 10%的高氯酸镁和 10%的硫酸构成， 并含有 3%的钼酸钠为辅助剂。 石墨棒 上不含催化剂。 所得开路电压和短路电流分别是 0. 58V和 43μΑΑ πι2。 The catholyte consists of 10% magnesium perchlorate and 10% sulfuric acid and contains 3% sodium molybdate as an adjuvant. The graphite rod does not contain a catalyst. The resulting open circuit voltage and short circuit current are 0.58 V and 43 μΑΑ πι 2 , respectively .
实施例 4:  Example 4:
阴极液由 10%的高氯酸镁和 10%的硫酸构成， 并含有 3%的钼酸钠（Na2Mo04)为辅助 剂。 石墨棒上载有氧化钼和钼酸为催化剂。 所得开路电压和短路电流分别是 0. 65V和 265 A/cm2。 The catholyte consists of 10% magnesium perchlorate and 10% sulfuric acid and contains 3% sodium molybdate (Na2Mo04) as an adjuvant. The graphite rod carries molybdenum oxide and molybdic acid as catalysts. The resulting open circuit voltage and short circuit current are 0.65 V and 265 A/cm 2 , respectively .
实施例 5:  Example 5
阴极液由 10%的氯酸钠和 10%的硫酸构成， 不含辅助剂。 石墨棒上不含催化剂。 所 得开路电压和短路电流分别是 0. 44V和 10μΑΑ:ιη2。 The catholyte consists of 10% sodium chlorate and 10% sulfuric acid and contains no adjuvant. The graphite rod does not contain a catalyst. The resulting open circuit voltage and short circuit current are 0.44 V and 10 μΑΑ: iη 2 .
实施例 6:  Example 6:
阴极液由 10%的氯酸钠和 10%的硫酸构成， 并含有 3%的溴化钠为辅助剂， 石墨棒上 不含催化剂。 所得开路电压和短路电流分别是 0. 55V和 20μΑ/( ΐι2。 The catholyte consists of 10% sodium chlorate and 10% sulfuric acid, and contains 3% sodium bromide as an adjuvant. The graphite rod does not contain a catalyst. The resulting open circuit voltage and short circuit current are 0.55 V and 20 μΑ/( ΐι 2 , respectively .
实施例 7:  Example 7
阴极液由 10%的氯酸钠和 10%的硫酸构成， 并含有 3%的溴化钠以及 2%的钒酸钠 ( NaV03)为辅助剂， 石墨棒上不含催化剂。 所得开路电压和短路电流分别是 0. 50V和 100μΑ/<:πι2。 阴极液由 10%的高氯酸镁构成， 不含硫酸和辅助剂， pH值为中性。 石墨棒上不含 催化剂。所得开路电压和短路电流分别是 0. 56V和 2 A/Cm2。 与例 2相比此例说明了酸对 催化还原的影响。 The catholyte consists of 10% sodium chlorate and 10% sulfuric acid, and contains 3% sodium bromide and 2% sodium vanadate (NaV03) as an adjuvant. The graphite rod contains no catalyst. The resulting open circuit voltage and short circuit current are 0.50 V and 100 μΑ/<:πι 2 , respectively . The catholyte consists of 10% magnesium perchlorate, contains no sulfuric acid and adjuvant, and has a neutral pH. The graphite rod does not contain a catalyst. The resulting open circuit voltage and short circuit current are 0.56 V and 2 A/ C m 2 , respectively . This example illustrates the effect of acid on catalytic reduction compared to Example 2.
