WO2021057334A1 - Preparation method for and application of nano cubic bimetal selenide material - Google Patents

Preparation method for and application of nano cubic bimetal selenide material Download PDF

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WO2021057334A1
WO2021057334A1 PCT/CN2020/109571 CN2020109571W WO2021057334A1 WO 2021057334 A1 WO2021057334 A1 WO 2021057334A1 CN 2020109571 W CN2020109571 W CN 2020109571W WO 2021057334 A1 WO2021057334 A1 WO 2021057334A1
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nanocubic
selenide material
bimetallic
bimetal
nanocube
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PCT/CN2020/109571
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French (fr)
Chinese (zh)
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杨涛
翟赟
胡朴
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苏州潜寻新能源科技有限公司
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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 invention relates to the technical field of sodium ion batteries, in particular to a preparation method and application of a nano cubic bimetal selenide material.
  • lithium-ion battery As a new type of high-efficiency electric energy storage device, lithium-ion battery has the advantages of high capacity and long cycle life, and has attracted more and more researchers' attention and attention. As we all know, lithium-ion batteries have gone through several generations of innovation and have penetrated into people's daily lives. However, as a national strategic resource, metallic lithium, its expensive price and limited storage capacity all limit the application prospects of lithium-ion batteries. In comparison, sodium ion batteries have become a new type of energy device with great potential in recent years due to the wide distribution of sodium in the earth's crust, the rich content, the environmental friendliness, and the low redox potential.
  • the purpose of the present invention is to provide a method for preparing nanocubic bimetal selenide material and its application in sodium ion batteries, so as to solve the battery specific capacity of the current negative electrode materials of sodium ion batteries proposed in the background art. Smaller, poorer cycle performance.
  • step 2) Weigh the selenium source and the nanocube bimetallic hydroxide obtained in step 1), and perform selenization by a hydrothermal method or a calcination method to obtain the nanocube bimetallic selenide material;
  • the metal precursor is a hydrochloride, nitrate, sulfate or potassium salt containing transition metals (including late transition metals) such as copper, zinc, nickel, cobalt, or tin.
  • the metal in the metal precursor is one of transition metals (including late transition metals) such as copper, zinc, nickel, cobalt, or tin, and the precursor is the corresponding hydrochloride, nitrate, and sulfuric acid of the respective metal.
  • transition metals including late transition metals
  • the precursor is the corresponding hydrochloride, nitrate, and sulfuric acid of the respective metal.
  • the hydrochloride, nitrate, sulfate or potassium salt containing transition metals (including late transition metals) such as copper, zinc, nickel, cobalt or tin are potassium stannate, zinc sulfate, Copper nitrate, nickel nitrate or cobalt chloride.
  • the selenium source is selenium powder or selenium dioxide.
  • the dispersion concentration of the metal precursor in deionized water is 0.15-0.3 g ⁇ mL -1 .
  • step 1) the temperature of the magnetic stirring is 10-50°C.
  • step 2) the molar ratio of the nanocubic double metal hydroxide to the selenium source is 0.001-100:1.
  • step 2) the conditions of the hydrothermal selenization are: dispersing the nanocubic double metal hydroxide and the selenium source in deionized water, and then placing it in a polytetrafluoroethylene reactor
  • sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 150-300°C, and the reaction time is 1-12 hours.
  • step 2) the conditions for the calcining method for selenization are: the nanocubic double metal hydroxide and the selenium source are respectively placed in different arks (containers), and the hydrogen/argon The calcination is carried out in an air atmosphere, the temperature increase rate of the calcination is 1-10°C/min, the temperature of the calcination is 300-800°C, and the holding time of the calcination is 1-5 hours.
  • the invention also provides a nano-cubic bimetal selenide material prepared by the above-mentioned preparation method.
  • the preparation method of the nanocubic bimetal selenide material is applied in the preparation of sodium ion battery products.
  • the process flow of the present invention is short and the equipment is simple.
  • the prepared nanocubic bimetallic hydroxide material forms bimetallic selenide microcrystalline boundaries, which can provide a buffer area and effectively suppress the volume expansion problem during charging and discharging.
  • the cubic block structure can significantly improve the structural stability of the material, thereby improving the cycle performance and life of the battery.
  • the present invention has strong structural advantages by introducing nanocubic bimetallic selenide as the active material, which can effectively improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery, and the nanostructure can be effectively shortened Sodium ions are inserted into the distance of the material, thereby effectively increasing the specific capacity of the battery.
  • the raw materials of the preparation method of the present invention are cheap and easy to obtain, environmentally friendly, and the process parameters are simple and controllable, which facilitates the realization of technology promotion, and solves the problem that the negative electrode materials of the existing sodium ion battery have a small battery specific capacity and poor cycle performance.
  • the problem has broad market prospects.
  • Figure 1 is a scanning electron micrograph of nanocubic zinc tin selenide prepared in Example 1 of the present invention.
  • Example 2 is a graph showing the first two cycles of charge and discharge curves of the nanocubic zinc tin selenide prepared in Example 1 of the present invention used as a negative electrode material for a sodium ion battery.
  • Example 3 is a cycle diagram of specific discharge capacity of nanocubic zinc tin selenide prepared in Example 1 of the present invention as a negative electrode material of a sodium ion battery.
