WO2021253836A1 - Method for preparing alkali metal-doped iron-air battery negative electrode and iron-air battery negative electrode obtained thereby - Google Patents

Method for preparing alkali metal-doped iron-air battery negative electrode and iron-air battery negative electrode obtained thereby Download PDF

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WO2021253836A1
WO2021253836A1 PCT/CN2021/074350 CN2021074350W WO2021253836A1 WO 2021253836 A1 WO2021253836 A1 WO 2021253836A1 CN 2021074350 W CN2021074350 W CN 2021074350W WO 2021253836 A1 WO2021253836 A1 WO 2021253836A1
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alkali metal
iron
air battery
negative electrode
metal salt
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French (fr)
Chinese (zh)
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王建强
彭程
张诗雨
程李威
杨云
关成志
肖国萍
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中国科学院上海应用物理研究所
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0048—Molten electrolytes used at high temperature

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  • the invention relates to the preparation of an iron oxide electrode material, and more particularly to a method for preparing an alkali metal doped iron-air battery negative electrode and the resulting iron-air battery negative electrode.
  • Metal-air batteries have always received extensive attention because of their extremely high theoretical specific energy values.
  • iron has become one of the popular candidates for the negative electrode active material of metal-air battery due to its abundant reserves and low cost.
  • Conventional iron-air batteries use alkaline solutions as electrolytes, and there are problems of electrolyte carbonation and evaporation and drying up, which greatly affects the long-term stability of the battery.
  • the low electrochemical reaction activity at room temperature causes the actual energy density of the battery to be far lower than the theoretical value, which severely weakens the advantages of the metal-air battery.
  • Research and design of iron-air batteries with high-efficiency oxygen ion transport capacity at high temperatures is an effective solution to this type of problem.
  • the research team of George Washington University in the United States designed an iron-air battery with molten lithium carbonate as the electrolyte, and its actual specific energy reached 1.9Wh/g Fe ; the research team of ITAE in Italy used the perovskite ceramic material electrolyte with ion conductivity at high temperature The specific energy of the iron-air battery is 0.46Wh/g Fe .
  • the research team of the Shanghai Institute of Applied Physics, Chinese Academy of Sciences designed a dual-electrolyte high-temperature iron-air battery with molten potassium sodium carbonate as the electrolyte, which effectively improved the volatilization and fluidity problems of molten salt batteries at high temperatures.
  • the present invention provides a method for preparing an alkali metal doped iron-air battery negative electrode and the resulting iron-air battery negative electrode .
  • the present invention provides a method for preparing an alkali metal doped iron-air battery negative electrode, which includes the steps: S1, mixing iron oxide (Fe 2 O 3 ) and an alkali metal salt; S2, heating to a constant temperature after the alkali metal salt is melted , The constant stirring makes the iron oxide and the alkali metal salt fully contact the solid-liquid reaction to form the alkali metal intercalated ferrite; S3, after natural cooling to room temperature, remove the excess alkali metal salt to obtain the alkali metal doped iron air Battery negative.
  • the alkali metal salt is carbonate, chloride or sulfate. It should be understood that the alkali metal salt may also be other high melting point salts. More preferably, the alkali metal salt is a non-toxic and harmless salt.
  • the alkali metal salt is a lithium salt, a sodium salt or a potassium salt.
  • the alkali metal salt is lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ) or potassium carbonate (K 2 CO 3 ).
  • the doping amount of the alkali metal in the negative electrode of the iron-air battery is adjusted according to the different ratio of the alkali metal salt and the iron oxide.
  • the molar ratio of the alkali metal salt to the iron oxide in the negative electrode of the iron-air battery is 1:1, 1:2, or 1:4.
  • the final product of the reaction between Li 2 CO 3 and iron oxide is LiFeO 2 , and the initial amounts of Fe 2 O 3 and Li 2 CO 3 are weighed according to the Li:Fe metering ratio of 1:1.
