WO2023273835A1 - Positive electrode material of aqueous zinc-ion battery having neutral or slightly acidic system, preparation method therefor, and application thereof - Google Patents

Positive electrode material of aqueous zinc-ion battery having neutral or slightly acidic system, preparation method therefor, and application thereof Download PDF

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WO2023273835A1
WO2023273835A1 PCT/CN2022/098188 CN2022098188W WO2023273835A1 WO 2023273835 A1 WO2023273835 A1 WO 2023273835A1 CN 2022098188 W CN2022098188 W CN 2022098188W WO 2023273835 A1 WO2023273835 A1 WO 2023273835A1
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positive electrode
manganese
electrode material
bismuth
ion battery
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PCT/CN2022/098188
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French (fr)
Chinese (zh)
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傅洋
田毅
倪珂帆
于春雨
陈璞
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陈璞
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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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the disclosure belongs to the technical field of zinc-ion batteries, and in particular relates to a neutral or weakly acidic water-based zinc-ion battery positive electrode material and a preparation method and application thereof.
  • lithium-ion batteries have also exposed Some deficiencies: the shortage of lithium resources has caused its price to rise year by year, the negative electrode is easy to form lithium dendrites and cause short circuits, and the organic electrolyte is flammable, all of which have certain safety hazards. Compared with lithium, zinc has more abundant resources and lower cost, and the water-based zinc-ion battery eliminates the dangers of fire and explosion that may be caused by organic electrolytes. In addition, two electrons are transferred during the redox process of zinc ions, so it has a high theoretical capacity.
  • an object of the present disclosure is to propose a neutral or weakly acidic water-based zinc-ion battery positive electrode material and its preparation method and application.
  • the positive electrode material has a stable structure and can be used in zinc-ion batteries to solve the The problem of poor battery cycle performance.
  • the present disclosure proposes a neutral or weakly acidic water-based zinc-ion battery positive electrode material.
  • the positive electrode material includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0 ⁇ y/z ⁇ 1,0 ⁇ x ⁇ y.
  • a positive electrode material which includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein, 0 ⁇ y/z ⁇ 1, 0 ⁇ x ⁇ y .
  • Bi x Mn yx O z is an oxide of bismuth, that is, Bi x Mn yx O z includes bismuth oxide and/or bismuth manganese oxide, wherein both bismuth oxide and bismuth manganese oxide can be Isolate the manganese-containing compound from the electrolyte to reduce the occurrence of side reactions between the electrolyte and the manganese-containing compound.
  • bismuth manganese oxide makes the structure of the positive electrode material more stable during charging and discharging, thereby improving the cycle performance of the battery.
  • Bismuth manganese oxide can reduce the generation of inert substances, improve the reversibility of active substances, and reduce the fluctuation of the internal resistance of the battery cell.
  • This application adopts the method of in-situ combination.
  • the Bi element is uniformly distributed on the surface of the primary particles of manganese-containing compounds; When manganese compound is doped with Bi, Bi is mainly distributed on the surface of the secondary particles, and it is difficult to distribute evenly. Protective effect on the positive electrode.
  • the cathode material can be applied to a neutral or weakly acidic aqueous zinc-ion battery, which solves the problem of poor cycle performance of the zinc-ion battery, thereby obtaining a zinc-ion battery with good electrochemical performance, high specific capacity, and superior cycle performance.
  • the neutral or weakly acidic water-based zinc-ion battery positive electrode material can also have the following additional technical features:
  • the manganese-containing compound includes at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
  • the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0.
  • the present disclosure proposes a method for preparing the above-mentioned cathode material.
  • the method includes:
  • the manganese-containing material, the bismuth-containing compound and water are mixed with stirring, the bismuth-containing compound is uniformly dispersed in the water, coated on the surface of the manganese-containing material, and a part contains
  • the bismuth compound reacts with the manganese-containing material, that is, the bismuth element in the bismuth-containing compound replaces the manganese element in the lattice of the manganese-containing material, and bismuth-manganese oxide is formed in the subsequent sintering process, making the structure of the positive electrode material more stable during charging and discharging.
  • bismuth manganese oxide can reduce the generation of inert substances, improve the reversibility of the active material, reduce the fluctuation of the internal resistance of the cell, and then coat the bismuth-containing compound on the surface of the manganese-containing material.
  • the precursor is obtained after the material is dried; then the obtained precursor is sintered, and the bismuth-containing compound that has not reacted with the manganese-containing material is converted into Bi 2 O 3 that is insoluble in water, and the bismuth element in the bismuth compound in the precursor replaces
  • the manganese-containing material in the lattice of the manganese element is sintered to form bismuth-manganese oxide.
  • Bi 2 O 3 and/or bismuth-manganese oxide can isolate the manganese-containing material from the electrolyte and reduce the gap between the electrolyte and the manganese-containing material. The occurrence of side reactions between them improves the cycle performance of the battery.
  • This application is the first time to apply this method to a neutral or acidic water-based zinc-ion battery.
  • the solution method solves the problem of uneven distribution of coatings.
  • the proportion of the coating layer is controllable, and the preparation process is simple and the cost of raw materials is low. It can be applied in large-scale industrial production.
  • the surface of the prepared positive electrode material contains bismuth element, which makes the structure of the positive electrode material more stable during the charge and discharge process, and its application in zinc ion batteries can improve the electrochemical performance, specific capacity and cycle performance of the battery.
  • step (1) the stirring time is 1 min ⁇ 100 h.
  • the coating of the positive electrode material is uniformly distributed.
  • the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, excluding the endpoint 0.
  • the coating ratio can be controlled.
  • the manganese-containing material includes at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
  • the bismuth-containing compound includes Bi 2 O 3 , Bi(NO 3 ) 3 , bismuth subnitrate, Bi 2 (SO 4 ) 3 , BiCl 3 , Bi(CH 3 COO) 3 , at least one of bismuth subcarbonate and Bi 2 (C 2 O 4 ) 3 .
  • the sintering temperature is 50° C. to 900° C. and the time is 1 min to 30 h.
  • the present disclosure provides a positive electrode sheet.
  • the positive electrode sheet has the above-mentioned positive electrode material or a positive electrode material prepared by the above-mentioned method. Therefore, assembling the positive pole piece into a neutral or weakly acidic aqueous zinc-ion battery can improve the electrochemical performance, specific capacity and cycle performance of the battery.
  • the present disclosure proposes a neutral or weakly acidic aqueous zinc-ion battery.
  • the battery has the above-mentioned positive electrode sheet.
  • the Zn-ion battery has good electrochemical performance, high specific capacity and high cycle performance.
  • FIG. 1 is a schematic flow diagram of a method for preparing a positive electrode material according to an embodiment of the present disclosure
  • Fig. 2 is the SEM picture of the cathode material prepared in embodiment 1;
  • Fig. 3 is the EDS figure of the cathode material that embodiment 1 prepares
  • FIG. 4 is a comparison chart of cycle performance of positive electrode materials prepared in Examples 1-2 and Comparative Example 1.
  • FIG. 4 is a comparison chart of cycle performance of positive electrode materials prepared in Examples 1-2 and Comparative Example 1.
  • the present disclosure proposes a positive electrode material for a neutral or weakly acidic water-based zinc-ion battery.
  • the positive electrode material includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0 ⁇ y/z ⁇ 1, 0 ⁇ x ⁇ y .
  • the positive electrode material of the present application includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0 ⁇ y/z ⁇ 1, 0 ⁇ x ⁇ y.
  • Bi x Mn yx O z is an oxide of bismuth, that is, Bi x Mnyx O z includes bismuth oxide and/or bismuth manganese oxide, wherein the bismuth oxide combines manganese-containing compounds with the electrolyte Isolation reduces the occurrence of side reactions between the electrolyte and manganese-containing compounds.
  • Bismuth manganese oxide makes the structure of the positive electrode material more stable during charge and discharge, thereby improving the cycle performance of the battery cell. At the same time, bismuth manganese oxide can reduce the inertia
  • the production of substances improves the reversibility of active substances and reduces the fluctuation of the internal resistance of the battery.
  • This application adopts the method of in-situ combination.
  • the Bi element is uniformly distributed on the surface of the primary particles of manganese-containing compounds; When manganese compound is doped with Bi, Bi is mainly distributed on the surface of the secondary particles, and it is difficult to distribute evenly. Protective effect on the positive electrode.
  • the cathode material can be applied to a neutral or weakly acidic aqueous zinc-ion battery, which solves the problem of poor cycle performance of the zinc-ion battery, thereby obtaining a zinc-ion battery with good electrochemical performance, high specific capacity, and superior cycle performance.
  • the manganese-containing compound includes at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
  • the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0.
  • the inventors have found that if the molar ratio is too large, the gram capacity of the cell will be severely reduced, because in bismuth manganese oxide, Mn is used as an active material to gain and lose electrons, thereby providing gram capacity, while Bi element does not provide or provides less gram capacity. Therefore, adopting the molar ratio of the present application can avoid the reduction of its gram capacity while improving the cycle performance of the cell.
  • the present disclosure proposes a method for preparing the above-mentioned cathode material.
