WO2023045336A1 - 一种中空纳米硒化物及其制备方法和应用 - Google Patents

一种中空纳米硒化物及其制备方法和应用 Download PDF

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WO2023045336A1
WO2023045336A1 PCT/CN2022/090535 CN2022090535W WO2023045336A1 WO 2023045336 A1 WO2023045336 A1 WO 2023045336A1 CN 2022090535 W CN2022090535 W CN 2022090535W WO 2023045336 A1 WO2023045336 A1 WO 2023045336A1
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sodium
preparation
selenide
pba
cobalt
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French (fr)
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盛天都
李长东
刘勇奇
曹凯峰
刘芳凌
彭海龙
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Guangdong Brunp Recycling Technology Co Ltd
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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
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative 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 invention relates to the technical field of selenides and sodium ion batteries, in particular to a hollow nano-selenide and its preparation method and application.
  • sodium-ion working battery and lithium-ion working battery have very similar energy storage theory, because sodium resource reserves are very abundant and the price is very cheap, sodium-ion battery is considered to be an energy storage technology with broad application and development prospects, the most fundamental challenge is to find suitable sodium-ion electrode materials for efficient energy storage.
  • lithium and lithium have similar physical and chemical properties
  • most materials suitable for lithium-ion working batteries cannot be directly applied to sodium-ion batteries because the effective radius of sodium ions is larger than that of lithium ions.
  • high-capacity anode materials that can be used in lithium-ion batteries and sodium-ion batteries include simple metals, alloys, cobalt-based metal oxides, and transition metal selenium compounds.
  • Cobalt-based metal oxides and transition metal selenium compounds have attracted great attention due to their robust structure, low cost, facile preparation, and high theoretical capacity.
  • transition metal selenides undergo significant volume changes and slow reaction kinetics during charge and discharge, resulting in a rapid capacity drop.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. Therefore, the present invention provides a hollow nano-selenide and its preparation method and application.
  • the hollow nano-selenide can improve the cycle life and rate performance of electrode materials.
  • the present invention adopts the following technical solutions:
  • a hollow nano-selenide whose chemical formula is M-CoSe 2 , wherein M is one of Cu, Ag, and Au.
  • the specific surface area of the hollow nano-selenide is 42.5-46.5m 2 /g.
  • a preparation method of hollow nano-selenide comprising the following steps:
  • the cobalt salt is at least one of cobalt acetate, cobalt nitrate, cobalt carbonate or cobalt sulfate.
  • the cobalt salt is cobalt acetate.
  • the concentration of the cobalt acetate is 0.6-0.8 mmol.
  • the concentration of the sodium citrate is 0.9-1.0 mmol.
  • the mass ratio of the cobalt salt to sodium citrate is (1-2):3.
  • the hexacyanocobaltate is one of potassium hexacyanocobaltate and sodium hexacyanocobaltate.
  • the hexacyanocobaltate is potassium hexacyanocobaltate.
  • the concentration of the potassium hexacyanocobaltate is 0.4-0.6 mmol.
  • step (1) after adding the hexacyanocobaltate and mixing the reaction, the precipitate obtained from the reaction is subjected to standing aging; the standing time is 20-30 hours.
  • the organic solvent is absolute ethanol.
  • the lye is one of ammonia water and sodium hydroxide solution.
  • the lye is ammonia water.
  • the reducing agent is one of sodium borohydride and hydrazine hydrate.
  • the reducing agent is hydrazine hydrate.
  • the temperature of the hydrothermal reaction is 120-180°C, and the time of the hydrothermal reaction is 4-8h.
  • step (4) after the solid-liquid separation, drying the solid phase is also included, the drying temperature is 60-80°C, and the drying time is 12-20h.
  • the hydrogen selenate is one of sodium selenide and potassium selenide.
  • the hydrogen selenate is sodium selenide.
  • the heavy metal salt is one of copper nitrate and silver nitrate.
  • the heavy metal in the heavy metal salt is Cu.
  • the invention provides a negative electrode of a sodium ion battery, comprising the hollow nano-selenide.
  • the present invention prepares nanomaterials with a hollow structure whose morphology can be controlled by methods such as template method and etching, specifically as follows: firstly, after reacting Co-like Prussian blue analogues, standing and aging to obtain Co-Co PBA nanocubes, Then use lye (ammonia) to etch to obtain Co-Co NFS nanocubes, and then perform anion exchange reaction with Se 2- ions to transform into layered and hollow CoSe 2 nanocubes; finally use metal ions (copper, gold, silver) In the cation exchange reaction of CoSe2 nanocubes, metal ions (copper, gold, silver) were doped into CoSe2 nanocubes to obtain M- CoSe2 nanocubes.