  • the final product of the reaction between Na 2 CO 3 and iron oxide is NaFeO 2 , and the initial amounts of Fe 2 O 3 and Na 2 CO 3 are weighed according to the Na:Fe metering ratio of 1:1.
  • K 2 CO 3 and iron oxide such as K 2 Fe 10 O 16 , K 2 FeO 4 , KFeO 2, etc.
  • the doping ratio is adjusted according to specific requirements.
  • this step S1 is specifically: the iron oxide and the alkali metal salt are thoroughly ground and then mixed uniformly.
  • the heating rate of this step S2 is 5-20° C./min, the temperature is raised to 850-1100° C. until the alkali metal salt is melted, and the constant temperature reaction is 3-6 hours.
  • the focus of this step is the process of melting at a constant temperature after the temperature is raised to the melting point.
  • the constant temperature process is the reaction process, which can make the alkali metal doping fully proceed.
  • this step S3 is specifically: washing with water at room temperature to remove excess alkali metal salt, followed by suction filtration and drying to obtain an alkali metal-doped iron-air battery negative electrode.
  • the present invention also provides the iron-air battery negative electrode obtained by the above-mentioned preparation method.
  • the iron-air battery negative electrode obtained by the above-mentioned preparation method is formed by a method such as sheet pressing or coating.
  • the alkali metal doped iron-air battery negative electrode has the ability to complete the insertion and detachment of alkali metal ions during the charging and discharging process, has good iron redox catalytic properties at high temperatures, and can reduce the energy loss at the battery negative electrode.
  • the alkali metal doped iron-air battery negative electrode has a strong ability to conduct oxygen ions to the electrolyte, thereby avoiding the problems of leakage and internal heat consumption.
  • the molten salt method is used—alkali metal salt melts at a temperature higher than the melting point (>800°C) and reacts with iron oxide to achieve doping. It can be used as iron oxide anode material for iron-air batteries.
  • the iron-air battery negative electrode according to the present invention has high catalytic activity at high temperatures and is suitable for high-temperature molten salt iron-air batteries.
  • the high-temperature molten salt iron-air battery uses high-temperature molten salt as the electrolyte, so that the iron oxide electrode doped by the molten salt method has better compatibility with the high-temperature molten salt.
  • the operation is simple, safe and controllable, fast reaction, low energy consumption, adjustable ratio, wide source of raw materials, low cost, and great industrial application. prospect.
  • Example 1 is an XRD pattern of the product obtained by reacting Li 2 CO 3 molten salt and iron oxide at 850° C. according to Example 1 of the present invention
  • Example 2 is an XRD pattern of the product obtained by reacting Na 2 CO 3 molten salt and iron oxide at 1000° C. according to Example 2 of the present invention
  • Example 3 is an XRD pattern of the product obtained by reacting K 2 CO 3 molten salt and iron oxide at 1100° C. according to Example 3 of the present invention.

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

A method for preparing an alkali metal-doped iron-air battery negative electrode, the method comprising the steps of: mixing iron oxide and an alkali metal salt; heating same until the alkali metal salt melts and then keeping the temperature constant, and continuously stirring same to enable the iron oxide and the alkali metal salt to be sufficiently in contact with one another and be subjected to a solid-liquid reaction so as to form an alkali metal-embedded ferrate; and after naturally cooling same to room temperature, removing the excess alkali metal salt to obtain an alkali metal-doped iron-air battery negative electrode. Also provided is an iron-air battery negative electrode obtained by the preparation method. According to the preparation method of the alkali metal-doped iron-air battery negative electrode, a molten salt method is used, i.e. an alkali metal salt melts at a temperature higher than the melting point, and reacts with iron oxide to achieve doping, thereby obtaining an iron oxide negative electrode material which can be used in an iron-air battery. The iron-air battery negative electrode has a high catalytic activity at a high temperature, and is suitable for a high-temperature molten salt iron-air battery.