  • the method includes:
  • the manganese-containing material is dispersed in water with stirring (such as magnetic stirring), then the bismuth-containing compound is added, the stirring is continued for a period of time and then dried to obtain the precursor.
  • stirring such as magnetic stirring
  • the bismuth-containing compound uniformly coats the manganese-containing material in water, and a part of the bismuth-containing compound reacts with the manganese-containing material, that is, the bismuth element in the bismuth-containing compound replaces the manganese element in the lattice of the manganese-containing material,
  • bismuth manganese oxide is formed, which makes the structure of the positive electrode material more stable during charge and discharge, thereby improving the cycle performance of the battery cell.
  • bismuth manganese oxide can reduce the generation of inert substances and improve the active material Reversibility, reducing the fluctuation of the internal resistance of the cell. It should be noted that the specific types of the above-mentioned manganese-containing materials and bismuth-containing compounds are not particularly limited, and those skilled in the art can select according to actual needs.
  • the manganese-containing materials include MnO 2 , MnO, Mn 2 O 3 and Mn At least one of 3 O 4 ;
  • Bismuth-containing compounds include Bi 2 O 3 , Bi(NO 3 ) 3 , bismuth subnitrate, Bi 2 (SO 4 ) 3 , BiCl 3 , Bi(CH 3 COO) 3 , alkali at least one of the formula bismuth carbonate and Bi 2 (C 2 O 4 ) 3 .
  • the above stirring time is 1 min ⁇ 100 h, and according to an embodiment of the present disclosure, the above stirring time is 1 h ⁇ 8 h.
  • the inventors have found that if the stirring time is too long, other side reactions may occur; and if the stirring time is too short, the reaction cannot fully occur due to insufficient contact between different substances, and the mixing between materials will become difficult. Not evenly.
  • adopting the stirring time of the present application can make the materials mix evenly, the reaction can be fully carried out, and the generation of side reactions can be avoided simultaneously.
  • the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, excluding the endpoint 0.
  • the inventors have found that if the molar ratio is too large, the gram capacity of the cell will be severely reduced, because in bismuth manganese oxide, Mn is used as an active material to gain and lose electrons, thereby providing gram capacity, while Bi element does not provide or provides less gram capacity. Therefore, adopting the molar ratio of the present application can avoid the reduction of its gram capacity while improving the cycle performance of the cell.
  • the positive electrode material can be obtained by sintering the precursor.
  • the sintering process can be performed in a box furnace.
  • the inventors have found that the sintering process converts the bismuth-containing compound in the cladding layer that has not reacted with the manganese-containing material into Bi 2 O 3 that is insoluble in water, and at the same time, the bismuth element in the bismuth compound in the precursor replaces the bismuth in the lattice of the manganese-containing material Manganese-containing materials are sintered to form bismuth-manganese oxides.
  • Bi 2 O 3 and/or bismuth-manganese oxides can isolate the manganese-containing materials from the electrolyte, reducing the occurrence of side reactions between the electrolyte and the manganese-containing materials. Thereby improving the cycle performance of the cell.
  • the above-mentioned sintering temperature is 50°C-900°C. According to the embodiment of the present disclosure, the above-mentioned sintering temperature is 300-470°C, and the time is 1min-30h. According to the embodiment of the present disclosure, the time is 1h-8h.
  • the inventors have found that if the temperature is too low, the Bi salt cannot reach the reaction temperature for sufficient decomposition, so that it cannot fully react to form Bi2O3 or bismuth manganese oxide ; and if the temperature is too high, the material will undergo a phase transition . At the same time, if the time is too long, the phase transition of the material will occur; and if the time is too short, the reaction will not fully occur. Therefore, using the sintering conditions of the present application, the reaction can be fully carried out, and at the same time, the phase change of the material can be avoided.
  • the inventors found that by mixing the manganese-containing material, the bismuth-containing compound and water with stirring, the bismuth-containing compound is uniformly dispersed in the water and coated on the surface of the manganese-containing material, and a part of the bismuth-containing compound reacts with the manganese-containing material, That is, the bismuth element in the bismuth-containing compound replaces the manganese element in the lattice of the manganese-containing material, and bismuth-manganese oxide is formed in the subsequent sintering process, which makes the structure of the positive electrode material more stable during the charging and discharging process, thereby improving the cycle performance of the battery cell , at the same time, bismuth manganese oxide can reduce the generation of inert substances, improve the reversibility of active substances, and reduce the fluctuation of the internal resistance of the cell, and then dry the material after the bismuth-containing compound is coated on the surface of the manganese-containing material to obtain a precursor; then The obtained precursor is
  • This application is the first time to apply this method to a neutral or acidic water-based zinc-ion battery.
  • the solution method solves the problem of uneven distribution of coatings.
  • the proportion of the coating layer is controllable, and the preparation process is simple and the cost of raw materials is low. It can be applied in large-scale industrial production.
  • the bismuth element contained in the coating layer of the prepared positive electrode material makes the structure of the positive electrode material more stable during the charge and discharge process, and its application in zinc ion batteries can improve the electrochemical performance, specific capacity and cycle performance of the battery.
  • the present disclosure provides a positive electrode sheet.
  • the positive electrode sheet has the above-mentioned positive electrode material or the positive electrode material prepared by the above-mentioned method. Therefore, assembling the positive pole piece into a neutral or weakly acidic aqueous zinc-ion battery can improve the electrochemical performance, specific capacity and cycle performance of the battery.
  • the mixing ratio of the positive electrode material, the conductive agent and the binder and the specific types of the conductive agent, the binder and the base film in the above-mentioned process of preparing the positive electrode sheet are all conventional settings in the field, for example, the conductive agent is acetylene black; The binder is CMC and/or SBR; the base film is a conductive PE film.
  • the characteristics and advantages described above for the positive electrode material and its preparation method are also applicable to the positive electrode sheet, and will not be repeated here.
  • the present disclosure proposes a neutral or weakly acidic aqueous zinc-ion battery.
  • the battery has the above-mentioned positive electrode sheet.
  • the Zn-ion battery has good electrochemical performance, high specific capacity and high cycle performance.
  • the specific types of the negative pole piece and the diaphragm in the above battery assembly process are conventional settings in the field, for example, the negative pole piece is zinc foil or zinc powder; the diaphragm is an AGM diaphragm, and the electrolyte is a neutral or weakly acidic system.
  • the features and advantages described above for the positive electrode sheet are also applicable to the zinc-ion battery, and will not be repeated here.
  • solution A Using MnSO4 as raw material, configure solution A with a concentration of 0.5mol/L and a total volume of 500ml.
  • solution B Using Na 2 CO 3 as raw material, prepare solution B with a concentration of 0.5 mol/L and a total volume of 500 ml.
  • the sintering temperature is 410 °C
  • the sintering time is 4 h.
  • the sintering temperature is 465°C
  • the sintering time is 4h.
  • Battery assembly (positive electrode: the positive electrode material prepared above; negative electrode: a zinc powder negative electrode made by drawing a slurry from a copper net current collector; diaphragm: AGM diaphragm; electrolyte: a concentration of 1.8mol/L zinc sulfate+0.2 mol/L manganese sulfate aqueous solution)
  • the positive electrode material prepared above and the negative electrode Zn powder were combined to assemble the battery.
  • the negative electrode was replaced with zinc foil, and the rest were the same as in Example 1. From the SEM test results of the obtained positive electrode material, it can be seen that the material has high sphericity, regular shape, and the secondary particle size is about 4 microns. From the EDS test results, it can be seen that the Bi element is evenly distributed in the material.
  • the highest specific capacity of the zinc-ion battery is 203mAh/g at a current density of 50mA/g, 200 cycles at 125mA/g, and the capacity retention rate is 90%.
  • the highest specific capacity of the zinc ion battery is 214mAh/g at a current density of 50mA/g, 180 cycles at 125mA/g, and the capacity retention rate is 95%.
  • the highest specific capacity of the zinc ion battery is 212mAh/g at a current density of 50mA/g, 130 cycles at 125mA/g, and the capacity retention rate is 83%.
  • the highest specific capacity of the zinc-ion battery is 122mAh/g at a current density of 50mA/g, 230 cycles at 125mA/g, and the capacity retention rate is 95%.
  • the highest specific capacity of the zinc ion battery is 136mAh/g at a current density of 50mA/g, 280 cycles at 125mA/g, and the capacity retention rate is 93%.
  • the highest specific capacity of the zinc-ion battery is 45mAh/g at a current density of 50mA/g, 685 cycles at 125mA/g, and the capacity retention rate is 95%.
  • the Bi(NO 3 ) 3 was replaced by Bi 2 (SO 4 ) 3 , the Bi/Mn molar ratio was replaced by 0.75:1, and the rest were the same as in Example 1.
  • the highest specific capacity of the zinc ion battery is 122mAh/g at a current density of 50mA/g, 462 cycles at 125mA/g, and the capacity retention rate is 90%.
  • the Bi(NO 3 ) 3 was replaced by BiCl 3 , the Bi/Mn molar ratio was replaced by 0.25:1, and the rest were the same as in Example 1.