实施例 9:  Example 9
此例采用实施例 1的电池结构，但是阴极燃料 8除 20%的高氯酸铵和 5%的硫酸混合 液外采用了额外的反应辅助剂： 5%的溴化钠。 阳极燃料 9仍然是由 10%的硼氢化钠， 10% 的氢氧化钠构成的混合液。 燃料电池的其他条件与实施例 1同。 溴化钠的加入提高了 高氯酸铵的还原速率， 进而提高了放电电流。 图 3显示整个电池的电流（current)电压 (voltage)曲线提高的情况。 与实施例 1比， 单位面积输出功率提高了将近一倍。  This example uses the cell structure of Example 1, except that the cathode fuel 8 uses an additional reaction aid in addition to 20% ammonium perchlorate and 5% sulfuric acid mixture: 5% sodium bromide. The anode fuel 9 is still a mixture of 10% sodium borohydride and 10% sodium hydroxide. Other conditions of the fuel cell are the same as in the first embodiment. The addition of sodium bromide increases the rate of reduction of ammonium perchlorate, which in turn increases the discharge current. Figure 3 shows the increase in the current voltage curve of the entire battery. Compared with the embodiment 1, the output power per unit area is nearly doubled.
实施例 10:  Example 10
此例采用实施例 1中的电池结构，但是阴极燃料 8采用了 20%的高氯酸钾和 5%的硫 酸混合液。与实施例 1不同的是这里高氯酸钾来代替高氯酸铵。阳极燃料 9仍然是由 10% 的硼氢化钠， 10%的氢氧化钠构成的的混合液。 燃料电池的其他条件与实施例 1相同。 采用高氯酸钾导致比高氯酸铵略高的开路电压。 图 4显示整个电池的电流（current)电 压（voltage)曲线。 与实施例 1相比， 单位面积输出功率提高了略 5%。  This example uses the battery structure of Example 1, but the cathode fuel 8 employs a mixture of 20% potassium perchlorate and 5% sulfuric acid. The difference from Example 1 is that potassium perchlorate is used here instead of ammonium perchlorate. The anode fuel 9 is still a mixture of 10% sodium borohydride and 10% sodium hydroxide. Other conditions of the fuel cell were the same as in the first embodiment. The use of potassium perchlorate results in a slightly higher open circuit voltage than ammonium perchlorate. Figure 4 shows the current curve of the entire battery. Compared with Example 1, the output power per unit area was increased by a slight 5%.
此外，卤素含氧酸还可以与其它辅助剂混合在一起，作为普通干电池的阴极材料。 比如， 它可以取代锌锰电池中的二氧化锰作为干电池阴极的氧化剂。 具体实施如图 5. 图 5中， 1-碳棒（正极）， 2-镀镍钢外壳（阳极）， 3-硼氢化钠和多孔碳的胶状混合物 （阴 极物质） ，4-卤素含氧酸和多孔碳的胶状混合物 （阳极物质） ， 5-隔膜。  In addition, halogen oxyacids can also be mixed with other adjuvants as cathode materials for ordinary dry batteries. For example, it can replace manganese dioxide in zinc-manganese batteries as an oxidant for dry battery cathodes. Figure 5. In Figure 5, 1-carbon rod (positive), 2-nickel steel shell (anode), colloidal mixture of sodium 3-borohydride and porous carbon (cathode), 4-halogen oxygen A colloidal mixture of acid and porous carbon (anode material), 5- septum.