Description

一种碱金属掺杂的铁空电池负极的制备方法以及由此得到的铁空电池负极Preparation method of alkali metal doped iron-air battery negative electrode and iron-air battery negative electrode obtained thereby 技术领域Technical field
本发明涉及氧化铁电极材料的制备，更具体地涉及一种碱金属掺杂的铁空电池负极的制备方法以及由此得到的铁空电池负极。The invention relates to the preparation of an iron oxide electrode material, and more particularly to a method for preparing an alkali metal doped iron-air battery negative electrode and the resulting iron-air battery negative electrode.
背景技术Background technique
金属空气电池因其具有极高的理论比能量值一直受到人们的广泛关注。其中，铁由于储量丰富、成本低而成为金属空气电池负极活性物质的热门候选之一。常规的铁空电池以碱性溶液作为电解质，存在电解液碳酸盐化以及挥发干涸的问题，极大地影响了电池的长期运行稳定性。另外，室温条件下电化学反应活性低导致电池的实际能量密度远远低于理论值，严重削弱了金属空气电池的优势。研究设计高温下具有高效氧离子传输能力的电解质的铁空电池是这类问题的一个有效解决方法。其中，美国乔治华盛顿大学的研究团队设计以熔融碳酸锂作为电解质的铁空电池其实际比能量达到1.9Wh/g Fe；意大利ITAE的研究团队利用高温下具有离子导电性的钙钛矿陶瓷材料电解质的铁空电池其比能量为0.46Wh/g Fe。中国科学院上海应用物理研究所的研究团队设计了以熔融的碳酸钾钠盐作为电解质的双电解质的高温铁空电池，有效改善了熔盐电池在高温下的挥发和流动性问题。 Metal-air batteries have always received extensive attention because of their extremely high theoretical specific energy values. Among them, iron has become one of the popular candidates for the negative electrode active material of metal-air battery due to its abundant reserves and low cost. Conventional iron-air batteries use alkaline solutions as electrolytes, and there are problems of electrolyte carbonation and evaporation and drying up, which greatly affects the long-term stability of the battery. In addition, the low electrochemical reaction activity at room temperature causes the actual energy density of the battery to be far lower than the theoretical value, which severely weakens the advantages of the metal-air battery. Research and design of iron-air batteries with high-efficiency oxygen ion transport capacity at high temperatures is an effective solution to this type of problem. Among them, the research team of George Washington University in the United States designed an iron-air battery with molten lithium carbonate as the electrolyte, and its actual specific energy reached 1.9Wh/g Fe ; the research team of ITAE in Italy used the perovskite ceramic material electrolyte with ion conductivity at high temperature The specific energy of the iron-air battery is 0.46Wh/g Fe . The research team of the Shanghai Institute of Applied Physics, Chinese Academy of Sciences designed a dual-electrolyte high-temperature iron-air battery with molten potassium sodium carbonate as the electrolyte, which effectively improved the volatilization and fluidity problems of molten salt batteries at high temperatures.
但在上述高温铁空电池的研究过程中，中国科学院上海应用物理研究所的团队发现，铁负极的电化学活性对于电池性能的提升至关重要，常规的高温铁空电池负极活性物质是氧化铁，因此设计选择高温下具有高效电催化活性以及导电性的铁负极材料是高温铁空电池研究的重中之重。However, in the research process of the above-mentioned high-temperature iron-air battery, the team from the Shanghai Institute of Applied Physics of the Chinese Academy of Sciences found that the electrochemical activity of the iron anode is crucial to the improvement of battery performance. The conventional high-temperature iron-air battery anode active material is iron oxide Therefore, the design and selection of iron anode materials with high-efficiency electrocatalytic activity and conductivity at high temperatures is the top priority of the research on high-temperature iron-air batteries.
发明内容Summary of the invention
为了解决现有技术中的常规的铁空电池的铁负极的电化学活性偏低等问题，本发明提供一种碱金属掺杂的铁空电池负极的制备方法以及由此得到的铁空电池负极。In order to solve the problems of low electrochemical activity of the iron negative electrode of the conventional iron-air battery in the prior art, the present invention provides a method for preparing an alkali metal doped iron-air battery negative electrode and the resulting iron-air battery negative electrode .