  • the sintering temperature was changed to 300° C., the sintering time was changed to 8 hours, and the rest were the same as in Example 1.
  • the highest specific capacity of the zinc ion battery is 192mAh/g at a current density of 50mA/g, 125 cycles at 125mA/g, and the capacity retention rate is 81%.
  • the sintering temperature was changed to 50° C., the sintering time was changed to 30 h, and the rest were the same as in Example 1.
  • the highest specific capacity of the zinc-ion battery is 210mAh/g at a current density of 50mA/g, 100 cycles at 125mA/g, and the capacity retention rate is 75%.
  • the sintering temperature was changed to 900° C., the sintering time was changed to 10 minutes, and the rest were the same as in Example 1.
  • the highest specific capacity of the zinc ion battery is 223mAh/g at a current density of 50mA/g, 85 cycles at 125mA/g, and the capacity retention rate is 70%.
  • the positive electrode material was replaced with Bi 0.2 Mn 0.8 O 2 , and then the process of making battery pole pieces and assembling the battery was the same as in Example 1.
  • the highest specific capacity of the zinc ion battery is 223mAh/g at a current density of 50mA/g, 85 cycles at 125mA/g, and the capacity retention rate is 70%.

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Abstract

A positive electrode material of an aqueous zinc-ion battery having a neutral or slightly acidic system, a preparation method therefor, and an application thereof. The positive electrode material comprises BixMny-xOz and a manganese-containing compound. The BixMny-xOz is distributed on the surface of the manganese-containing compound, wherein 0<y/z≤1 and 0<x≤y. The manganese-containing compound comprises at least one among MnO2, MnO, Mn2O3 and Mn3O4.

Description

中性或弱酸性体系水系锌离子电池正极材料及其制备方法与应用Neutral or weakly acidic system water-based zinc-ion battery positive electrode material and its preparation method and application
优先权信息priority information
本申请请求于2021年07月01日向中国国家知识产权局提交的、专利申请号为202110745904.7、申请名称为“中性或弱酸性体系水系锌离子电池正极材料及其制备方法与应用”的中国专利申请的优先权，并且其全部内容通过引用结合在本公开中。This application requests a Chinese patent submitted to the State Intellectual Property Office of China on July 01, 2021, with the patent application number 202110745904.7 and the application name "Neutral or Weak Acid System Aqueous Zinc-ion Battery Cathode Material and Its Preparation Method and Application" application, and its entirety is incorporated by reference into this disclosure.
技术领域technical field
本公开属于锌离子电池技术领域，具体涉及一种中性或弱酸性体系水系锌离子电池正极材料及其制备方法与应用。The disclosure belongs to the technical field of zinc-ion batteries, and in particular relates to a neutral or weakly acidic water-based zinc-ion battery positive electrode material and a preparation method and application thereof.
背景技术Background technique
随着电脑、手机、平板等便携式电子设备的普及，以及绿色环保的电动汽车的大力发展，人们对二次电池的需求越来越大，锂离子电池作为应用最广泛的二次电池也暴露出一些不足：锂资源的短缺导致其价格逐年攀升，负极易形成锂枝晶导致短路，有机电解液易燃，都存在着一定的安全隐患。锌相比较于锂，资源更加丰富，成本较低，且水系锌离子电池排除了有机电解液可能引起的火灾、爆炸等危险。此外，锌离子的氧化还原过程中传递2个电子，所以有着较高的理论容量。With the popularity of portable electronic devices such as computers, mobile phones, and tablets, and the vigorous development of green and environmentally friendly electric vehicles, people's demand for secondary batteries is increasing. As the most widely used secondary battery, lithium-ion batteries have also exposed Some deficiencies: the shortage of lithium resources has caused its price to rise year by year, the negative electrode is easy to form lithium dendrites and cause short circuits, and the organic electrolyte is flammable, all of which have certain safety hazards. Compared with lithium, zinc has more abundant resources and lower cost, and the water-based zinc-ion battery eliminates the dangers of fire and explosion that may be caused by organic electrolytes. In addition, two electrons are transferred during the redox process of zinc ions, so it has a high theoretical capacity.
目前已报道的中性或弱酸性体系水系锌离子电池正极材料中，大多数采用未包覆Bi化合物的二氧化锰作为水系锌离子电池的正极材料。MnO 2正极材料中+4价Mn容易被还原成+2价Mn，从而使得正极材料溶解到电解液中，导致循环性能变差。 Among the positive electrode materials for aqueous zinc-ion batteries in neutral or weakly acidic systems reported so far, most of them use manganese dioxide not coated with Bi compounds as the positive electrode material for aqueous zinc-ion batteries. The +4-valent Mn in the MnO 2 cathode material is easily reduced to +2-valent Mn, which makes the cathode material dissolve into the electrolyte, resulting in poor cycle performance.
因此，现有的中性或弱酸性体系水系锌离子电池正极材料有待改进。Therefore, the existing neutral or weakly acidic water-based zinc-ion battery cathode materials need to be improved.
公开内容public content
本公开旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本公开的一个目的在于提出一种中性或弱酸性体系水系锌离子电池正极材料及其制备方法与应用，该正极材料结构稳定，将其应用于锌离子电池中，可以解决锌离子电池循环性能差的问题。The present disclosure aims to solve one of the technical problems in the related art at least to a certain extent. Therefore, an object of the present disclosure is to propose a neutral or weakly acidic water-based zinc-ion battery positive electrode material and its preparation method and application. The positive electrode material has a stable structure and can be used in zinc-ion batteries to solve the The problem of poor battery cycle performance.
在本公开的一个方面，本公开提出了一种中性或弱酸性体系水系锌离子电池正极材料。根据本公开的实施例，所述正极材料包括Bi xMn y-xO z和含锰化合物，Bi xMn y-xO z分布于所述含锰化合物表面，其中，0<y/z≤1,0<x≤y。 In one aspect of the present disclosure, the present disclosure proposes a neutral or weakly acidic water-based zinc-ion battery positive electrode material. According to an embodiment of the present disclosure, the positive electrode material includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0<y/z≤1,0< x≤y.
根据本公开实施例的正极材料，其包括Bi xMn y-xO z和含锰化合物，Bi xMn y-xO z分布于含锰化合物表面，其中，0<y/z≤1,0<x≤y。当x＝y时，Bi xMn y-xO z为铋的氧化物，即Bi xMn y-xO z 包括铋的氧化物和/或铋锰氧化物，其中铋的氧化物和铋锰氧化物均可以将含锰化合物与电解液隔离开，减少电解液与含锰化合物之间副反应的发生，同时铋锰氧化物使得正极材料在充放电过程中结构更加稳定，从而提升电芯的循环性能，另外铋锰氧化物可减少惰性物质产生，提高活性物质的可逆性，降低电芯内阻的波动。本申请采用原位结合的方式，在含锰化合物合成的过程中，将Bi元素均匀的分布在含锰化合物的一次颗粒表面；而若直接将铋的氧化物与含锰化合物混合或直接将含锰化合物掺Bi，Bi主要是在二次颗粒表面分布，且很难分布均匀，分子间的作用力也比原位结合差很多，从而导致在材料充放电过程中，Bi很容易向负极迁移，失去对正极的保护作用。该正极材料可以应用于中性或弱酸性体系水系锌离子电池中，解决了锌离子电池循环性能差的问题，从而得到电化学性能好，比容量高，循环性能优越的锌离子电池。 A positive electrode material according to an embodiment of the present disclosure, which includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein, 0<y/z≤1, 0<x≤y . When x=y, Bi x Mn yx O z is an oxide of bismuth, that is, Bi x Mn yx O z includes bismuth oxide and/or bismuth manganese oxide, wherein both bismuth oxide and bismuth manganese oxide can be Isolate the manganese-containing compound from the electrolyte to reduce the occurrence of side reactions between the electrolyte and the manganese-containing compound. At the same time, bismuth manganese oxide makes the structure of the positive electrode material more stable during charging and discharging, thereby improving the cycle performance of the battery. Bismuth manganese oxide can reduce the generation of inert substances, improve the reversibility of active substances, and reduce the fluctuation of the internal resistance of the battery cell. This application adopts the method of in-situ combination. During the synthesis process of manganese-containing compounds, the Bi element is uniformly distributed on the surface of the primary particles of manganese-containing compounds; When manganese compound is doped with Bi, Bi is mainly distributed on the surface of the secondary particles, and it is difficult to distribute evenly. Protective effect on the positive electrode. The cathode material can be applied to a neutral or weakly acidic aqueous zinc-ion battery, which solves the problem of poor cycle performance of the zinc-ion battery, thereby obtaining a zinc-ion battery with good electrochemical performance, high specific capacity, and superior cycle performance.
另外，根据本公开上述实施例的中性或弱酸性体系水系锌离子电池正极材料还可以具有如下附加的技术特征：In addition, according to the above-mentioned embodiments of the present disclosure, the neutral or weakly acidic water-based zinc-ion battery positive electrode material can also have the following additional technical features:
根据本公开的一些实施例，所述含锰化合物包括MnO 2、MnO，Mn 2O 3和Mn 3O 4中的至少之一。 According to some embodiments of the present disclosure, the manganese-containing compound includes at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
根据本公开的一些实施例，所述正极材料中Bi元素与Mn元素的摩尔比在0～1之间，不包括端点0。According to some embodiments of the present disclosure, the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0.