  • a preparation method of nano cubic bimetal selenide material the steps are as follows:
  • the above-mentioned nanocubic zinc tin selenide material is used as a negative electrode material of a sodium ion battery for electrochemical testing.
  • the nano cubic zinc tin selenide material is used as the negative electrode material to prepare a sodium ion battery by using the prior art method, and the electrochemical performance test is performed on it.
  • FIG. 2 and FIG. 3 show the electrochemistry of the sodium ion battery.
  • Figure 2 is the first two rounds of charge and discharge curves of the nanocubic zinc selenide prepared in this embodiment as the negative material of the sodium ion battery
  • Figure 3 is the nano cubic zinc selenide prepared in this embodiment Cycle diagram of specific discharge capacity of tin used as a negative electrode material for sodium ion batteries.
  • the prepared nanocubic zinc tin selenide material when used as a negative electrode material for a sodium ion battery, the first two turns can reach a discharge specific capacity of about 560mAh ⁇ g -1 ; as can be seen from Figure 3,
  • the prepared nanocubic zinc tin selenide material has excellent cycle performance when used as a negative electrode material of a sodium ion battery, and can maintain a stable discharge specific capacity when it is cycled to 50 cycles without rapid decay.
  • the nano cubic bimetal selenide material prepared by the above preparation method has strong structural advantages, and the nano cubic bimetal selenide material can be used as a negative electrode material of a sodium ion battery.
  • the preparation method of the nanocubic bimetal selenide material is applied in the preparation of sodium ion battery products.
  • a preparation method of nano cubic bimetal selenide material the steps are as follows:
  • a preparation method of nano cubic bimetal selenide material the steps are as follows:
  • nickel nitrate and zinc sulfate with a molar ratio of 0.5:1 and dissolve them in deionized water.
  • the dispersion concentration of the nickel nitrate and zinc sulfate in deionized water are both 0.15 g ⁇ mL -1 , and mix them after they are fully dissolved. Evenly, place it on a magnetic stirrer and stir at 10°C for 1 hour to obtain a suspension. After centrifugation, washing with water and alcohol washing, nanocubic double metal hydroxide is obtained;
  • nanocube double metal hydroxide and selenium dioxide weigh the nanocube double metal hydroxide and selenium dioxide and disperse them in deionized water (the molar ratio of the nanocube double metal hydroxide and selenium dioxide is 0.001:1), and then place them in a polytetrafluoroethylene reactor
  • sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 150°C, the reaction time is 1 hour, and the reaction time is 1 hour.
  • the reaction temperature is 150°C
  • the reaction time is 1 hour
  • the reaction time is 1 hour.
  • the materials are prepared for sodium ion batteries.
  • a preparation method of nano cubic bimetal selenide material the steps are as follows:
  • nanocubic double metal hydroxide and selenium dioxide weigh the nanocubic double metal hydroxide and selenium dioxide and disperse them in deionized water (the molar ratio of the nanocube double metal hydroxide and selenium dioxide is 100:1), and then place them in a polytetrafluoroethylene reactor
  • sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 300°C, the reaction time is 12 hours, and the reaction time is 12 hours.
  • the nanocubic double metal hydroxide material is obtained by natural cooling to room temperature, which can be used as the negative electrode of sodium ion battery. The materials are prepared for sodium ion batteries.
  • the beneficial effects of the present invention are as follows.
  • the nanocubic double metal hydroxide material prepared by the present invention combines two advantages.
  • the formed double metal selenide microcrystalline boundary can provide a buffer area and effectively suppress the volume expansion problem during charging and discharging.
  • the cubic block structure can significantly improve the structural stability of the material, thereby improving the cycle performance and life of the battery; moreover, the nanocubic bimetallic selenide prepared by the invention has strong structural advantages and effectively improves the transition metal as a sodium ion battery
  • the specific capacity and cycle life of the battery in the case of the negative electrode material can effectively improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery.
  • the preparation method of the present invention has a short process flow, simple equipment, and cheap and easy-to-obtain raw materials. , Environment-friendly, simple and controllable process parameters, easy to realize technology promotion.
  • the present invention addresses the problems of low reversible capacity and poor cycle performance of current sodium ion battery negative materials, and introduces nanocubic bimetallic selenide as the active material, which has strong structural advantages and can be effective Improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery; the nanostructure can effectively shorten the distance of the sodium ion intercalation material, thereby effectively increasing the specific capacity of the battery, and the bimetallic selenide combines the two advantages.
  • the formed microcrystalline boundary can provide a buffer area and effectively suppress the volume expansion problem during charging and discharging. Combined with the cubic block structure, the structural stability of the material can be significantly improved, thereby improving the cycle performance and life of the battery, and has a broad market prospect.