本发明提供一种碱金属掺杂的铁空电池负极的制备方法，其包括步骤： S1，将氧化铁(Fe 2O 3)和碱金属盐混合；S2，升温至碱金属盐熔化后保持恒温，不断搅拌使得氧化铁和碱金属盐充分接触发生固液间反应，形成碱金属嵌入的铁酸盐；S3，自然冷却至室温后，去除多余的碱金属盐，得到碱金属掺杂的铁空电池负极。 The present invention provides a method for preparing an alkali metal doped iron-air battery negative electrode, which includes the steps: S1, mixing iron oxide (Fe 2 O 3 ) and an alkali metal salt; S2, heating to a constant temperature after the alkali metal salt is melted , The constant stirring makes the iron oxide and the alkali metal salt fully contact the solid-liquid reaction to form the alkali metal intercalated ferrite; S3, after natural cooling to room temperature, remove the excess alkali metal salt to obtain the alkali metal doped iron air Battery negative.
优选地，该碱金属盐为碳酸盐、氯盐或硫酸盐。应该理解，该碱金属盐还可以是其他高熔点盐。更优选地，该碱金属盐为无毒无害盐。Preferably, the alkali metal salt is carbonate, chloride or sulfate. It should be understood that the alkali metal salt may also be other high melting point salts. More preferably, the alkali metal salt is a non-toxic and harmless salt.
优选地，该碱金属盐为锂盐、钠盐或钾盐。Preferably, the alkali metal salt is a lithium salt, a sodium salt or a potassium salt.
优选地，该碱金属盐为碳酸锂(Li 2CO 3)、碳酸钠(Na 2CO 3)或碳酸钾(K 2CO 3)。 Preferably, the alkali metal salt is lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ) or potassium carbonate (K 2 CO 3 ).
优选地，铁空电池负极中的碱金属的掺杂量根据碱金属盐与氧化铁的不同配比进行调整。Preferably, the doping amount of the alkali metal in the negative electrode of the iron-air battery is adjusted according to the different ratio of the alkali metal salt and the iron oxide.
优选地，铁空电池负极中的碱金属盐与氧化铁的摩尔比为1:1、1:2或1:4。Preferably, the molar ratio of the alkali metal salt to the iron oxide in the negative electrode of the iron-air battery is 1:1, 1:2, or 1:4.
优选地，Li 2CO 3与氧化铁反应的最终产物为LiFeO 2，根据Li:Fe的计量比为1:1称取初始量的Fe 2O 3和Li 2CO 3。 Preferably, the final product of the reaction between Li 2 CO 3 and iron oxide is LiFeO 2 , and the initial amounts of Fe 2 O 3 and Li 2 CO 3 are weighed according to the Li:Fe metering ratio of 1:1.
优选地，Na 2CO 3与氧化铁反应的最终产物为NaFeO 2，根据Na:Fe的计量比为1:1称取初始量的Fe 2O 3和Na 2CO 3。 Preferably, the final product of the reaction between Na 2 CO 3 and iron oxide is NaFeO 2 , and the initial amounts of Fe 2 O 3 and Na 2 CO 3 are weighed according to the Na:Fe metering ratio of 1:1.
优选地，K 2CO 3与氧化铁反应的产物有多种，如K 2Fe 10O 16、K 2FeO 4、KFeO 2等，根据具体要求来调整掺杂比。 Preferably, there are multiple products of the reaction between K 2 CO 3 and iron oxide, such as K 2 Fe 10 O 16 , K 2 FeO 4 , KFeO 2, etc. The doping ratio is adjusted according to specific requirements.
优选地，该步骤S1具体为：氧化铁和碱金属盐经研磨充分后混合均匀。Preferably, this step S1 is specifically: the iron oxide and the alkali metal salt are thoroughly ground and then mixed uniformly.