在本公开的第二个方面，本公开提出了一种制备上述正极材料的方法。根据本公开的实施例，所述方法包括：In a second aspect of the present disclosure, the present disclosure proposes a method for preparing the above-mentioned cathode material. According to an embodiment of the present disclosure, the method includes:
(1)伴随着搅拌，将含锰物料、含铋化合物和水混合，然后干燥，以便得到前驱体；(1) With stirring, the manganese-containing material, the bismuth-containing compound and water are mixed, and then dried to obtain a precursor;
(2)将所述前驱体进行烧结，以便得到正极材料。(2) Sintering the precursor to obtain the positive electrode material.
根据本公开实施例的制备上述正极材料的方法，通过伴随着搅拌将含锰物料、含铋化合物和水混合，含铋化合物在水中均匀地分散开，包覆在含锰物料表面，并且一部分含铋化合物与含锰物料发生反应，即含铋化合物中的铋元素替代了含锰物料晶格中的锰元素，在后续烧结过程中生成铋锰氧化物，使得正极材料在充放电过程中结构更加稳定，从而提升电芯的循环性能，同时铋锰氧化物可减少惰性物质产生，提高活性物质的可逆性，降低电芯内阻的波动，然后将含铋化合物包覆在含锰物料表面后的物料干燥后得到前驱体；然后将得到的前驱体进行烧结，其中未与含锰物料反应的含铋化合物转化为难溶于水的Bi 2O 3，同时前驱体中铋化合物中的铋元素替代了含锰物料晶格中的锰元素后的物料经烧结生成铋锰氧化物，Bi 2O 3和/或铋锰氧化物可以将含锰物料与电解液隔离开，减少电解液与含锰物料之间副反应的发生，从而提升电芯的循环性能。本申请首次将该方法应用于中性或酸性体系水系锌离子电池，通过溶液法解决了包覆物分布不均匀的问题，包覆层比例可控，且制备工艺简单，原材料成本低，可应用于大规模工业化生产。另外，制备得到的正极材料表 面含有铋元素使得正极材料在充放电过程中结构更加稳定，将其应用于锌离子电池中，可以提高电池的电化学性能、比容量和循环性能。 According to the method for preparing the above-mentioned positive electrode material according to an embodiment of the present disclosure, the manganese-containing material, the bismuth-containing compound and water are mixed with stirring, the bismuth-containing compound is uniformly dispersed in the water, coated on the surface of the manganese-containing material, and a part contains The bismuth compound reacts with the manganese-containing material, that is, the bismuth element in the bismuth-containing compound replaces the manganese element in the lattice of the manganese-containing material, and bismuth-manganese oxide is formed in the subsequent sintering process, making the structure of the positive electrode material more stable during charging and discharging. Stable, thereby improving the cycle performance of the cell, while bismuth manganese oxide can reduce the generation of inert substances, improve the reversibility of the active material, reduce the fluctuation of the internal resistance of the cell, and then coat the bismuth-containing compound on the surface of the manganese-containing material. The precursor is obtained after the material is dried; then the obtained precursor is sintered, and the bismuth-containing compound that has not reacted with the manganese-containing material is converted into Bi 2 O 3 that is insoluble in water, and the bismuth element in the bismuth compound in the precursor replaces The manganese-containing material in the lattice of the manganese element is sintered to form bismuth-manganese oxide. Bi 2 O 3 and/or bismuth-manganese oxide can isolate the manganese-containing material from the electrolyte and reduce the gap between the electrolyte and the manganese-containing material. The occurrence of side reactions between them improves the cycle performance of the battery. This application is the first time to apply this method to a neutral or acidic water-based zinc-ion battery. The solution method solves the problem of uneven distribution of coatings. The proportion of the coating layer is controllable, and the preparation process is simple and the cost of raw materials is low. It can be applied in large-scale industrial production. In addition, the surface of the prepared positive electrode material contains bismuth element, which makes the structure of the positive electrode material more stable during the charge and discharge process, and its application in zinc ion batteries can improve the electrochemical performance, specific capacity and cycle performance of the battery.
在本公开的一些实施例中，在步骤(1)中，所述搅拌时间为1min～100h。由此，正极材料的包覆物分布均匀。In some embodiments of the present disclosure, in step (1), the stirring time is 1 min˜100 h. Thus, the coating of the positive electrode material is uniformly distributed.
在本公开的一些实施例中，在步骤(1)中，所述含铋化合物中Bi元素与所述含锰物料中Mn元素的摩尔比在0～1之间，不包括端点0。由此，包覆物比例可控。In some embodiments of the present disclosure, in step (1), the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, excluding the endpoint 0. Thus, the coating ratio can be controlled.
在本公开的一些实施例中，所述含锰物料包括MnO 2、MnO，Mn 2O 3和Mn 3O 4中的至少之一。 In some embodiments of the present disclosure, the manganese-containing material includes at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
在本公开的一些实施例中，所述含铋化合物包括Bi 2O 3、Bi(NO 3) 3、碱式硝酸铋、Bi 2(SO 4) 3、BiCl 3、Bi(CH 3COO) 3、碱式碳酸铋和Bi 2(C 2O 4) 3中的至少之一。 In some embodiments of the present disclosure, the bismuth-containing compound includes Bi 2 O 3 , Bi(NO 3 ) 3 , bismuth subnitrate, Bi 2 (SO 4 ) 3 , BiCl 3 , Bi(CH 3 COO) 3 , at least one of bismuth subcarbonate and Bi 2 (C 2 O 4 ) 3 .
在本公开的一些实施例中，在步骤(2)中，所述烧结的温度为50℃～900℃，时间为1min～30h。In some embodiments of the present disclosure, in step (2), the sintering temperature is 50° C. to 900° C. and the time is 1 min to 30 h.
在本公开的第三个方面，本公开提出了一种正极极片。根据本公开的实施例，所述正极极片具有上述的正极材料或采用上述方法制备得到的正极材料。由此，将该正极极片组装成中性或弱酸性体系水系锌离子电池，可以提高电池的电化学性能、比容量和循环性能。In a third aspect of the present disclosure, the present disclosure provides a positive electrode sheet. According to an embodiment of the present disclosure, the positive electrode sheet has the above-mentioned positive electrode material or a positive electrode material prepared by the above-mentioned method. Therefore, assembling the positive pole piece into a neutral or weakly acidic aqueous zinc-ion battery can improve the electrochemical performance, specific capacity and cycle performance of the battery.
在本公开的第四个方面，本公开提出了一种中性或弱酸性体系水系锌离子电池。根据本公开的实施例，该电池具有上述正极极片。由此，该锌离子电池具有良好的电化学性能、高比容量和高循环性能。In the fourth aspect of the present disclosure, the present disclosure proposes a neutral or weakly acidic aqueous zinc-ion battery. According to an embodiment of the present disclosure, the battery has the above-mentioned positive electrode sheet. Thus, the Zn-ion battery has good electrochemical performance, high specific capacity and high cycle performance.
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。Additional aspects and advantages of the disclosure will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the disclosure.
附图说明Description of drawings
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：The drawings described here are used to provide a further understanding of the application and constitute a part of the application. The schematic embodiments and descriptions of the application are used to explain the application and do not constitute an improper limitation to the application. In the attached picture:
图1是根据本公开的一个实施例的制备正极材料的方法流程示意图；1 is a schematic flow diagram of a method for preparing a positive electrode material according to an embodiment of the present disclosure;
图2是实施例1制备的正极材料的SEM图；Fig. 2 is the SEM picture of the cathode material prepared in embodiment 1;
图3是实施例1制备的正极材料的EDS图；Fig. 3 is the EDS figure of the cathode material that embodiment 1 prepares;
图4是实施例1～2和对比例1制备的正极材料的循环性能对比图。FIG. 4 is a comparison chart of cycle performance of positive electrode materials prepared in Examples 1-2 and Comparative Example 1. FIG.
具体实施方式detailed description
下面通过参考附图描述的实施例是示例性的，旨在用于解释本公开，而不能理解为对本公开的限制。The embodiments described below by referring to the figures are exemplary and are intended to explain the present disclosure and should not be construed as limiting the present disclosure.
在本公开的第一个方面，本公开提出了一种中性或弱酸性体系水系锌离子电池正极材料。根据本公开的实施例，该正极材料包括Bi xMn y-xO z和含锰化合物，Bi xMn y-xO z分布于含锰化合物表面，其中，0<y/z≤1,0<x≤y。 In the first aspect of the present disclosure, the present disclosure proposes a positive electrode material for a neutral or weakly acidic water-based zinc-ion battery. According to an embodiment of the present disclosure, the positive electrode material includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0<y/z≤1, 0<x≤y .