例 1 1到例 14是关于将卤素含氧酸作为干电池的阴极材料的几个实例：  Examples 1 1 to 14 are examples of the use of halogen oxyacids as cathode materials for dry cells:
实施例 1 1 :  Example 1 1 :
在一个烧杯中将高氯酸， 碳粉， 纳米级分散的硅胶溶液， 和水以重量比 2 : 3： 2： 3的比例混合均匀， 所得的粘稠糊状物作为图 5中的阴极胶状混合物 4。 阳极胶状混合 物制作方法是： 在一个烧杯中将硼氢化钠， 碳粉， 羧甲基纤维素钠， 和水以重量比 2 : 3： 1： 4的比例混合均勾。 所得的粘稠糊状物作为图 5中的阳极胶状混合物 3。 最后， 以 Nafion膜（Nafion 111 到 117均可）作为隔膜， 将阴极胶状物和阳极胶状物填充到一 个不锈钢的圆柱形筒中， 以碳棒作为阴极的电流收集极， 以不锈钢外壳作为阳极电流 的收集极。 最后的电池结构如图 5。 所得电池的开路电压为 0. 9V,短路电流密度为 20mA/cm2 (以不锈钢外表面计算）。  In a beaker, perchloric acid, carbon powder, nano-dispersed silica gel solution, and water were uniformly mixed at a weight ratio of 2:3:2:3, and the obtained viscous paste was used as the cathodic rubber in FIG. Mixture 4. The anode colloidal mixture is prepared by mixing sodium borohydride, carbon powder, sodium carboxymethylcellulose, and water in a ratio of 2:3:1:4 by weight in a beaker. The resulting viscous paste was used as the anode colloidal mixture 3 in Fig. 5. Finally, the Nafion membrane (Nafion 111 to 117 can be used as a membrane), the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder, the carbon rod is used as the cathode current collector, and the stainless steel shell is used as the anode. The collector of the current. The final battery structure is shown in Figure 5. The open circuit voltage of the obtained battery was 0.9 V, and the short-circuit current density was 20 mA/cm 2 (calculated as the outer surface of the stainless steel).
实施例 12 :  Example 12:
在一个烧杯中将溴酸， 碳粉， 纳米级分散的硅胶溶液， 和水以重量比 2 : 3： 2： 3 的比例混合均匀， 所得的粘稠糊状物作为图 5中的阴极胶状混合物 4。 阳极胶状混合物 制作方法是：在一个烧杯中将硼氢化钠， 碳粉， 羧甲基纤维素钠， 和水以重量比 2 : 3： 1： 4的比例混合均匀。 所得的粘稠糊状物作为图 5中的阳极胶状混合物 3。 最后， 以 Nafion膜（Nafion 111 到 117均可）作为隔膜， 将阴极胶状物和阳极胶状物填充到一个 不锈钢的圆柱形筒中， 以碳棒作为阴极的电流收集极， 以不锈钢外壳作为阳极电流的 收集极。 最后的电池结构如图 5。 所得电池的开路电压为 1. 9V，短路电流密度为 100mA/cm2 (以不锈钢外表面计算）。 In a beaker, bromic acid, carbon powder, nano-dispersed silica gel solution, and water in a weight ratio of 2:3:2:3 The ratio was uniformly mixed, and the resulting viscous paste was used as the cathode colloidal mixture 4 in Fig. 5. The anode colloidal mixture is prepared by mixing sodium borohydride, carbon powder, sodium carboxymethylcellulose, and water in a beaker at a weight ratio of 2:3:1:4. The resulting viscous paste was used as the anode colloidal mixture 3 in FIG. Finally, the Nafion membrane (Nafion 111 to 117 can be used as a membrane), the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder, the carbon rod is used as the cathode current collector, and the stainless steel shell is used as the anode. The collector of the current. The final battery structure is shown in Figure 5. The open circuit voltage of the obtained battery was 1. 9 V, and the short circuit current density was 100 mA/cm 2 (calculated as the outer surface of the stainless steel).