优选地，该步骤S2的升温速率为5-20℃/min，升温至850-1100℃至碱金属盐熔化，恒温反应3-6h。应该理解，该步骤的重点在于升温至熔点后恒温使其熔化的过程，恒温过程即为反应过程，该过程可使得碱金属的掺杂充分进行。Preferably, the heating rate of this step S2 is 5-20° C./min, the temperature is raised to 850-1100° C. until the alkali metal salt is melted, and the constant temperature reaction is 3-6 hours. It should be understood that the focus of this step is the process of melting at a constant temperature after the temperature is raised to the melting point. The constant temperature process is the reaction process, which can make the alkali metal doping fully proceed.
优选地，该步骤S3具体为：室温下水洗除去多余的碱金属盐，再经抽滤、烘干得到碱金属掺杂的铁空电池负极。Preferably, this step S3 is specifically: washing with water at room temperature to remove excess alkali metal salt, followed by suction filtration and drying to obtain an alkali metal-doped iron-air battery negative electrode.
本发明还提供由上述的制备方法得到的铁空电池负极。优选地，由上述的制备方法得到的铁空电池负极通过压片或涂覆等方法实现电极成型。研究表明，碱金属掺杂的铁空电池负极在充放电过程中具有完成碱金属离子嵌 入和脱离的能力，在高温下具有较好的铁氧化还原催化特性，能够降低电池负极处的能量损失，另外，碱金属掺杂的铁空电池负极具备较强的将氧离子传导给电解质的能力，从而避免了漏电以及内部热量消耗的问题。The present invention also provides the iron-air battery negative electrode obtained by the above-mentioned preparation method. Preferably, the iron-air battery negative electrode obtained by the above-mentioned preparation method is formed by a method such as sheet pressing or coating. Studies have shown that the alkali metal doped iron-air battery negative electrode has the ability to complete the insertion and detachment of alkali metal ions during the charging and discharging process, has good iron redox catalytic properties at high temperatures, and can reduce the energy loss at the battery negative electrode. In addition, the alkali metal doped iron-air battery negative electrode has a strong ability to conduct oxygen ions to the electrolyte, thereby avoiding the problems of leakage and internal heat consumption.
根据本发明的碱金属掺杂的铁空电池负极的制备方法，利用熔盐法——碱金属盐在高于熔点的温度(>800℃)下熔化并与氧化铁发生反应实现掺杂，得到可用作铁空电池的氧化铁负极材料。根据本发明的铁空电池负极，在高温下具有高催化活性，适用于高温熔盐铁空电池。特别地，高温熔盐铁空电池以高温熔融的盐作为电解质，使得熔盐法掺杂得到的氧化铁电极与高温熔盐之间的兼容性更好。另外，根据本发明的碱金属掺杂的铁空电池负极的制备方法，操作简单，安全可控，反应快，能耗低，比例可调，原料来源广泛，成本低，有极大的工业应用前景。According to the preparation method of the alkali metal-doped iron-air battery negative electrode of the present invention, the molten salt method is used—alkali metal salt melts at a temperature higher than the melting point (>800°C) and reacts with iron oxide to achieve doping. It can be used as iron oxide anode material for iron-air batteries. The iron-air battery negative electrode according to the present invention has high catalytic activity at high temperatures and is suitable for high-temperature molten salt iron-air batteries. In particular, the high-temperature molten salt iron-air battery uses high-temperature molten salt as the electrolyte, so that the iron oxide electrode doped by the molten salt method has better compatibility with the high-temperature molten salt. In addition, according to the preparation method of the alkali metal-doped iron-air battery negative electrode of the present invention, the operation is simple, safe and controllable, fast reaction, low energy consumption, adjustable ratio, wide source of raw materials, low cost, and great industrial application. prospect.