发明人发现，本申请的正极材料包括Bi xMn y-xO z和含锰化合物，Bi xMn y-xO z分布于含锰化合物表面，其中，0<y/z≤1,0<x≤y。当x＝y时，Bi xMn y-xO z为铋的氧化物，即Bi xMn y-xO z包括铋的氧化物和/或铋锰氧化物，其中铋的氧化物将含锰化合物与电解液隔离开，减少了电解液与含锰化合物之间副反应的发生，铋锰氧化物使得正极材料在充放电过程中结构更加稳定，从而提升电芯的循环性能，同时铋锰氧化物可减少惰性物质产生，提高活性物质的可逆性，降低电芯内阻的波动。本申请采用原位结合的方式，在含锰化合物合成的过程中，将Bi元素均匀的分布在含锰化合物的一次颗粒表面；而若直接将铋的氧化物与含锰化合物混合或直接将含锰化合物掺Bi，Bi主要是在二次颗粒表面分布，且很难分布均匀，分子间的作用力也比原位结合差很多，从而导致在材料充放电过程中，Bi很容易向负极迁移，失去对正极的保护作用。该正极材料可以应用于中性或弱酸性体系水系锌离子电池中，解决了锌离子电池循环性能差的问题，从而得到电化学性能好，比容量高，循环性能优越的锌离子电池。 The inventors found that the positive electrode material of the present application includes Bi x Mn yx O z and a manganese-containing compound, and Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0<y/z≤1, 0<x≤y. When x=y, Bi x Mn yx O z is an oxide of bismuth, that is, Bi x Mnyx O z includes bismuth oxide and/or bismuth manganese oxide, wherein the bismuth oxide combines manganese-containing compounds with the electrolyte Isolation reduces the occurrence of side reactions between the electrolyte and manganese-containing compounds. Bismuth manganese oxide makes the structure of the positive electrode material more stable during charge and discharge, thereby improving the cycle performance of the battery cell. At the same time, bismuth manganese oxide can reduce the inertia The production of substances improves the reversibility of active substances and reduces the fluctuation of the internal resistance of the battery. This application adopts the method of in-situ combination. During the synthesis process of manganese-containing compounds, the Bi element is uniformly distributed on the surface of the primary particles of manganese-containing compounds; When manganese compound is doped with Bi, Bi is mainly distributed on the surface of the secondary particles, and it is difficult to distribute evenly. Protective effect on the positive electrode. The cathode material can be applied to a neutral or weakly acidic aqueous zinc-ion battery, which solves the problem of poor cycle performance of the zinc-ion battery, thereby obtaining a zinc-ion battery with good electrochemical performance, high specific capacity, and superior cycle performance.
需要说明的是，本领域技术人员可以根据实际需要对含锰化合物的具体类型进行选择，例如，含锰化合物包括MnO 2、MnO，Mn 2O 3和Mn 3O 4中的至少之一。 It should be noted that those skilled in the art can select the specific type of manganese-containing compound according to actual needs, for example, the manganese-containing compound includes at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
进一步地，上述正极材料中Bi元素与Mn元素的摩尔比在0～1之间，不包括端点0。发明人发现，若摩尔比过大，电芯的克容量会严重降低，因为在铋锰氧化物中，Mn作为活性物质进行得失电子，从而提供克容量，而Bi元素不提供或提供较少的克容量。由此，采用本申请的摩尔比可以在提升电芯循环性能的同时避免其克容量降低。Further, the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0. The inventors have found that if the molar ratio is too large, the gram capacity of the cell will be severely reduced, because in bismuth manganese oxide, Mn is used as an active material to gain and lose electrons, thereby providing gram capacity, while Bi element does not provide or provides less gram capacity. Therefore, adopting the molar ratio of the present application can avoid the reduction of its gram capacity while improving the cycle performance of the cell.
在本公开的第二个方面，本公开提出了一种制备上述正极材料的方法。根据本公开的实施例，参考图1，该方法包括：In a second aspect of the present disclosure, the present disclosure proposes a method for preparing the above-mentioned cathode material. According to an embodiment of the present disclosure, referring to FIG. 1, the method includes:
S100：伴随着搅拌，将含锰物料、含铋化合物和水混合，然后干燥S100: Mix manganese-containing material, bismuth-containing compound and water with stirring, then dry
该步骤中，伴随着搅拌(例如磁力搅拌)，将含锰物料分散于水中，然后加入含铋化合物，继续搅拌一段时间后烘干，即可得到前驱体。发明人发现，含铋化合物在水中对含锰物料进行均匀包覆，并且一部分含铋化合物与含锰物料发生反应，即含铋化合物中的铋元素替代了含锰物料晶格中的锰元素，在后续烧结过程中生成铋锰氧化物，铋锰氧化物使得正极材料在充放电过程中结构更加稳定，从而提升电芯的循环性能，同时铋锰氧化物可减少惰性物质产生，提高活性物质的可逆性，降低电芯内阻的波动。需要说明的是，上述含锰物料和含铋化合物的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，例如，含锰物料包括MnO 2、MnO，Mn 2O 3和Mn 3O 4中的至少之一；含铋化合物包括 Bi 2O 3、Bi(NO 3) 3、碱式硝酸铋、Bi 2(SO 4) 3、BiCl 3、Bi(CH 3COO) 3、碱式碳酸铋和Bi 2(C 2O 4) 3中的至少之一。 In this step, the manganese-containing material is dispersed in water with stirring (such as magnetic stirring), then the bismuth-containing compound is added, the stirring is continued for a period of time and then dried to obtain the precursor. The inventors found that the bismuth-containing compound uniformly coats the manganese-containing material in water, and a part of the bismuth-containing compound reacts with the manganese-containing material, that is, the bismuth element in the bismuth-containing compound replaces the manganese element in the lattice of the manganese-containing material, In the subsequent sintering process, bismuth manganese oxide is formed, which makes the structure of the positive electrode material more stable during charge and discharge, thereby improving the cycle performance of the battery cell. At the same time, bismuth manganese oxide can reduce the generation of inert substances and improve the active material Reversibility, reducing the fluctuation of the internal resistance of the cell. It should be noted that the specific types of the above-mentioned manganese-containing materials and bismuth-containing compounds are not particularly limited, and those skilled in the art can select according to actual needs. For example, the manganese-containing materials include MnO 2 , MnO, Mn 2 O 3 and Mn At least one of 3 O 4 ; Bismuth-containing compounds include Bi 2 O 3 , Bi(NO 3 ) 3 , bismuth subnitrate, Bi 2 (SO 4 ) 3 , BiCl 3 , Bi(CH 3 COO) 3 , alkali at least one of the formula bismuth carbonate and Bi 2 (C 2 O 4 ) 3 .
进一步地，上述搅拌时间为1min～100h，根据本公开的实施例，上述搅拌时间为1h～8h。发明人发现，若搅拌时间过长，可能会导致其他的一些副反应发生；而若搅拌时间过短，由于不同物质之间未能充分接触，使得反应不能充分发生，材料之间的混合会变得不均匀。由此，采用本申请的搅拌时间可以使材料混合均匀，反应进行充分，同时可以避免副反应的发生。Further, the above stirring time is 1 min˜100 h, and according to an embodiment of the present disclosure, the above stirring time is 1 h˜8 h. The inventors have found that if the stirring time is too long, other side reactions may occur; and if the stirring time is too short, the reaction cannot fully occur due to insufficient contact between different substances, and the mixing between materials will become difficult. Not evenly. Thus, adopting the stirring time of the present application can make the materials mix evenly, the reaction can be fully carried out, and the generation of side reactions can be avoided simultaneously.
进一步地，上述含铋化合物中Bi元素与含锰物料中Mn元素的摩尔比在0～1之间，不包括端点0。发明人发现，若摩尔比过大，电芯的克容量会严重降低，因为在铋锰氧化物中，Mn作为活性物质进行得失电子，从而提供克容量，而Bi元素不提供或提供较少的克容量。由此，采用本申请的摩尔比可以在提升电芯循环性能的同时避免其克容量降低。Further, the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, excluding the endpoint 0. The inventors have found that if the molar ratio is too large, the gram capacity of the cell will be severely reduced, because in bismuth manganese oxide, Mn is used as an active material to gain and lose electrons, thereby providing gram capacity, while Bi element does not provide or provides less gram capacity. Therefore, adopting the molar ratio of the present application can avoid the reduction of its gram capacity while improving the cycle performance of the cell.