Abstract

The invention relates to the technical field of sodium-ion batteries. Specifically disclosed are a preparation method for and an application of a nano cubic bimetal selenide material. The method comprises the following steps: 1) weighing two different metal precursors, dissolving same in deionized water, mixing evenly and then stirring to obtain a suspension, centrifuging, washing with water and washing with alcohol to obtain a nano cubic bimetal hydroxide; and 2) weighing a selenium source and the nano cubic bimetal hydroxide, and selenizing same. In order to improve the specific capacity and cycle life of a sodium-ion battery when a transition metal is used as the negative electrode material of the battery, in the present invention, a cubic bimetal hydroxide precursor is prepared by a solution method by weighing a certain amount of transition metal precursors, and then selenization treatment is performed by a hydrothermal method or a calcination method to obtain the nano cubic bimetal selenide material, which can be used for preparing a sodium-ion battery product, and can effectively improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery.

Description

一种纳米立方体双金属硒化物材料的制备方法及其应用Preparation method and application of nano cubic bimetal selenide material 技术领域Technical field
本发明涉及钠离子电池技术领域，具体是一种纳米立方体双金属硒化物材料的制备方法及其应用。The invention relates to the technical field of sodium ion batteries, in particular to a preparation method and application of a nano cubic bimetal selenide material.
背景技术Background technique
随着社会的发展和科技的进步，能源匮乏和环境污染已成为当今社会发展面临的重大问题。而锂离子电池作为一种新型高效的电能存储装置，具有容量高、循环寿命长等优点，受到越来越多研究者们的关注与重视。众所周知，锂离子电池历经数代革新，已经渗透到人们的日常生活中。但是，金属锂作为国家战略资源，其昂贵的价格和有限的存储量无一不限制着锂离子电池的应用前景。相较而言，钠离子电池因钠元素在地壳中广泛分布、含量丰富、对环境友好并具有较低的氧化还原电势等优点，近年来成为一种颇具潜力的新型能源器件。然而，钠离子电池研究尚处于初级阶段，如何提高钠离子电池性能(如长循环寿命、高能量/功率密度、优异的倍率性能以及稳定的低温高温性能等)就成了目前研究者们亟待解决的主要问题。With the development of society and the advancement of science and technology, energy scarcity and environmental pollution have become major problems facing the development of today's society. As a new type of high-efficiency electric energy storage device, lithium-ion battery has the advantages of high capacity and long cycle life, and has attracted more and more researchers' attention and attention. As we all know, lithium-ion batteries have gone through several generations of innovation and have penetrated into people's daily lives. However, as a national strategic resource, metallic lithium, its expensive price and limited storage capacity all limit the application prospects of lithium-ion batteries. In comparison, sodium ion batteries have become a new type of energy device with great potential in recent years due to the wide distribution of sodium in the earth's crust, the rich content, the environmental friendliness, and the low redox potential. However, the research on sodium ion batteries is still in its infancy. How to improve the performance of sodium ion batteries (such as long cycle life, high energy/power density, excellent rate performance and stable low temperature and high temperature performance, etc.) has become an urgent solution for researchers. The main problem.
但是，目前所研究的钠离子电池负极材料中，大多为脱嵌机制(碳基、钛基等)的材料，其中，大多的碳材料在不同程度上存在首次库伦效率低和循环性能差的问题，而电极材料的高比容量对于电池充放电过程的安全性有着重要意义。However, most of the negative electrode materials for sodium ion batteries currently studied are materials with a deintercalation mechanism (carbon-based, titanium-based, etc.). Among them, most of the carbon materials have the problems of low first-time coulombic efficiency and poor cycle performance to varying degrees. , And the high specific capacity of the electrode material is of great significance to the safety of the battery charging and discharging process.
因此，为了解决当前钠离子电池的负极材料所存在的电池比容量较小、循环性能较差的问题，设计一种纳米立方体双金属硒化物材料的制备方法及其应用，成为目前亟需解决的问题。Therefore, in order to solve the problems of small battery specific capacity and poor cycle performance existing in the current negative electrode materials of sodium-ion batteries, the design of a preparation method and application of nanocubic bimetallic selenide materials has become an urgent need to solve at present. problem.
发明内容Summary of the invention
本发明的目的在于提供一种纳米立方体双金属硒化物材料的制备方法及其在钠离子电池中的应用，用以解决上述背景技术中提出的当前钠离子电池的负极材料所存在的电池比容量较小、循环性能较差的问题。The purpose of the present invention is to provide a method for preparing nanocubic bimetal selenide material and its application in sodium ion batteries, so as to solve the battery specific capacity of the current negative electrode materials of sodium ion batteries proposed in the background art. Smaller, poorer cycle performance.
为实现上述目的，本发明提供如下技术方案：In order to achieve the above objectives, the present invention provides the following technical solutions:
一种纳米立方体双金属硒化物材料的制备方法，其特征在于，它包括以下步骤：A method for preparing nanocubic bimetal selenide material is characterized in that it comprises the following steps:
1)称取摩尔比为0.5-1:1的两种不同的金属前驱体，分别溶解在去离子水中，待充分溶解后混合均匀，磁力搅拌1-24小时得到悬浊液，通过离心、水洗、醇洗后得到纳米立方体双金属氢氧化物；1) Weigh two different metal precursors with a molar ratio of 0.5-1:1, and dissolve them in deionized water. After they are fully dissolved, they are mixed uniformly, and the suspension is obtained by magnetic stirring for 1-24 hours. The suspension is obtained by centrifugation and water washing. , Obtain nanocubic double metal hydroxide after alcohol washing;
2)称取硒源和步骤1)中得到的纳米立方体双金属氢氧化物，通过水热法或煅烧法进行硒化，得到所述的纳米立方体双金属硒化物材料；2) Weigh the selenium source and the nanocube bimetallic hydroxide obtained in step 1), and perform selenization by a hydrothermal method or a calcination method to obtain the nanocube bimetallic selenide material;
其中，步骤1)中，所述金属前驱体为含铜、锌、镍、钴或锡等过渡金属(包括后过渡金属)的盐酸盐、硝酸盐、硫酸盐或钾酸盐。Wherein, in step 1), the metal precursor is a hydrochloride, nitrate, sulfate or potassium salt containing transition metals (including late transition metals) such as copper, zinc, nickel, cobalt, or tin.