附图说明Description of the drawings
图1是根据本发明的实施例1的Li 2CO 3熔盐与氧化铁在850℃反应得到的产物的XRD图； 1 is an XRD pattern of the product obtained by reacting Li 2 CO 3 molten salt and iron oxide at 850° C. according to Example 1 of the present invention;
图2是根据本发明的实施例2的Na 2CO 3熔盐与氧化铁在1000℃反应得到的产物的XRD图； 2 is an XRD pattern of the product obtained by reacting Na 2 CO 3 molten salt and iron oxide at 1000° C. according to Example 2 of the present invention;
图3是根据本发明的实施例3的K 2CO 3熔盐与氧化铁在1100℃反应得到的产物的XRD图。 3 is an XRD pattern of the product obtained by reacting K 2 CO 3 molten salt and iron oxide at 1100° C. according to Example 3 of the present invention.
具体实施方式detailed description
下面结合附图，给出本发明的较佳实施例，并予以详细描述。In the following, in conjunction with the accompanying drawings, a preferred embodiment of the present invention is given and described in detail.
实施例1Example 1
称取70gFe 2O 3与70g Li 2CO 3经研磨充分混合，装入坩埚中，置于管式炉中，设置升温速率为10℃/min，升温至850℃，恒温6h之后自然冷却至室温，取出样品，水洗除去多余的Li 2CO 3，再经抽滤、烘干得到最终的产物。产物XRD表征结果如图1，其明显存在LiFeO 2的峰，而碳酸锂溶于水，铁酸锂难溶于水，故而经过水洗可得到掺杂了锂的铁酸锂材料。 Weigh 70g Fe 2 O 3 and 70g Li 2 CO 3 and mix them thoroughly after grinding, put them in a crucible, place in a tube furnace, set the heating rate to 10℃/min, heat up to 850℃, and cool to room temperature after 6h at constant temperature , Take out the sample, wash with water to remove excess Li 2 CO 3 , and then filter and dry to obtain the final product. The XRD characterization result of the product is shown in Fig. 1, which clearly has a peak of LiFeO 2 , while lithium carbonate is soluble in water, and lithium ferrite is hardly soluble in water. Therefore, after washing with water, a lithium ferrite material doped with lithium can be obtained.
实施例2Example 2
称取70gFe 2O 3与70gNa 2CO 3经研磨充分混合，装入坩埚中，置于管式炉中，设置升温速率为15℃/min，升温至1000℃，恒温4h之后自然冷却至室温，取出样品，水洗除去多余的Na 2CO 3，再经抽滤、烘干得到最终的产物。产物XRD表征结果如图2。 Weigh 70g of Fe 2 O 3 and 70g of Na 2 CO 3 and mix them thoroughly after grinding, put them in a crucible, and place them in a tube furnace. Set the heating rate to 15°C/min, raise the temperature to 1000°C, and cool to room temperature after 4 hours of constant temperature. Take out the sample, wash with water to remove excess Na 2 CO 3 , and then filter and dry to obtain the final product. The XRD characterization results of the product are shown in Figure 2.
实施例3Example 3
称取70gFe 2O 3与70gK 2CO 3经研磨充分混合，装入坩埚中，置于管式炉中，设置升温速率为15℃/min，升温至1100℃，恒温3h之后自然冷却至室温，取出样品，水洗除去多余的K 2CO 3，再经抽滤、烘干得到最终的产物。产物XRD表征结果如图3。 Weigh 70g of Fe 2 O 3 and 70g of K 2 CO 3 by grinding and mixing them thoroughly, put them in a crucible, and place them in a tube furnace. Set the heating rate to 15°C/min, raise the temperature to 1100°C, and cool to room temperature after 3 hours of constant temperature. Take out the sample, wash with water to remove excess K 2 CO 3 , and then filter and dry to obtain the final product. The XRD characterization results of the product are shown in Figure 3.
以上所述的，仅为本发明的较佳实施例，并非用以限定本发明的范围，本发明的上述实施例还可以做出各种变化。即凡是依据本发明申请的权利要求书及说明书内容所作的简单、等效变化与修饰，皆落入本发明专利的权利要求保护范围。本发明未详尽描述的均为常规技术内容。The foregoing descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Various changes can be made to the foregoing embodiments of the present invention. That is to say, all simple and equivalent changes and modifications made in accordance with the claims of the present invention and the contents of the description fall into the protection scope of the patent of the present invention. What is not described in detail in the present invention is conventional technical content.