S200：将前驱体进行烧结S200: Sintering the precursor
该步骤中，通过将前驱体进行烧结，即可得到正极材料。具体的，烧结过程可以在箱式炉中进行。发明人发现，烧结过程使包覆层中未与含锰物料反应的含铋化合物转化为难溶于水的Bi 2O 3，同时前驱体中铋化合物中的铋元素替代了含锰物料晶格中的锰元素后的物料经烧结生成铋锰氧化物，Bi 2O 3和/或铋锰氧化物可以将含锰物料与电解液隔离开，减少电解液与含锰物料之间副反应的发生，从而提升电芯的循环性能。进一步地，上述烧结的温度为50℃～900℃，根据本公开的实施例，上述烧结的温度为300～470℃，时间为1min～30h，根据本公开的实施例，时间为1h～8h。发明人发现，若温度过低，会使得Bi盐达不到充分分解的反应温度，从而无法进行充分反应形成Bi 2O 3或铋锰氧化物；而若温度过高，会导致材料发生相变。同时，若时间过长会导致材料发生相变；而若时间过短，会导致反应未充分发生。由此，采用本申请的烧结条件，可以使反应进行充分，同时可以避免材料发生相变。 In this step, the positive electrode material can be obtained by sintering the precursor. Specifically, the sintering process can be performed in a box furnace. The inventors have found that the sintering process converts the bismuth-containing compound in the cladding layer that has not reacted with the manganese-containing material into Bi 2 O 3 that is insoluble in water, and at the same time, the bismuth element in the bismuth compound in the precursor replaces the bismuth in the lattice of the manganese-containing material Manganese-containing materials are sintered to form bismuth-manganese oxides. Bi 2 O 3 and/or bismuth-manganese oxides can isolate the manganese-containing materials from the electrolyte, reducing the occurrence of side reactions between the electrolyte and the manganese-containing materials. Thereby improving the cycle performance of the cell. Further, the above-mentioned sintering temperature is 50°C-900°C. According to the embodiment of the present disclosure, the above-mentioned sintering temperature is 300-470°C, and the time is 1min-30h. According to the embodiment of the present disclosure, the time is 1h-8h. The inventors have found that if the temperature is too low, the Bi salt cannot reach the reaction temperature for sufficient decomposition, so that it cannot fully react to form Bi2O3 or bismuth manganese oxide ; and if the temperature is too high, the material will undergo a phase transition . At the same time, if the time is too long, the phase transition of the material will occur; and if the time is too short, the reaction will not fully occur. Therefore, using the sintering conditions of the present application, the reaction can be fully carried out, and at the same time, the phase change of the material can be avoided.
发明人发现，通过伴随着搅拌将含锰物料、含铋化合物和水混合，含铋化合物在水中均匀地分散开，包覆在含锰物料表面，并且一部分含铋化合物与含锰物料发生反应，即含铋化合物中的铋元素替代了含锰物料晶格中的锰元素，在后续烧结过程中生成铋锰氧化物，使得正极材料在充放电过程中结构更加稳定，从而提升电芯的循环性能，同时铋锰氧化物可减少惰性物质产生，提高活性物质的可逆性，降低电芯内阻的波动，然后将含铋化合物包覆在含锰物料表面后的物料干燥后得到前驱体；然后将得到的前驱体进行烧结，其中未与含锰物料反应的含铋化合物转化为难溶于水的Bi 2O 3，同时前驱体中铋化合物中的铋元素替代了含锰物料晶格中的锰元素后的物料经烧结生成铋锰氧化物，Bi 2O 3和/或铋锰氧化物可以将含锰物料与电解液隔离开，减少电解液与含锰物料之间副反应的发生，从而提升电芯 的循环性能。本申请首次将该方法应用于中性或酸性体系水系锌离子电池，通过溶液法解决了包覆物分布不均匀的问题，包覆层比例可控，且制备工艺简单，原材料成本低，可应用于大规模工业化生产。另外，制备得到的正极材料包覆层中含有铋元素使得正极材料在充放电过程中结构更加稳定，将其应用于锌离子电池中，可以提高电池的电化学性能、比容量和循环性能。 The inventors found that by mixing the manganese-containing material, the bismuth-containing compound and water with stirring, the bismuth-containing compound is uniformly dispersed in the water and coated on the surface of the manganese-containing material, and a part of the bismuth-containing compound reacts with the manganese-containing material, That is, the bismuth element in the bismuth-containing compound replaces the manganese element in the lattice of the manganese-containing material, and bismuth-manganese oxide is formed in the subsequent sintering process, which makes the structure of the positive electrode material more stable during the charging and discharging process, thereby improving the cycle performance of the battery cell , at the same time, bismuth manganese oxide can reduce the generation of inert substances, improve the reversibility of active substances, and reduce the fluctuation of the internal resistance of the cell, and then dry the material after the bismuth-containing compound is coated on the surface of the manganese-containing material to obtain a precursor; then The obtained precursor is sintered, and the bismuth-containing compound that has not reacted with the manganese-containing material is converted into Bi 2 O 3 that is insoluble in water, and the bismuth element in the bismuth compound in the precursor replaces the manganese element in the lattice of the manganese-containing material After the material is sintered to form bismuth manganese oxide, Bi 2 O 3 and/or bismuth manganese oxide can isolate the manganese-containing material from the electrolyte, reduce the occurrence of side reactions between the electrolyte and the manganese-containing material, thereby improving the battery life. Core cycle performance. This application is the first time to apply this method to a neutral or acidic water-based zinc-ion battery. The solution method solves the problem of uneven distribution of coatings. The proportion of the coating layer is controllable, and the preparation process is simple and the cost of raw materials is low. It can be applied in large-scale industrial production. In addition, the bismuth element contained in the coating layer of the prepared positive electrode material makes the structure of the positive electrode material more stable during the charge and discharge process, and its application in zinc ion batteries can improve the electrochemical performance, specific capacity and cycle performance of the battery.
在本公开的第三个方面，本公开提出了一种正极极片。根据本公开的实施例，该正极极片具有上述的正极材料或采用上述方法制备得到的正极材料。由此，将该正极极片组装成中性或弱酸性体系水系锌离子电池，可以提高电池的电化学性能、比容量和循环性能。In a third aspect of the present disclosure, the present disclosure provides a positive electrode sheet. According to an embodiment of the present disclosure, the positive electrode sheet has the above-mentioned positive electrode material or the positive electrode material prepared by the above-mentioned method. Therefore, assembling the positive pole piece into a neutral or weakly acidic aqueous zinc-ion battery can improve the electrochemical performance, specific capacity and cycle performance of the battery.
此外，上述制备正极极片过程中正极材料、导电剂和粘结剂的混合比例以及导电剂、粘结剂和基膜的具体类型等均为本领域常规设置，例如，导电剂为乙炔黑；粘结剂为CMC和/或SBR；基膜为导电PE膜，同时，针对上述正极材料及其制备方法所描述的特征和优点同样适用于该正极极片，此处不再赘述。In addition, the mixing ratio of the positive electrode material, the conductive agent and the binder and the specific types of the conductive agent, the binder and the base film in the above-mentioned process of preparing the positive electrode sheet are all conventional settings in the field, for example, the conductive agent is acetylene black; The binder is CMC and/or SBR; the base film is a conductive PE film. At the same time, the characteristics and advantages described above for the positive electrode material and its preparation method are also applicable to the positive electrode sheet, and will not be repeated here.
在本公开的第四个方面，本公开提出了一种中性或弱酸性体系水系锌离子电池。根据本公开的实施例，该电池具有上述正极极片。由此，该锌离子电池具有良好的电化学性能、高比容量和高循环性能。In the fourth aspect of the present disclosure, the present disclosure proposes a neutral or weakly acidic aqueous zinc-ion battery. According to an embodiment of the present disclosure, the battery has the above-mentioned positive electrode sheet. Thus, the Zn-ion battery has good electrochemical performance, high specific capacity and high cycle performance.
此外，上述组装电池过程中负极极片和隔膜的具体类型为本领域常规设置，例如，负极极片为锌箔或锌粉；隔膜为AGM隔膜，另外，电解液为中性或弱酸性体系，同时针对上述正极极片所描述的特征和优点同样适用于该锌离子电池，此处不再赘述。In addition, the specific types of the negative pole piece and the diaphragm in the above battery assembly process are conventional settings in the field, for example, the negative pole piece is zinc foil or zinc powder; the diaphragm is an AGM diaphragm, and the electrolyte is a neutral or weakly acidic system. At the same time, the features and advantages described above for the positive electrode sheet are also applicable to the zinc-ion battery, and will not be repeated here.
下面详细描述本公开的实施例，需要说明的是下面描述的实施例是示例性的，仅用于解释本公开，而不能理解为对本公开的限制。另外，如果没有明确说明，在下面的实施例中所采用的所有试剂均为市场上可以购得的，或者可以按照本文或已知的方法合成的，对于没有列出的反应条件，也均为本领域技术人员容易获得的。Embodiments of the present disclosure are described in detail below, and it should be noted that the embodiments described below are exemplary, and are only used to explain the present disclosure, and should not be construed as limiting the present disclosure. In addition, if not clearly stated, all reagents used in the following examples are commercially available, or can be synthesized according to this article or known methods, and for the reaction conditions not listed, they are all readily available to those skilled in the art.
实施例1Example 1
(1)以MnSO 4为原料，配置溶液A，浓度为0.5mol/L，总体积为500ml。以Na 2CO 3为原料，配置溶液B，浓度为0.5mol/L，总体积为500ml。 ( 1 ) Using MnSO4 as raw material, configure solution A with a concentration of 0.5mol/L and a total volume of 500ml. Using Na 2 CO 3 as raw material, prepare solution B with a concentration of 0.5 mol/L and a total volume of 500 ml.
(2)将A、B溶液等速同时添加到2L烧杯中，并进行磁力搅拌2h，随后使用蒸馏水洗涤材料3次，并在70℃下干燥，得到MnCO 3粉末。 (2) The A and B solutions were added to a 2L beaker at the same speed at the same time, and magnetically stirred for 2 h, then the material was washed with distilled water for 3 times, and dried at 70 °C to obtain MnCO 3 powder.