具体的，所述金属前驱体中的金属为铜、锌、镍、钴或锡等过渡金属(包括后过渡金属)中的一种，前驱体为各自金属对应的盐酸盐、硝酸盐、硫酸盐、钾酸盐中的一种。Specifically, the metal in the metal precursor is one of transition metals (including late transition metals) such as copper, zinc, nickel, cobalt, or tin, and the precursor is the corresponding hydrochloride, nitrate, and sulfuric acid of the respective metal. One of salt and potash.
作为本发明进一步的方案：所述含铜、锌、镍、钴或锡等过渡金属(包括后过渡金属)的盐酸盐、硝酸盐、硫酸盐或钾酸盐为锡酸钾、硫酸锌、硝酸铜、硝酸镍或氯化钴。As a further solution of the present invention: the hydrochloride, nitrate, sulfate or potassium salt containing transition metals (including late transition metals) such as copper, zinc, nickel, cobalt or tin are potassium stannate, zinc sulfate, Copper nitrate, nickel nitrate or cobalt chloride.
作为本发明再进一步的方案：步骤2)中，所述硒源为硒粉或二氧化硒。As a further solution of the present invention: in step 2), the selenium source is selenium powder or selenium dioxide.
作为本发明再进一步的方案：步骤1)中，所述金属前驱体在去离子水中的分散浓度为0.15-0.3g·mL -1。 As a further solution of the present invention: in step 1), the dispersion concentration of the metal precursor in deionized water is 0.15-0.3 g·mL -1 .
作为本发明再进一步的方案：步骤1)中，所述磁力搅拌的温度为10-50℃。As a further solution of the present invention: in step 1), the temperature of the magnetic stirring is 10-50°C.
作为本发明再进一步的方案：步骤2)中，所述纳米立方体双金属氢氧化物和硒源的摩尔比为0.001-100:1。As a further solution of the present invention: in step 2), the molar ratio of the nanocubic double metal hydroxide to the selenium source is 0.001-100:1.
作为本发明再进一步的方案：步骤2)中，所述水热法硒化的条件为：将纳米立方体双金属氢氧化物和硒源分散在去离子水中，然后置于聚四氟乙烯反应釜中，加入氢氧化钠和硼氢化钠进行硒化反应，反应温度为150-300℃，反应时间为1-12小时。As a further solution of the present invention: in step 2), the conditions of the hydrothermal selenization are: dispersing the nanocubic double metal hydroxide and the selenium source in deionized water, and then placing it in a polytetrafluoroethylene reactor In the process, sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 150-300°C, and the reaction time is 1-12 hours.
作为本发明再进一步的方案：步骤2)中，所述煅烧法硒化的条件为：将纳米立方体双金属氢氧化物和硒源分别置于不同的方舟(容器)中，共同在氢气/氩气的气氛下进行煅烧，所述煅烧的升温速度为1-10℃/min，所述煅烧的温度300-800℃，所述煅烧的保温时间为1-5小时。As a further solution of the present invention: in step 2), the conditions for the calcining method for selenization are: the nanocubic double metal hydroxide and the selenium source are respectively placed in different arks (containers), and the hydrogen/argon The calcination is carried out in an air atmosphere, the temperature increase rate of the calcination is 1-10°C/min, the temperature of the calcination is 300-800°C, and the holding time of the calcination is 1-5 hours.
本发明还提供了一种采用上述的制备方法制备得到的纳米立方体双金属硒化物材料。The invention also provides a nano-cubic bimetal selenide material prepared by the above-mentioned preparation method.
所述的纳米立方体双金属硒化物材料在钠离子电池中的应用。The application of the nanocubic bimetallic selenide material in the sodium ion battery.
所述的纳米立方体双金属硒化物材料的制备方法在制备钠离子电池产品中的应用。The preparation method of the nanocubic bimetal selenide material is applied in the preparation of sodium ion battery products.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明的工艺流程短，设备简单，制备得到的纳米立方体双金属氢氧化物材料形成了双金属硒化物微晶界，可以提供缓冲区域并有效抑制充放电过程中的体积膨胀问题，结合立方块状结构可以显著提高材料的结构稳定性，从而提高电池的循环性能和寿命。1. The process flow of the present invention is short and the equipment is simple. The prepared nanocubic bimetallic hydroxide material forms bimetallic selenide microcrystalline boundaries, which can provide a buffer area and effectively suppress the volume expansion problem during charging and discharging. The cubic block structure can significantly improve the structural stability of the material, thereby improving the cycle performance and life of the battery.