实施例 13 :  Example 13:
在一个烧杯中将高氯酸， 碳粉， 纳米级分散的硅胶溶液， 和水以重量比 2 : 3： 2： 3的比例混合均匀， 所得的粘稠糊状物作为图 5中的阴极胶状混合物 4。 阳极胶状混合 物制作方法是： 在一个烧杯中将二氯化锡， 碳粉， 羧甲基纤维素钠， 和水以重量比 2 : 3： 1： 4的比例混合均匀。 所得的粘稠糊状物作为图 5中的阳极胶状混合物 3。 最后， 以 Nafion膜（Nafion 111 到 117均可）作为隔膜， 将阴极胶状物和阳极胶状物填充到一 个不锈钢的圆柱形筒中， 以碳棒作为阴极的电流收集极， 以不锈钢外壳作为阳极电流 的收集极。 最后的电池结构如图 5。 所得电池的开路电压为 0. 95V,短路电流密度为 20mA/cm2 (以不锈钢外表面计算）。  In a beaker, perchloric acid, carbon powder, nano-dispersed silica gel solution, and water were uniformly mixed at a weight ratio of 2:3:2:3, and the obtained viscous paste was used as the cathodic rubber in FIG. Mixture 4. The anode colloidal mixture is prepared by mixing tin dichloride, carbon powder, sodium carboxymethylcellulose, and water in a beaker at a weight ratio of 2:3:1:4. The resulting viscous paste was used as the anode colloidal mixture 3 in Fig. 5. Finally, the Nafion membrane (Nafion 111 to 117 can be used as a membrane), the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder, the carbon rod is used as the cathode current collector, and the stainless steel shell is used as the anode. The collector of the current. The final battery structure is shown in Figure 5. The obtained battery had an open circuit voltage of 0.95 V and a short-circuit current density of 20 mA/cm 2 (calculated on the outer surface of the stainless steel).
实施例 14 :  Example 14:
在一个烧杯中将高氯酸， 碳粉， 纳米级分散的硅胶溶液， 和水以重量比 2: 3： 2： 3的比例混合均匀， 所得的粘稠糊状物作为图 5中的阴极胶状混合物 4。 阳极胶状混合 物制作方法是： 在一个烧杯中将硫酸亚铁， 碳粉， 羧甲基纤维素钠， 和水以重量比 2 : 3： 1： 4的比例混合均匀。 所得的粘稠糊状物作为图 5中的阳极胶状混合物 3。 最后， 以 Nafion膜（Nafion 111 到 117均可）作为隔膜， 将阴极胶状物和阳极胶状物填充到一 个不锈钢的圆柱形筒中， 以碳棒作为阴极的电流收集极， 以不锈钢外壳作为阳极电流 的收集极。 最后的电池结构如图 5。 所得电池的开路电压为 0. 85V,短路电流密度为 50mA/cm2 (以不锈钢外表面计算）。 Perchloric acid, carbon powder, nano-dispersed silica gel solution, and water were uniformly mixed in a ratio of 2:3:2:3 in a beaker, and the obtained viscous paste was used as the cathodic rubber in FIG. Mixture 4. The anode colloidal mixture is prepared by mixing ferrous sulfate, carbon powder, sodium carboxymethylcellulose, and water in a beaker at a weight ratio of 2 : 3:1:4. The resulting viscous paste was used as the anode colloidal mixture 3 in FIG. Finally, the Nafion membrane (Nafion 111 to 117 can be used as a membrane), the cathode gel and the anode gel are filled into a stainless steel cylindrical cylinder, the carbon rod is used as the cathode current collector, and the stainless steel shell is used as the anode. The collector of the current. The final battery structure is shown in Figure 5. The open circuit voltage of the obtained battery was 0.85 V, and the short-circuit current density was 50 mA/cm 2 (calculated as the outer surface of the stainless steel).
以上所述， 仅是本发明的较佳实施例而已， 并非是对本发明作其它形式的限制， 任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变 化的等效实施例。 但是凡是未脱离本发明技术方案内容， 依据本发明的技术实质对以 上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。  The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any person skilled in the art may use the above-disclosed technical contents to change or modify the equivalent equivalent. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments in accordance with the technical scope of the present invention are still within the scope of protection of the technical solutions of the present invention.