(3)将MnCO 3粉末放入箱式炉中进行热处理，烧结温度为410℃，烧结时间为4h。 (3) Put the MnCO 3 powder into a box furnace for heat treatment, the sintering temperature is 410 °C, and the sintering time is 4 h.
(4)待其冷却至室温后，将材料取出，并用玛瑙研钵进行研磨，得到MnO 2。 (4) After cooling to room temperature, the material was taken out and ground with an agate mortar to obtain MnO 2 .
(5)将MnO 2分散在水中，并进行磁力搅拌，随后按照Bi/Mn比例为0.04:1(摩尔比)进行添加Bi(NO 3) 3，并磁力搅拌3h，随后进行烘干。 (5) Disperse MnO 2 in water and perform magnetic stirring, then add Bi(NO 3 ) 3 according to the Bi/Mn ratio of 0.04:1 (molar ratio), and magnetically stir for 3 hours, and then dry.
(6)将烘干的材料放入箱式炉中进行烧结，烧结温度为465℃，烧结时间为4h。(6) Put the dried material into a box furnace for sintering, the sintering temperature is 465°C, and the sintering time is 4h.
(7)待其冷却至室温后，将材料取出，并用玛瑙研钵进行研磨，得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。 (7) After it is cooled to room temperature, the material is taken out and ground with an agate mortar to obtain a coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1 , y=1, z=2).
(8)电池正极极片制作：以正极材料：乙炔黑：CMC：SBR＝80:15:2:3的比例进行匀浆，随后将搅拌均匀的正极浆料均匀的涂到导电PE膜上，并在室温下干燥。(8) Production of positive electrode sheet of battery: Homogenize with the ratio of positive electrode material: acetylene black: CMC: SBR = 80:15:2:3, and then apply the evenly stirred positive electrode slurry evenly on the conductive PE film, and dry at room temperature.
(9)电池组装：(正极：上述制备得到的正极材料；负极：采用铜网集流体拉浆制得的锌粉负极；隔膜：AGM隔膜；电解液：浓度为1.8mol/L硫酸锌+0.2mol/L硫酸锰水溶液)(9) Battery assembly: (positive electrode: the positive electrode material prepared above; negative electrode: a zinc powder negative electrode made by drawing a slurry from a copper net current collector; diaphragm: AGM diaphragm; electrolyte: a concentration of 1.8mol/L zinc sulfate+0.2 mol/L manganese sulfate aqueous solution)
将AGM隔膜在液体电解液中充分浸泡后，配合上述制备得到的正极材料，负极Zn粉，组装电池。After fully immersing the AGM diaphragm in the liquid electrolyte, the positive electrode material prepared above and the negative electrode Zn powder were combined to assemble the battery.
(10)电池测试：正极极片面密度为20mg/cm 2，25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为200mAh/g，125mA/g电流密度下循环200圈，容量保持率为93％。正极材料SEM和EDS测试结果分别如图2和图3所示，从图2可以看出材料球形度高，形貌规则，二次颗粒粒径在4微米左右，从图3可以看出Bi元素在材料中分布均匀；电池循环性能如图4所示。 (10) Battery test: the surface density of the positive electrode is 20mg/cm 2 , the highest specific capacity of the zinc ion battery at 50mA/g current density at 25°C is 200mAh/g, and the capacity is 200 cycles at 125mA/g current density. The retention rate was 93%. The SEM and EDS test results of the positive electrode material are shown in Figure 2 and Figure 3, respectively. From Figure 2, it can be seen that the material has a high degree of sphericity, a regular shape, and the particle size of the secondary particles is about 4 microns. It can be seen from Figure 3 that the Bi element It is evenly distributed in the material; the cycle performance of the battery is shown in Figure 4.
实施例2Example 2
将负极更换为锌箔，其余同实施例1。从得到的正极材料的SEM测试结果可以看出，材料球形度高，形貌规则，二次颗粒粒径在4微米左右，从其EDS测试结果可以看出Bi元素在材料中分布均匀。The negative electrode was replaced with zinc foil, and the rest were the same as in Example 1. From the SEM test results of the obtained positive electrode material, it can be seen that the material has high sphericity, regular shape, and the secondary particle size is about 4 microns. From the EDS test results, it can be seen that the Bi element is evenly distributed in the material.
(11)电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为203mAh/g，125mA/g下循环200圈，容量保持率为82％。电池循环性能如图4所示。(11) Battery test: the highest specific capacity of the zinc ion battery at 50mA/g current density at 25°C is 203mAh/g, 200 cycles at 125mA/g, and the capacity retention rate is 82%. The cycle performance of the battery is shown in Figure 4.
实施例3Example 3
将Bi/Mn摩尔比更换为0.06:1，其余同实施例1。The Bi/Mn molar ratio was changed to 0.06:1, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，二次颗粒粒径在4微米左右，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀，且Bi/Mn比例接近0.06:1 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained cathode material, it can be seen that the material is a spherical particle with a regular shape, and the secondary particle size is about 4 microns. It can be seen from the EDS test results that the Bi element is very uniformly distributed in the material. And the ratio of Bi/Mn is close to 0.06:1
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为203mAh/g，125mA/g下循环200圈，容量保持率90％。Battery test: at 25°C, the highest specific capacity of the zinc-ion battery is 203mAh/g at a current density of 50mA/g, 200 cycles at 125mA/g, and the capacity retention rate is 90%.
实施例4Example 4
将Bi(NO 3) 3更换为Bi(CH 3COO) 3，其余同实施例1。 Replace Bi(NO 3 ) 3 with Bi(CH 3 COO) 3 , and the rest are the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，二次颗粒粒径在4微米左右，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is spherical particles with regular shape, and the secondary particle size is about 4 microns. It can be seen from the EDS test results that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为214mAh/g，125mA/g下循环180圈，容量保持率为95％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 214mAh/g at a current density of 50mA/g, 180 cycles at 125mA/g, and the capacity retention rate is 95%.
实施例5Example 5
将Bi(NO 3) 3更换为碱式碳酸铋，其余同实施例1。 Replace Bi(NO 3 ) 3 with bismuth subcarbonate, and the rest are the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，二次颗粒粒径在4微米左右，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is spherical particles with regular shape, and the secondary particle size is about 4 microns. It can be seen from the EDS test results that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为210mAh/g，125mA/g下循环230圈，容量保持率为85％。Battery test: the highest specific capacity of the zinc-ion battery at 50mA/g current density at 25°C is 210mAh/g, 230 cycles at 125mA/g, and the capacity retention rate is 85%.
实施例6Example 6
将Bi(NO 3) 3更换为Bi 2O 3，其余同实施例1。 Replace Bi(NO 3 ) 3 with Bi 2 O 3 , and the rest are the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，二次颗粒粒径在4微米左右，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is spherical particles with regular shape, and the secondary particle size is about 4 microns. It can be seen from the EDS test results that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为212mAh/g，125mA/g下循环130圈，容量保持率为83％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 212mAh/g at a current density of 50mA/g, 130 cycles at 125mA/g, and the capacity retention rate is 83%.
实施例7Example 7
将MnO 2更换为Mn 2O 3，其余同实施例1。 Replace MnO 2 with Mn 2 O 3 , and the rest are the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤2，y＝2，z＝3)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤2, y=2, z=3). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为122mAh/g，125mA/g下循环230圈，容量保持率为95％。Battery test: at 25°C, the highest specific capacity of the zinc-ion battery is 122mAh/g at a current density of 50mA/g, 230 cycles at 125mA/g, and the capacity retention rate is 95%.
实施例8Example 8
将MnO 2更换为Mn 3O 4，其余同实施例1。 Replace MnO 2 with Mn 3 O 4 , and the rest are the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤3，y＝3，z＝4)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤3, y=3, z=4). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为92mAh/g， 125mA/g下循环300圈，容量保持率为92％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 92mAh/g at a current density of 50mA/g, and after 300 cycles at 125mA/g, the capacity retention rate is 92%.
实施例9Example 9
将Bi/Mn摩尔比更换为0.5:1，其余同实施例1。The Bi/Mn molar ratio was changed to 0.5:1, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为136mAh/g，125mA/g下循环280圈，容量保持率为93％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 136mAh/g at a current density of 50mA/g, 280 cycles at 125mA/g, and the capacity retention rate is 93%.
实施例10Example 10
将Bi/Mn摩尔比更换为0.95:1，其余同实施例1。The Bi/Mn molar ratio was changed to 0.95:1, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为45mAh/g，125mA/g下循环685圈，容量保持率为95％。Battery test: at 25°C, the highest specific capacity of the zinc-ion battery is 45mAh/g at a current density of 50mA/g, 685 cycles at 125mA/g, and the capacity retention rate is 95%.