Claims (10)

  1. 一种碱金属掺杂的铁空电池负极的制备方法，其包括步骤：A method for preparing an alkali metal doped iron-air battery negative electrode, which comprises the steps:
    S1，将氧化铁和碱金属盐混合；S1, mixing iron oxide and alkali metal salt;
    S2，升温至碱金属盐熔化后保持恒温，不断搅拌使得氧化铁和碱金属盐充分接触发生固液间反应，形成碱金属嵌入的铁酸盐；S2, keep the temperature at a constant temperature after the alkali metal salt melts, and keep stirring so that the iron oxide and the alkali metal salt are in full contact to cause a solid-liquid reaction to form an alkali metal-embedded ferrite;
    S3，自然冷却至室温后，去除多余的碱金属盐，得到碱金属掺杂的铁空电池负极。S3, after natural cooling to room temperature, remove excess alkali metal salt to obtain an alkali metal doped iron-air battery negative electrode.
  2. 根据权利要求1所述的制备方法，其特征在于，该碱金属盐为碳酸盐、氯盐或硫酸盐。The preparation method according to claim 1, wherein the alkali metal salt is carbonate, chloride or sulfate.
  3. 根据权利要求1所述的制备方法，其特征在于，该碱金属盐为锂盐、钠盐或钾盐。The preparation method according to claim 1, wherein the alkali metal salt is a lithium salt, a sodium salt or a potassium salt.
  4. 根据权利要求1所述的制备方法，其特征在于，该碱金属盐为碳酸锂、碳酸钠或碳酸钾。The preparation method according to claim 1, wherein the alkali metal salt is lithium carbonate, sodium carbonate or potassium carbonate.
  5. 根据权利要求1所述的制备方法，其特征在于，铁空电池负极中的碱金属的掺杂量根据碱金属盐与氧化铁的不同配比进行调整。The preparation method according to claim 1, wherein the doping amount of the alkali metal in the negative electrode of the iron-air battery is adjusted according to the different ratios of the alkali metal salt and the iron oxide.
  6. 根据权利要求5所述的制备方法，其特征在于，铁空电池负极中的碱金属盐与氧化铁的摩尔比为1:1、1:2或1:4。The preparation method according to claim 5, wherein the molar ratio of the alkali metal salt to the iron oxide in the negative electrode of the iron-air battery is 1:1, 1:2, or 1:4.
  7. 根据权利要求1所述的制备方法，其特征在于，该步骤S1具体为：氧化铁和碱金属盐经研磨充分后混合均匀。The preparation method according to claim 1, wherein the step S1 is specifically: the iron oxide and the alkali metal salt are thoroughly ground and then mixed uniformly.
  8. 根据权利要求1所述的制备方法，其特征在于，该步骤S2的升温速率为5-20℃/min，升温至850-1100℃至碱金属盐熔化，恒温反应3-6h。The preparation method according to claim 1, characterized in that the heating rate of step S2 is 5-20°C/min, the temperature is raised to 850-1100°C until the alkali metal salt is melted, and the reaction is held at a constant temperature for 3-6 hours.
  9. 根据权利要求1所述的制备方法，其特征在于，该步骤S3具体为：室温下水洗除去多余的碱金属盐，再经抽滤、烘干得到碱金属掺杂的铁空电池负极。The preparation method according to claim 1, wherein the step S3 is specifically: washing with water at room temperature to remove excess alkali metal salt, and then suction filtration and drying to obtain an alkali metal-doped iron-air battery negative electrode.
  10. 一种根据权利要求1-9中任一项所述的制备方法得到的铁空电池负极。An iron-air battery negative electrode obtained by the preparation method according to any one of claims 1-9.
PCT/CN2021/074350 2020-06-18 2021-01-29 Method for preparing alkali metal-doped iron-air battery negative electrode and iron-air battery negative electrode obtained thereby WO2021253836A1 (en)

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