  • template method and etching specifically as follows: firstly, after reacting Co-like Prussian blue analogues, standing and aging to obtain Co-Co PBA nanocubes, Then use lye (ammonia) to etch to obtain Co-
  • the M- CoSe2 nanocube prepared in the present invention combines the advantages of hollow nanostructure and metal ion doping, and can be applied to sodium ion batteries to enhance the sodium storage performance. Since the hollow interior can effectively adapt to the volume expansion changes during the intercalation and desodiation process, and the nanocube structure can expand the contact area between the electrode and the electrolyte to improve the electrochemical kinetic performance, it has excellent sodium storage performance.
  • the hollow nano selenide is firstly prepared, and then metal ions are doped to improve the cycle life and rate performance of the electrode material.
  • the electrochemical performance test results show that at a current density of 0.1A g -1 , the specific capacity after 100 cycles is 450mA h g -1 , and the effective capacity retention rate is 90.0%.
  • the present invention obtains M-CoSe 2 nanocubes, which have hollow nanostructures with unique structures, and the surface area can reach more than 42.5 m 2 g -1 .
  • Fig. 1 is the XRD pattern of (a) Co-Co PBA and Co-Co PBA NFS nano cube of Example 1 of the present invention, the SEM figure of (b-c) Co-Co PBA nano cube, (d-g) Co-Co PBA NFS nano SEM images of cubes, TEM images of (h-k) Co-Co PBA NFS nanocubes;
  • Fig. 2 is the SEM picture of (ab) CoSe 2 nanocube of the embodiment 1 of the present invention, the SEM picture of (cd) Cu-CoSe 2 nanocube, the XRD figure of (e) CoSe 2 nanocube, (f) Cu-CoSe XRD patterns of 2nm cubes;
  • Fig. 3 is the TEM figure of (ab) Cu-CoSe 2 nano cubes of embodiment 1, (c) the mapping figure of Cu, Co and Se element in the Cu-CoSe 2 of embodiment 1;
  • (a) of Fig. 4 is Cu-CoSe 2 nano-cube material of embodiment 1 and the CoSe 2 nano-cube material of comparative example 1 under the charge-discharge curve of 0.1Ag -1 electric current density;
  • (b) is the Cu-CoSe of embodiment 1 The rate performance of CoSe 2 nanocube material and the CoSe 2 nanocube material of Comparative Example 1 at a current density of 0.1-2A g -1 ;
  • (c) is the Cu-CoSe 2 nanocube material of Example 1 and the CoSe of Comparative Example 1 Cycling stability of 2 nanocube materials at a current density of 0.1 A g -1 .
  • Embodiment 1 the preparation of hollow nano-selenide
  • the hollow nano-selenide compound of this embodiment has a chemical formula of Cu—CoSe 2 .
  • Co-Co PBA nanocubes Dissolve 0.6mmol of cobalt acetate and 0.9mmol of sodium citrate in 20mL of deionized water as chemical solution A, and then add 0.4mmol of potassium hexacyanocobaltate Dissolve in 20mL of deionized water, as chemical solution B, mix chemical solution A and chemical solution B with magnetic force for 3min, and let stand at room temperature for 20h, centrifuge, collect precipitate, wash with deionized water and ethanol, in Dry in a vacuum oven at 60 °C for 24 h to obtain Co-Co PBA nanocubes.
  • Co-Co PBA NFS nanocubes 20 mg of Co-Co PBA powder was dissolved in 10 mL of absolute ethanol to obtain A chemical solution, and 20 mL of deionized water was poured into 5 mL with a mass fraction of 28% Ammonia water to obtain chemical solution B, mix chemical solution A and chemical solution B, and mix under magnetic stirring for 10 minutes, centrifuge, collect the precipitate, wash with deionized water and absolute ethanol, and then vacuum dry in a vacuum oven at 60°C for 24 hours. Get Co-Co PBA NFS nanocubes.
  • the Cu-CoSe 2 nanocubes prepared in this example have a specific surface area of 45.2 m 2 g -1 .
  • Embodiment 2 the preparation of hollow nano-selenide
  • the hollow nano-selenide compound of this embodiment has a chemical formula of Cu—CoSe 2 .
  • Co-Co PBA nanocubes Dissolve 0.6mmol of cobalt acetate and 0.9mmol of sodium citrate in 20mL of deionized water as chemical solution A, and then add 0.4mmol of potassium hexacyanocobaltate Dissolve in 20mL of deionized water, as chemical solution B, mix chemical solution A and chemical solution B with magnetic force for 3min, and let stand at room temperature for 20h, centrifuge, collect precipitate, wash with deionized water and ethanol, in Dry in a vacuum oven at 60 °C for 24 h to obtain Co-Co PBA nanocubes.