Claims

权 利 要 求 书 Claim
1 . 一种燃料电池， 结构上由阴极燃料， 阴极， 隔膜， 阳极， 阳极燃料构成， 其 特征是：该燃料电池包含有重量百分比浓度 1%— 100%的卤素含氧酸或卤素含氧酸盐的 酸性液体溶液为阴极燃料， 并使其在阴极上直接或间接放电以获得电能。 What is claimed is: 1. A fuel cell comprising: a cathode fuel, a cathode, a diaphragm, an anode, and an anode fuel, characterized in that the fuel cell comprises a halogen oxyacid or a halogen oxyacid in a concentration of 1% to 100% by weight; The acidic liquid solution of the salt is a cathode fuel and is directly or indirectly discharged on the cathode to obtain electrical energy.
2. 根据权利要求 1 所述的燃料电池， 其特征在于卤素含氧酸或卤素含氧酸盐， 由以下酸或其酸盐中的一个或几个中选出： 次氯酸， 亚氯酸， 氯酸， 及高氯酸， 次溴 酸， 亚溴酸， 溴酸， 及高溴酸， 次碘酸， 亚碘酸， 碘酸， 及高碘酸。  2. The fuel cell according to claim 1, characterized in that the halogen oxyacid or halogen oxyacid salt is selected from one or more of the following acids or acid salts thereof: hypochlorous acid, chlorous acid , chloric acid, and perchloric acid, hypobromous acid, bromic acid, bromic acid, and perbromic acid, hypoiodous acid, iodic acid, iodic acid, and periodic acid.
3. 根据权利要求 1 所述的燃料电池， 其特征在于卤素含氧酸或卤素含氧酸盐的 溶液中卤素含氧酸或卤素含氧酸盐所占的重量百分比浓度为 1%— 100%。  3. The fuel cell according to claim 1, wherein the concentration of the halogen oxyacid or the halogen oxyacid salt in the halogen oxyacid or halogen oxyacid salt solution is from 1% to 100% by weight. .
4. 根据权利要求 1 所述的燃料电池， 其特征在于阴极由导电耐酸材料制成， 该 阴极材料由以下几种材料中的一个或几个中选出： 碳粉， 碳毡， 碳布， 玻璃碳， 活性 碳， 碳纤维， 氧化铅， 氧化铋， 多孔镍， Raney nickel, 以及钛合金。  4. The fuel cell according to claim 1, wherein the cathode is made of an electrically conductive acid-resistant material selected from one or more of the following materials: carbon powder, carbon felt, carbon cloth, Glassy carbon, activated carbon, carbon fiber, lead oxide, antimony oxide, porous nickel, Raney nickel, and titanium alloy.
5. 根据权利要求 1 所述的燃料电池， 其特征在于阴极上载有催化还原卤素含氧 酸的催化剂， 该催化剂由以下一种或几种化合物或单质中选出： 镍， 钯， 铂， 铜， 银， 金， 铅， 镉， 汞， 铋， 钌， 钒， 钼以及它们的合金或化合物。  5. The fuel cell according to claim 1, wherein the cathode is provided with a catalyst for catalytically reducing a halogen oxyacid, the catalyst being selected from one or more of the following compounds or elements: nickel, palladium, platinum, copper , silver, gold, lead, cadmium, mercury, antimony, antimony, vanadium, molybdenum and their alloys or compounds.
6. 根据权利要求 1所述的燃料电池， 其特征在于阴极酸性液体溶液中除含有卤素 含氧酸外， 还可以包含有以下一种或几种辅助剂： 溴单质及可溶性溴化物， 过氧化氢, 可溶性铈的盐， 可溶性铬的盐， 可溶性钴的盐， 可溶性铁的盐， 可溶性锰的盐， 可溶 性钼的盐， 可溶性铑的盐， 可溶性钌的盐， 可溶性锡的盐， 可溶性钒的盐。  6. The fuel cell according to claim 1, wherein the cathode acidic liquid solution may further comprise one or more of the following adjuvants in addition to the halogen oxyacid: bromine elemental substance and soluble bromide, peroxidation. Hydrogen, soluble barium salt, soluble chromium salt, soluble cobalt salt, soluble iron salt, soluble manganese salt, soluble molybdenum salt, soluble barium salt, soluble barium salt, soluble tin salt, soluble vanadium salt.