2、本发明通过引入纳米立方体双金属硒化物作为活性物质，具有很强的结构优势，可以有效提高在电池充放电过程中的结构稳定性，从而提高电池的循环稳定性，纳米结构可以有效缩短钠离子嵌入材料的距离，从而有效提高电池比容量。2. The present invention has strong structural advantages by introducing nanocubic bimetallic selenide as the active material, which can effectively improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery, and the nanostructure can be effectively shortened Sodium ions are inserted into the distance of the material, thereby effectively increasing the specific capacity of the battery.
3、本发明制备方法的原材料廉价易得、环境友好，工艺参数简单可控，便于实现技术推广，解决了现有钠离子电池的负极材料所存在的电池比容量较小、循环性能较差的问题，具有广阔的市场前景。3. The raw materials of the preparation method of the present invention are cheap and easy to obtain, environmentally friendly, and the process parameters are simple and controllable, which facilitates the realization of technology promotion, and solves the problem that the negative electrode materials of the existing sodium ion battery have a small battery specific capacity and poor cycle performance. The problem has broad market prospects.
附图说明Description of the drawings
图1为本发明实施例1制得的纳米立方体硒化锌锡的扫描电镜图。Figure 1 is a scanning electron micrograph of nanocubic zinc tin selenide prepared in Example 1 of the present invention.
图2为本发明实施例1制得的纳米立方体硒化锌锡用作钠离子电池负极材料的前两圈充放电曲线图。2 is a graph showing the first two cycles of charge and discharge curves of the nanocubic zinc tin selenide prepared in Example 1 of the present invention used as a negative electrode material for a sodium ion battery.
图3为本发明实施例1制得的纳米立方体硒化锌锡用作钠离子电池负极材料的放电比容量循环图。3 is a cycle diagram of specific discharge capacity of nanocubic zinc tin selenide prepared in Example 1 of the present invention as a negative electrode material of a sodium ion battery.
具体实施方式detailed description
下面结合附图和具体实施例对本发明作进一步详细地说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护苑围。The present invention will be further described in detail below with reference to the drawings and specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection zone of the present invention.
下面结合具体实施方式对本发明的技术方案作进一步详细地说明。The technical solution of the present invention will be described in further detail below in conjunction with specific embodiments.
实施例1Example 1
一种纳米立方体双金属硒化物材料的制备方法，步骤如下：A preparation method of nano cubic bimetal selenide material, the steps are as follows:
称取1.5g锡酸钾溶于5mL去离子水中，称取1.4g硫酸锌溶于45mL去离子水中，待充分溶解后混合，置于磁力搅拌器上在25℃下搅拌4小时后得到白色悬浊液，通过离心、水洗、醇洗后得到白色的立方块状ZnSn(OH) 6； Weigh 1.5g potassium stannate and dissolve it in 5mL deionized water, weigh 1.4g zinc sulfate and dissolve it in 45mL deionized water, mix after it is fully dissolved, place it on a magnetic stirrer and stir at 25℃ for 4 hours to obtain a white suspension Turbid liquid, after centrifugation, water washing, alcohol washing, white cubic block ZnSn(OH) 6 is obtained ;
称取1g制得的ZnSn(OH) 6和2g硒粉分别放在两个方舟中，在5％H 2/95％Ar气氛下在管式炉中煅烧处理，升温速度2℃/min，400℃保温3小时后自然冷却至室温，得到纳米立方体硒化锌锡材料，并对所述纳米立方体硒化锌锡材料进行扫描电镜表征，具体的扫描电镜图如图1所示，可以看出，制备得到的纳米立方体硒化锌锡材料颗粒均匀，且为立方体颗粒状。 Weigh 1g of the prepared ZnSn(OH) 6 and 2g of selenium powder in two arks, respectively, and calcinate in a tube furnace under a 5% H 2 /95% Ar atmosphere at a heating rate of 2°C/min, 400 After being kept at ℃ for 3 hours, it was naturally cooled to room temperature to obtain a nano cubic zinc tin selenide material, and the nano cubic zinc tin selenide material was characterized by scanning electron microscopy. The specific scanning electron microscopy diagram is shown in Fig. 1, and it can be seen that: The prepared nano cubic zinc tin selenide material particles are uniform and cubic particles.
进一步的，在本实施例中，将上述纳米立方体硒化锌锡材料作为钠离子电池负极材料进行电化学测试。具体的，采用现有技术方法将所述纳米立方体硒化锌锡材料作为负极材料制备成钠离子电池，并对其进行电化学性能测试，附图2和附图3为钠离子电池的电化学测试结果，其中，图2为本实施例制得的纳米立方体硒化锌锡用作钠离子电池负极材料的前两圈充放电曲线图，图3为本实施例制得的纳米立方体硒化锌锡用作钠离子电池负极材料的放电比容量循环图。Further, in this embodiment, the above-mentioned nanocubic zinc tin selenide material is used as a negative electrode material of a sodium ion battery for electrochemical testing. Specifically, the nano cubic zinc tin selenide material is used as the negative electrode material to prepare a sodium ion battery by using the prior art method, and the electrochemical performance test is performed on it. FIG. 2 and FIG. 3 show the electrochemistry of the sodium ion battery. Test results, among which, Figure 2 is the first two rounds of charge and discharge curves of the nanocubic zinc selenide prepared in this embodiment as the negative material of the sodium ion battery, and Figure 3 is the nano cubic zinc selenide prepared in this embodiment Cycle diagram of specific discharge capacity of tin used as a negative electrode material for sodium ion batteries.