  • Co-Co PBA NFS nanocubes 20 mg of Co-Co PBA powder was dissolved in 10 mL of absolute ethanol to obtain A chemical solution, and 20 mL of deionized water was poured into 5 mL with a mass fraction of 30% Ammonia water to obtain chemical solution B, mix chemical solution A and chemical solution B, and mix under magnetic stirring for 10 minutes, centrifuge, collect the precipitate, wash with deionized water and absolute ethanol, and then vacuum dry in a vacuum oven at 60°C for 24 hours. Get Co-Co PBA NFS nanocubes.
  • the Cu-CoSe 2 nanocubes prepared in this example have a specific surface area of 42.5 m 2 g -1 .
  • Embodiment 3 the preparation of hollow nano-selenide
  • the hollow nano-selenide compound of this embodiment has a chemical formula of Cu—CoSe 2 .
  • Co-Co PBA nanocubes Dissolve 0.6mmol of cobalt acetate and 0.9mmol of sodium citrate in 20mL of deionized water as chemical solution A, and then add 0.4mmol of potassium hexacyanocobaltate Dissolve in 20mL of deionized water, as chemical solution B, mix chemical solution A and chemical solution B with magnetic force for 3min, and let stand at room temperature for 20h, centrifuge, collect precipitate, wash with deionized water and ethanol, in Dry in a vacuum oven at 60 °C for 24 h to obtain Co-Co PBA nanocubes.
  • Co-Co PBA NFS nanocubes 20 mg of Co-Co PBA powder was dissolved in 10 mL of absolute ethanol to obtain A chemical solution, and 20 mL of deionized water was poured into 5 mL with a mass fraction of 30% Ammonia water to obtain chemical solution B, mix chemical solution A and chemical solution B, and mix under magnetic stirring for 10 minutes, centrifuge, collect the precipitate, wash with deionized water and absolute ethanol, and then vacuum dry in a vacuum oven at 60°C for 24 hours. Get Co-Co PBA NFS nanocubes.
  • the Cu-CoSe 2 nanocubes prepared in this example have a specific surface area of 43.7 m 2 g -1 .
  • Embodiment 4 the preparation of hollow nano-selenide
  • the hollow nano-selenide compound of this embodiment has a chemical formula of Ag-CoSe 2 .
  • Co-Co PBA nanocubes Dissolve 0.6mmol of cobalt acetate and 0.9mmol of sodium citrate in 20mL of deionized water as chemical solution A, and then add 0.4mmol of potassium hexacyanocobaltate Dissolve in 20mL of deionized water, as chemical solution B, mix chemical solution A and chemical solution B with magnetic force for 3min, and let stand at room temperature for 20h, centrifuge, collect precipitate, wash with deionized water and ethanol, in Dry in a vacuum oven at 60 °C for 24 h to obtain Co-Co PBA nanocubes.
  • Co-Co PBA NFS nanocubes 20 mg of Co-Co PBA powder was dissolved in 10 mL of absolute ethanol to obtain A chemical solution, and 20 mL of deionized water was poured into 5 mL with a mass fraction of 30% Ammonia water to obtain chemical solution B, mix chemical solution A and chemical solution B, and mix under magnetic stirring for 10 minutes, centrifuge, collect the precipitate, wash with deionized water and absolute ethanol, and then vacuum dry in a vacuum oven at 60°C for 24 hours. Get Co-Co PBA NFS nanocubes.
  • the specific surface area of the Ag-CoSe 2 nanocubes prepared in this example is 44.9 m 2 g -1 .
  • the preparation method of the hollow nano-selenide of this comparative example comprises the following steps:
  • Fig. 1 is the XRD picture of (a) Co-Co PBA and Co-Co PBA NFS nano cube of Example 1 of the present invention, (bc) SEM picture of Co-Co PBA nano cube, (dg) Co-Co PBA NFS nano cube The SEM image of cube, the TEM image of (hk) Co-Co PBA NFS nano cube; From the information that can be drawn from Fig. XRD characterization test, all the diffraction peaks corresponding to Figure 1(a) are the same as the diffraction peaks of the standard card Co 3 [Co(CN) 6 ] 2 (JCPDS no 77-1161), it can be concluded that the synthesis of this material is successful .
  • the Co-Co PBA NFS nanocubes also showed uniform and unique hollow structures,
  • the nanoframes are uniformly distributed and have a smooth surface, and the corners of the nanocubes expose more defects than the flat surfaces, so in this structure, the Co-Co PBA NFS nanocubes are etched at eight corners first.