7.根据权利要求 1所述的燃料电池， 其特征在于隔膜包括厚度在 0. 1.-200微米的 离子交换膜。  The fuel cell according to claim 1, wherein the separator comprises an ion exchange membrane having a thickness of from 0.1 to 200 μm.
8.根据权利要求 1所述的燃料电池， 其特征在于阴极和阳极可以在空间上以双极 板形式连接。  A fuel cell according to claim 1, wherein the cathode and the anode are spatially connected in the form of a bipolar plate.
9.根据权利要求 1所述的燃料电池， 其特征在于酸性液体溶液除含有卤素含氧酸 外， 可以包含有以下一种或几种占阴极液重量百分比浓度 0. 1%_95%的无机或有机酸： 盐酸， 硫酸， 硝酸， 磷酸， tri fluoroacet ic ac i d , 苯磺酸， 萘磺酸， 聚合物的酸。  1% _95%的无机或或1 Organic acids: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, tri fluoroacetic acid ac id, benzenesulfonic acid, naphthalenesulfonic acid, polymer acid.
10.—种一次性可封装性电池， 结构上由阴极， 阴极物质， 隔膜， 阳极， 阳极物质 构成， 其特徵是： 该一次性电池以含有卤素含氧酸或卤素含氧酸盐的酸性胶状物为阴 极物质， 并使其在阴极上直接或间接放电以获得电能。 10. A disposable encapsulatable battery, comprising: a cathode, a cathode material, a separator, an anode, and an anode material, wherein: the disposable battery is an acid gel containing a halogen oxyacid or a halogen oxyacid salt. The substance is a cathode material and is directly or indirectly discharged on the cathode to obtain electrical energy.
11.根据权利要求 10，其中的胶状物除了卤素含氧酸外还含有以下一种或几种物质： 胶化剂， 导电剂（包括碳粉， 碳毡， 碳布， 石墨粉， 碳纤维， 金属粉，金属纤维，导电 金属氧化物）。 11. The gel according to claim 10, wherein the gel contains one or more of the following substances in addition to the halogen oxyacid: a gelling agent, a conductive agent (including carbon powder, carbon felt, carbon cloth, graphite powder, carbon fiber, Metal powder, metal fiber, conductive metal oxide).
12.根据权利要求 10，所述的阴极或阴极物质上载有催化还原卤素含氧酸的催化剂， 该催化剂由以下一种或几种化合物或单质中选出： 镍， 钯， 铂， 铜， 银， 金， 铅， 镉， 汞， 铋， 钌， 钒， 钼以及它们的合金或化合物。  12. The cathode or cathode material according to claim 10, comprising a catalyst for catalytically reducing a halogen oxyacid, the catalyst being selected from one or more of the following compounds or elements: nickel, palladium, platinum, copper, silver , gold, lead, cadmium, mercury, antimony, antimony, vanadium, molybdenum and their alloys or compounds.
13.根据权利要求 10, 其中一次性电池的阳极物质除胶化剂， 导电剂外包括以下一 种或几种物质： 铅粉， 锡粉， 锌粉， 二价锡的盐， 二价铁的盐，亚铁盐， 胶化硼氢化 钠。  13. The method according to claim 10, wherein the anode material of the disposable battery comprises a gelling agent, and the conductive agent comprises one or more of the following substances: lead powder, tin powder, zinc powder, salt of divalent tin, ferrous iron. Salt, ferrous salt, gelatinized sodium borohydride.
14.根据权利要求 10， 所述的阳极或阳极物质上载有催化氧化硼氢化钠的催化剂， 该催化剂由以下一种或几种化合物或单质中选出： 镍， 钯， 铂， 铜， 银， 金， 铅， 镉， 汞， 铋， 钌， 钒， 钼以及它们的合金或化合物。  The anode or anode material according to claim 10, wherein the catalyst for carrying out sodium borohydride hydride is selected from one or more of the following compounds or elements: nickel, palladium, platinum, copper, silver, Gold, lead, cadmium, mercury, antimony, antimony, vanadium, molybdenum and their alloys or compounds.