从图2可以看出，将制备的纳米立方体硒化锌锡材料用作钠离子电池负极材料时，前两圈均能达到560mAh·g -1左右的放电比容量；从图3可以看出，制备的纳米立方体硒化锌锡材料用作钠离子电池负极材料时具有优秀的循环性能，循环至50圈时也能保持稳定的放电比容量，没有发生快速衰减。 It can be seen from Figure 2 that when the prepared nanocubic zinc tin selenide material is used as a negative electrode material for a sodium ion battery, the first two turns can reach a discharge specific capacity of about 560mAh·g -1 ; as can be seen from Figure 3, The prepared nanocubic zinc tin selenide material has excellent cycle performance when used as a negative electrode material of a sodium ion battery, and can maintain a stable discharge specific capacity when it is cycled to 50 cycles without rapid decay.
本实施例中，采用上述的制备方法制备得到的纳米立方体双金属硒化物材料具有很强的结构优势，所述的纳米立方体双金属硒化物材料可以作为钠离子电池的负极材料。In this embodiment, the nano cubic bimetal selenide material prepared by the above preparation method has strong structural advantages, and the nano cubic bimetal selenide material can be used as a negative electrode material of a sodium ion battery.
本实施例中，所述纳米立方体双金属硒化物材料的制备方法在制备钠离子电池产品中的应用。In this embodiment, the preparation method of the nanocubic bimetal selenide material is applied in the preparation of sodium ion battery products.
实施例2Example 2
一种纳米立方体双金属硒化物材料的制备方法，步骤如下：A preparation method of nano cubic bimetal selenide material, the steps are as follows:
称取1.5g硝酸铜溶于10mL去离子水中，称取1.4g硫酸锌溶于30mL去离子水中，待充分溶解后混合，置于磁力搅拌器上室温搅拌5小时后得到悬浊液，通过离心、水洗、醇洗后得到立方块状ZnCu(OH) 4； Weigh 1.5g copper nitrate and dissolve it in 10mL deionized water, weigh 1.4g zinc sulfate and dissolve it in 30mL deionized water, mix after it is fully dissolved, place it on a magnetic stirrer and stir at room temperature for 5 hours to obtain a suspension, which is centrifuged , After washing with water and alcohol, the cube-shaped ZnCu(OH) 4 is obtained ;
称取1g制得的ZnCu(OH) 4和3g硒粉分别放在两个方舟中，在5％H 2/95％Ar气氛下在管式炉中煅烧处理，升温速度5℃/min，500℃保温2小时后自然冷却至室温，得到所述纳米立方块状硒化锌铜材料，可以作为钠离子电池负极材料进行制备钠离子电池。 Weigh 1g of the prepared ZnCu(OH) 4 and 3g selenium powder in two arks respectively, and calcinate in a tube furnace under a 5% H 2 /95% Ar atmosphere at a heating rate of 5℃/min, 500 After being kept at °C for 2 hours, it is naturally cooled to room temperature to obtain the nanocubic block-shaped zinc copper selenide material, which can be used as a negative electrode material of a sodium ion battery to prepare a sodium ion battery.
实施例3Example 3
一种纳米立方体双金属硒化物材料的制备方法，步骤如下：A preparation method of nano cubic bimetal selenide material, the steps are as follows:
称取摩尔比为0.5:1的硝酸镍与硫酸锌，分别溶解在去离子水中，所述硝酸镍与硫酸锌在去离子水中的分散浓度均为0.15g·mL -1，待充分溶解后混合均匀，置于磁力搅拌器上在10℃下搅拌1小时，得到悬浊液，通过离心、水洗、醇洗后得到纳米立方体双金属氢氧化物； Weigh nickel nitrate and zinc sulfate with a molar ratio of 0.5:1 and dissolve them in deionized water. The dispersion concentration of the nickel nitrate and zinc sulfate in deionized water are both 0.15 g·mL -1 , and mix them after they are fully dissolved. Evenly, place it on a magnetic stirrer and stir at 10°C for 1 hour to obtain a suspension. After centrifugation, washing with water and alcohol washing, nanocubic double metal hydroxide is obtained;
称取纳米立方体双金属氢氧化物和二氧化硒分散在去离子水中(所述纳米立方体双金属氢氧化物和二氧化硒的摩尔比为0.001:1)，然后置于聚四氟乙烯反应釜中，加入氢氧化钠和硼氢化钠进行硒化反应，反应温度为150℃，反应时间为1小时，自然冷却至室温，得到所述纳米立方体双金属氢氧化物材料，可以作为钠离子电池负极材料进行制备钠离子电池。Weigh the nanocube double metal hydroxide and selenium dioxide and disperse them in deionized water (the molar ratio of the nanocube double metal hydroxide and selenium dioxide is 0.001:1), and then place them in a polytetrafluoroethylene reactor In the process, sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 150°C, the reaction time is 1 hour, and the reaction time is 1 hour. Naturally cool to room temperature to obtain the nanocubic double metal hydroxide material, which can be used as the negative electrode of the sodium ion battery. The materials are prepared for sodium ion batteries.