实施例11Example 11
将Bi(NO 3) 3更换为Bi 2(SO 4) 3，Bi/Mn摩尔比更换为0.75:1，其余同实施例1。 The Bi(NO 3 ) 3 was replaced by Bi 2 (SO 4 ) 3 , the Bi/Mn molar ratio was replaced by 0.75:1, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为122mAh/g，125mA/g下循环462圈，容量保持率为90％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 122mAh/g at a current density of 50mA/g, 462 cycles at 125mA/g, and the capacity retention rate is 90%.
实施例12Example 12
将Bi(NO 3) 3更换为BiCl 3，Bi/Mn摩尔比更换为0.25:1，其余同实施例1。 The Bi(NO 3 ) 3 was replaced by BiCl 3 , the Bi/Mn molar ratio was replaced by 0.25:1, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为168mAh/g，125mA/g下循环280圈，容量保持率为82％。Battery test: the highest specific capacity of the zinc ion battery at 50mA/g current density at 25°C is 168mAh/g, 280 cycles at 125mA/g, and the capacity retention rate is 82%.
实施例13Example 13
将烧结温度更换为300℃，烧结时间更换为8h，其余同实施例1。The sintering temperature was changed to 300° C., the sintering time was changed to 8 hours, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为192mAh/g，125mA/g下循环125圈，容量保持率为81％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 192mAh/g at a current density of 50mA/g, 125 cycles at 125mA/g, and the capacity retention rate is 81%.
实施例14Example 14
将烧结温度更换为50℃，烧结时间更换为30h，其余同实施例1。The sintering temperature was changed to 50° C., the sintering time was changed to 30 h, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为210mAh/g，125mA/g下循环100圈，容量保持率为75％。Battery test: at 25°C, the highest specific capacity of the zinc-ion battery is 210mAh/g at a current density of 50mA/g, 100 cycles at 125mA/g, and the capacity retention rate is 75%.
实施例15Example 15
将烧结温度更换为900℃，烧结时间更换为10min，其余同实施例1。The sintering temperature was changed to 900° C., the sintering time was changed to 10 minutes, and the rest were the same as in Example 1.
制备得到包覆好的正极材料(包覆层包括Bi 2O 3和Bi xMn y-xO z，0＜x≤1，y＝1，z＝2)。从得到的正极材料的SEM测试结果可以看出，材料为球形颗粒，形貌规则，从其EDS测试结果可以看出，Bi元素在材料中分布非常均匀。 Prepare the coated positive electrode material (the coating layer includes Bi 2 O 3 and Bi x Mn yx O z , 0<x≤1, y=1, z=2). From the SEM test results of the obtained positive electrode material, it can be seen that the material is a spherical particle with a regular shape. From the EDS test results, it can be seen that the Bi element is very uniformly distributed in the material.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为65mAh/g，125mA/g下循环300圈，容量保持率为95％。Battery test: the highest specific capacity of the zinc ion battery at 50mA/g current density at 25°C is 65mAh/g, 300 cycles at 125mA/g, and the capacity retention rate is 95%.
对比例1Comparative example 1
未包覆Bi元素合成MnO 2，随后制作电池极片和组装电芯的过程同实施例1。 The process of synthesizing MnO 2 from uncoated Bi elements, followed by making battery pole pieces and assembling batteries is the same as in Example 1.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为230mAh/g，125mA/g下循环70圈，容量保持率为63％。电池循环性能如图4所示。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 230mAh/g at a current density of 50mA/g, 70 cycles at 125mA/g, and the capacity retention rate is 63%. The cycle performance of the battery is shown in Figure 4.
对比例2Comparative example 2
在制备正极极片的匀浆过程中直接将Bi 2O 3与MnO 2混合，随后制作电池极片和组装电池的过程同实施例1。 In the homogenization process of preparing the positive electrode sheet, Bi 2 O 3 and MnO 2 were directly mixed, and then the process of making the battery electrode sheet and assembling the battery was the same as that in Example 1.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为223mAh/g，125mA/g下循环85圈，容量保持率为70％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 223mAh/g at a current density of 50mA/g, 85 cycles at 125mA/g, and the capacity retention rate is 70%.
对比例3Comparative example 3
将正极材料更换为Bi 0.2Mn 0.8O 2，随后制作电池极片和组装电池的过程同实施例1。 The positive electrode material was replaced with Bi 0.2 Mn 0.8 O 2 , and then the process of making battery pole pieces and assembling the battery was the same as in Example 1.
电池测试：25℃环境下锌离子电池在50mA/g电流密度下的最高比容量为223mAh/g，125mA/g下循环85圈，容量保持率为70％。Battery test: at 25°C, the highest specific capacity of the zinc ion battery is 223mAh/g at a current density of 50mA/g, 85 cycles at 125mA/g, and the capacity retention rate is 70%.
上面结合附图对本申请的实施例进行了描述，但是本申请并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本申请的启示下，在不脱离本申请宗旨和权利要求所保护的范围情况下，还可做出很多形式，均属于本申请的保护之内。The embodiments of the present application have been described above in conjunction with the accompanying drawings, but the present application is not limited to the above-mentioned specific implementations. The above-mentioned specific implementations are only illustrative and not restrictive. Those of ordinary skill in the art will Under the inspiration of this application, without departing from the purpose of this application and the scope of protection of the claims, many forms can also be made, all of which belong to the protection of this application.

Claims (11)

  1. 一种中性或弱酸性体系水系锌离子电池正极材料，其中，包括Bi xMn y-xO z和含锰化合物，Bi xMn y-xO z分布于所述含锰化合物表面，其中，0<y/z≤1，0<x≤y。 A neutral or weakly acidic water-based zinc-ion battery positive electrode material, which includes Bi x Mn yx O z and a manganese-containing compound, Bi x Mn yx O z is distributed on the surface of the manganese-containing compound, wherein 0<y/ z≤1, 0<x≤y.
  2. 根据权利要求1所述的正极材料，其中，所述含锰化合物包括MnO 2、MnO，Mn 2O 3和Mn 3O 4中的至少之一。 The positive electrode material according to claim 1, wherein the manganese-containing compound comprises at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
  3. 根据权利要求1或2所述的正极材料，其中，所述正极材料中Bi元素与Mn元素的摩尔比在0～1之间，不包括端点0。The positive electrode material according to claim 1 or 2, wherein the molar ratio of the Bi element to the Mn element in the positive electrode material is between 0 and 1, excluding the endpoint 0.
  4. 一种制备权利要求1～3中任一项所述正极材料的方法，其中，包括：A method for preparing the cathode material according to any one of claims 1 to 3, comprising:
    (1)伴随着搅拌，将含锰物料、含铋化合物和水混合，然后干燥，以便得到前驱体；(1) With stirring, the manganese-containing material, the bismuth-containing compound and water are mixed, and then dried to obtain a precursor;
    (2)将所述前驱体进行烧结，以便得到正极材料。(2) Sintering the precursor to obtain the positive electrode material.
  5. 根据权利要求4所述的方法，其中，在步骤(1)中，所述搅拌时间为1min～100h。The method according to claim 4, wherein, in step (1), the stirring time is 1 min˜100 h.
  6. 根据权利要求4或5所述的方法，其中，在步骤(1)中，所述含铋化合物中Bi元素与所述含锰物料中Mn元素的摩尔比在0～1之间，不包括端点0。The method according to claim 4 or 5, wherein, in step (1), the molar ratio of the Bi element in the bismuth-containing compound to the Mn element in the manganese-containing material is between 0 and 1, excluding endpoints 0.
  7. 根据权利要求4-6中任一项所述的方法，其中，所述含锰物料包括MnO 2、MnO，Mn 2O 3和Mn 3O 4中的至少之一。 The method according to any one of claims 4-6, wherein the manganese-containing material comprises at least one of MnO 2 , MnO, Mn 2 O 3 and Mn 3 O 4 .
  8. 根据权利要求4-7中任一项所述的方法，其中，所述含铋化合物包括Bi 2O 3、Bi(NO 3) 3、碱式硝酸铋、Bi 2(SO 4) 3、BiCl 3、Bi(CH 3COO) 3、碱式碳酸铋和Bi 2(C 2O 4) 3中的至少之一。 The method according to any one of claims 4-7, wherein the bismuth-containing compound comprises Bi 2 O 3 , Bi(NO 3 ) 3 , bismuth subnitrate, Bi 2 (SO 4 ) 3 , BiCl 3 , Bi(CH 3 COO) 3 , bismuth subcarbonate, and Bi 2 (C 2 O 4 ) 3 .
  9. 根据权利要求4-8中任一项所述的方法，其中，在步骤(2)中，所述烧结的温度为50℃～900℃，时间为1min～30h。The method according to any one of claims 4-8, wherein, in step (2), the temperature of the sintering is 50°C-900°C, and the time is 1min-30h.
  10. 一种正极极片，其中，具有权利要求1～3中任一项所述的正极材料或采用权利要求4～9中任一项所述的方法制备得到的正极材料。A positive electrode sheet, which has the positive electrode material according to any one of claims 1-3 or the positive electrode material prepared by the method according to any one of claims 4-9.
  11. 一种中性或弱酸性体系水系锌离子电池，其中，具有权利要求10所述的正极极片。A neutral or weakly acidic water system zinc ion battery, wherein, has the positive pole piece described in claim 10.
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