15.根据权利要求 10， 所述的电池隔膜包括阳离子交换膜，阴离子交换膜，枝接的亲 水性聚合物隔膜，或亲水性无机陶瓷纤维（含玻璃纤维）隔膜。  The battery separator according to claim 10, comprising a cation exchange membrane, an anion exchange membrane, a branched hydrophilic polymer membrane, or a hydrophilic inorganic ceramic fiber (glass-containing) membrane.
PCT/CN2007/002238 2006-09-12 2007-07-23 A liquid cathode fuel cell WO2008031318A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113299930A (en) * 2021-04-28 2021-08-24 湖南源达新材料有限公司 Air electrode containing bismuth oxide catalyst and preparation method thereof
WO2023044239A1 (en) * 2021-09-20 2023-03-23 Ess Tech, Inc. Hybrid redox fuel cell system

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103259032B (en) * 2013-04-28 2016-06-08 单萌 A kind of room-temperature thermal power generation and device thereof
CN107293826A (en) * 2016-12-28 2017-10-24 南京工业大学 A kind of high energy density charge-discharge battery being made up of metal and peroxide and its application
CN115516674A (en) * 2020-05-14 2022-12-23 罗伯特·博世有限公司 Proton exchange membrane fuel cell, preparation method thereof and proton exchange membrane fuel cell stack

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1209219A (en) * 1995-12-28 1999-02-24 Gp斯特雷泰格斯公司 Electroconversion cell
JP2002020123A (en) * 2000-07-04 2002-01-23 Nippon Chem Ind Co Ltd Method for producing trivalent and tetravalent mixture vanadium compound and method for producing vanadium- base electrolytic solution
CN1429416A (en) * 2000-03-24 2003-07-09 里珍西斯技术有限公司 Method of operating fuel cell
US20040234843A1 (en) * 2001-08-24 2004-11-25 Maria Skyllas-Kazacos Vanadium/polyhalide redox flow battery

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4469760A (en) * 1981-09-08 1984-09-04 Electric Power Research, Institute Redox battery including a bromine positive electrode and a chromium ion negative electrode, and method
US6444337B1 (en) * 2000-09-26 2002-09-03 Energetics, Inc. Fuel cell with low cathodic polarization and high power density
WO2003069709A1 (en) * 2002-02-14 2003-08-21 Hitachi Maxell, Ltd. Liquid fuel cell
AU2003901183A0 (en) * 2003-03-14 2003-03-27 Michael Kazacos Novel vanadium bromide redox flow cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1209219A (en) * 1995-12-28 1999-02-24 Gp斯特雷泰格斯公司 Electroconversion cell
CN1429416A (en) * 2000-03-24 2003-07-09 里珍西斯技术有限公司 Method of operating fuel cell
JP2002020123A (en) * 2000-07-04 2002-01-23 Nippon Chem Ind Co Ltd Method for producing trivalent and tetravalent mixture vanadium compound and method for producing vanadium- base electrolytic solution
US20040234843A1 (en) * 2001-08-24 2004-11-25 Maria Skyllas-Kazacos Vanadium/polyhalide redox flow battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113299930A (en) * 2021-04-28 2021-08-24 湖南源达新材料有限公司 Air electrode containing bismuth oxide catalyst and preparation method thereof
WO2023044239A1 (en) * 2021-09-20 2023-03-23 Ess Tech, Inc. Hybrid redox fuel cell system
US20230105427A1 (en) * 2021-09-20 2023-04-06 Ess Tech, Inc. Hybrid redox fuel cell system
US11996597B2 (en) 2021-09-20 2024-05-28 Ess Tech, Inc. Hybrid redox fuel cell system

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