实施例4Example 4
一种纳米立方体双金属硒化物材料的制备方法，步骤如下：A preparation method of nano cubic bimetal selenide material, the steps are as follows:
称取摩尔比为1:1的氯化钴与硫酸锌，分别溶解在去离子水中，所述氯化钴与硫酸锌在去离子水中的分散浓度均为0.3g·mL -1，待充分溶解后混合均匀，置于磁力搅拌器上在50℃下搅拌24小时，得到悬浊液，通过离心、水洗、醇洗后得到纳米立方体双金属氢氧化物； Weigh cobalt chloride and zinc sulfate with a molar ratio of 1:1, and dissolve them in deionized water. The dispersion concentrations of the cobalt chloride and zinc sulfate in deionized water are both 0.3 g·mL -1 , until they are fully dissolved After mixing uniformly, place it on a magnetic stirrer and stir at 50°C for 24 hours to obtain a suspension. After centrifugation, washing with water and alcohol washing, nanocubic double metal hydroxide is obtained;
称取纳米立方体双金属氢氧化物和二氧化硒分散在去离子水中(所述纳米立方体双金 属氢氧化物和二氧化硒的摩尔比为100:1)，然后置于聚四氟乙烯反应釜中，加入氢氧化钠和硼氢化钠进行硒化反应，反应温度为300℃，反应时间为12小时，自然冷却至室温，得到所述纳米立方体双金属氢氧化物材料，可以作为钠离子电池负极材料进行制备钠离子电池。Weigh the nanocubic double metal hydroxide and selenium dioxide and disperse them in deionized water (the molar ratio of the nanocube double metal hydroxide and selenium dioxide is 100:1), and then place them in a polytetrafluoroethylene reactor In the process, sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 300°C, the reaction time is 12 hours, and the reaction time is 12 hours. The nanocubic double metal hydroxide material is obtained by natural cooling to room temperature, which can be used as the negative electrode of sodium ion battery. The materials are prepared for sodium ion batteries.
本发明有益效果如下，本发明制备的纳米立方体双金属氢氧化物材料综合了两种优势，形成的双金属硒化物微晶界可以提供缓冲区域并有效抑制充放电过程中的体积膨胀问题，结合立方块状结构可以显著提高材料的结构稳定性，从而提高电池的循环性能和寿命；而且，本发明制备的纳米立方体双金属硒化物具有很强的结构优势，有效提高了过渡金属作为钠离子电池负极材料时的电池比容量和循环寿命，可以有效提高在电池充放电过程中的结构稳定性，从而提高电池的循环稳定性，此外，本发明制备方法工艺流程短、设备简单，原材料廉价易得、环境友好，工艺参数简单可控，便于实现技术推广。The beneficial effects of the present invention are as follows. The nanocubic double metal hydroxide material prepared by the present invention combines two advantages. The formed double metal selenide microcrystalline boundary can provide a buffer area and effectively suppress the volume expansion problem during charging and discharging. The cubic block structure can significantly improve the structural stability of the material, thereby improving the cycle performance and life of the battery; moreover, the nanocubic bimetallic selenide prepared by the invention has strong structural advantages and effectively improves the transition metal as a sodium ion battery The specific capacity and cycle life of the battery in the case of the negative electrode material can effectively improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery. In addition, the preparation method of the present invention has a short process flow, simple equipment, and cheap and easy-to-obtain raw materials. , Environment-friendly, simple and controllable process parameters, easy to realize technology promotion.
需要说明的是，本发明针对当前钠离子电池负极材料所存在的可逆容量较小、循环性能较差等问题，引入纳米立方体双金属硒化物作为活性物质，其具有很强的结构优势，可以有效提高在电池充放电过程中的结构稳定性，从而提高电池的循环稳定性；纳米结构可以有效缩短钠离子嵌入材料的距离，从而有效提高电池比容量，而双金属硒化物综合了两种优势，形成的微晶界可以提供缓冲区域并有效抑制充放电过程中的体积膨胀问题，结合立方块状结构可以显著提高材料的结构稳定性，从而提高电池的循环性能和寿命，具有广阔的市场前景。It should be noted that the present invention addresses the problems of low reversible capacity and poor cycle performance of current sodium ion battery negative materials, and introduces nanocubic bimetallic selenide as the active material, which has strong structural advantages and can be effective Improve the structural stability during the charging and discharging process of the battery, thereby improving the cycle stability of the battery; the nanostructure can effectively shorten the distance of the sodium ion intercalation material, thereby effectively increasing the specific capacity of the battery, and the bimetallic selenide combines the two advantages. The formed microcrystalline boundary can provide a buffer area and effectively suppress the volume expansion problem during charging and discharging. Combined with the cubic block structure, the structural stability of the material can be significantly improved, thereby improving the cycle performance and life of the battery, and has a broad market prospect.
上面对本发明的较佳实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明的保护范围之中。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the above-mentioned embodiments. Within the scope of knowledge possessed by those of ordinary skill in the art, various implementations can be made without departing from the purpose of the present invention. Kind of change. It is unnecessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims (10)

  1. 一种纳米立方体双金属硒化物材料的制备方法，其特征在于，它包括以下步骤：A method for preparing nanocubic bimetal selenide material is characterized in that it comprises the following steps:
    1)称取摩尔比为0.5-1:1的两种不同的金属前驱体，分别溶解在去离子水中，待充分溶解后混合均匀，磁力搅拌1-24小时得到悬浊液，通过离心、水洗、醇洗后得到纳米立方体双金属氢氧化物；1) Weigh two different metal precursors with a molar ratio of 0.5-1:1, and dissolve them in deionized water. After they are fully dissolved, they are mixed uniformly, and the suspension is obtained by magnetic stirring for 1-24 hours. The suspension is obtained by centrifugation and water washing. , Obtain nanocubic double metal hydroxide after alcohol washing;
    2)称取硒源和步骤1)中得到的纳米立方体双金属氢氧化物，通过水热法或煅烧法进行硒化，得到所述的纳米立方体双金属硒化物材料；2) Weigh the selenium source and the nanocube bimetallic hydroxide obtained in step 1), and perform selenization by a hydrothermal method or a calcination method to obtain the nanocube bimetallic selenide material;
    其中，所述金属前驱体为含铜、锌、镍、钴或锡的盐酸盐、硝酸盐、硫酸盐或钾酸盐。Wherein, the metal precursor is a hydrochloride, nitrate, sulfate or potassium salt containing copper, zinc, nickel, cobalt or tin.
  2. 根据权利要求1所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，所述含铜、锌、镍、钴或锡的盐酸盐、硝酸盐、硫酸盐或钾酸盐为锡酸钾、硫酸锌、硝酸铜、硝酸镍或氯化钴。The method for preparing nanocubic bimetal selenide material according to claim 1, wherein the hydrochloride, nitrate, sulfate or potassium salt containing copper, zinc, nickel, cobalt or tin is tin Potassium acid, zinc sulfate, copper nitrate, nickel nitrate or cobalt chloride.
  3. 根据权利要求2所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，步骤1)中，所述金属前驱体在去离子水中的分散浓度为0.15-0.3g·mL -1。 The method for preparing nanocube bimetallic selenide material according to claim 2, wherein in step 1), the dispersion concentration of the metal precursor in deionized water is 0.15-0.3 g·mL -1 .
  4. 根据权利要求2所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，步骤1)中，所述磁力搅拌的温度为10-50℃。The method for preparing nanocubic bimetal selenide material according to claim 2, wherein in step 1), the temperature of the magnetic stirring is 10-50°C.
  5. 根据权利要求1-4任一所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，步骤2)中，所述硒源为硒粉或二氧化硒。The method for preparing a nanocubic bimetallic selenide material according to any one of claims 1 to 4, wherein in step 2), the selenium source is selenium powder or selenium dioxide.
  6. 根据权利要求5所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，步骤2)中，所述纳米立方体双金属氢氧化物和硒源的摩尔比为0.001-100:1。The preparation method of nanocube bimetallic selenide material according to claim 5, wherein in step 2), the molar ratio of the nanocube bimetallic hydroxide to the selenium source is 0.001-100:1.
  7. 根据权利要求6所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，步骤2)中，所述水热法硒化的条件为：将纳米立方体双金属氢氧化物和硒源分散在去离子水中，然后置于聚四氟乙烯反应釜中，加入氢氧化钠和硼氢化钠进行硒化反应，反应温度为150-300℃，反应时间为1-12小时。The method for preparing nanocubic bimetallic selenide material according to claim 6, wherein in step 2), the condition of the hydrothermal selenization is: dispersing the nanocube bimetallic hydroxide and the selenium source In deionized water, then placed in a polytetrafluoroethylene reactor, sodium hydroxide and sodium borohydride are added to carry out the selenization reaction, the reaction temperature is 150-300°C, and the reaction time is 1-12 hours.
  8. 根据权利要求6所述的纳米立方体双金属硒化物材料的制备方法，其特征在于，步骤2)中，所述煅烧法硒化的条件为：将纳米立方体双金属氢氧化物和硒源分别置于不同的容器中，共同在氢气/氩气的气氛下进行煅烧，所述煅烧的升温速度为1-10℃/min，所述煅 烧的温度300-800℃，所述煅烧的保温时间为1-5小时。The method for preparing nanocube bimetallic selenide material according to claim 6, wherein in step 2), the condition of the calcining method for selenization is: separately placing the nanocube bimetallic hydroxide and the selenium source In different containers, the calcination is carried out together in a hydrogen/argon atmosphere, the heating rate of the calcination is 1-10°C/min, the temperature of the calcination is 300-800°C, and the holding time of the calcination is 1 -5 hours.
  9. 一种由权利要求1-8任一所述的方法制备得到的纳米立方体双金属硒化物材料。A nanocubic bimetal selenide material prepared by the method of any one of claims 1-8.
  10. 一种如权利要求9所述的纳米立方体双金属硒化物材料在钠离子电池中的应用。An application of the nanocubic bimetallic selenide material according to claim 9 in a sodium ion battery.
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