  • the nanocube morphology of Co-Co PBA NFS was also identified by TEM imaging, as shown in Figure 1(hk), the thickness of the edge of the Co-Co PBA NFS nanocube is about 80 nm, and the XRD pattern of the Co-Co PBA NFS nanocube shows The peaks of are identical to those of the Co-Co PBA nanocubes, demonstrating that there is no change in the crystalline phase during the chemical etching step.
  • Fig. 2 is the SEM picture of (ab) CoSe 2 nanocube of the embodiment 1 of the present invention, the SEM picture of (cd) Cu-CoSe 2 nanocube, the XRD figure of (e) CoSe 2 nanocube, (f) Cu-CoSe XRD pattern of 2 nanocubes; information that can be drawn from Figure 2:
  • the typical SEM image of the obtained CoSe 2 nanocube products is shown in Figure 2(a), which still retains the cubic morphology of the Co-Co PBA precursor and Size, but the surface is very rough, and many small nanoparticles appear, which may be some residual impurities.
  • the magnified SEM image of a single CoSe2 nanocube is shown in Fig.
  • the shell is composed of randomly assembled ultrathin nanosheets.
  • the SEM image of Cu-CoSe 2 nanocubes is shown in Fig. 2(cd), the structural morphology of CoSe 2 nanocubes is well maintained after doping Cu 2+ ions, and the hollow interior, hollow
  • the structure can be such that there is enough volume to support the volume expansion caused by the intercalation/extraction of sodium ions.
  • Fig. 3 is the TEM figure of (ab) Cu-CoSe 2 nano cube of embodiment 1, (c) the mapping figure of Cu, Co and Se element in the Cu-CoSe 2 of embodiment 1; From the information that can draw from Fig. 3 : TEM images of Cu- CoSe2 nanocubes are shown in Fig . 3(ab). Cu- CoSe2 nanocubes inherit the layered hollow structure of CoSe2 nanocubes. In 3a), it can be observed that the thickness is about 250 nm, and the structure with inner hollow can be clearly identified in the nanocube from the TEM image. The evolution of the hollow structure can be attributed to the diffusion effect.
  • Se 2- ions firstly react with cobalt ions to form a CoSe 2 thin layer, which is equivalent to a physical barrier that hinders the external Se 2- ions Chemical reaction with internal cobalt ions. Due to the small size of Co ions, the outward diffusion of Co ions is dominant compared with the inward diffusion of Se ions . The result is that the selenization reaction mainly occurs on the preformed CoSe2 shell, which eventually forms an inner hollow structure. The uniform distribution of Cu, Co, and Se elements was confirmed as shown in Fig. 3(c).
  • the electrochemical performance diagram is shown in Fig. 4 ((a) is the Cu-CoSe nano cube material of embodiment 1 and the CoSe nano cube material of comparative example 1 under 0.1Ag - 1 current density charge-discharge curve; (b) embodiment The rate performance of the Cu- CoSe2 nanocube material of 1 and the CoSe2 nanocube material of Comparative Example 1 at a current density of 0.1-2A g - 1; (c) the Cu- CoSe2 nanocube material of Example 1 and the comparative example 1 CoSe 2 nanocube material cycle stability at 0.1A g -1 current density) as shown in the electrochemical performance test of embodiment 1 after 100 cycles at a current density of 0.1A g -1
  • the specific capacity is 450mA h g ⁇ 1 , when the current density was 0.1 A g ⁇ 1 , a capacity retention of 90% was observed after 100 cycles.
  • the rate capability is that when the current density is 0.1, 0.2, 0.5, and 1A g -1 , the discharge capacities of Cu-CoSe 2 nanocubes are 470, 464, 448, and 407mAh g -1 , respectively. Even at a large current density of 2A g -1 , the Cu- CoSe2 nanocubes can still provide an excellent specific capacity of 387 mA h g -1 , which demonstrates the excellent specific capacity of the Cu- CoSe2 nanocube electrodes. In stark contrast, the specific capacity of CoSe 2 nanocubes without Cu doping in Comparative Example 1 will drop rapidly at high current density, and the capacity of CoSe 2 nanocubes without Cu doping after 80 cycles is rapid decline.

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Abstract

属于硒化物及钠离子电池技术领域，公开一种中空纳米硒化物及其制备方法和应用，中空纳米硒化物的化学式为M-CoSe 2，M为Cu、Ag、Au中的一种。M-CoSe 2纳米立方体结合中空纳米结构和金属离子掺杂的优势，应用于钠离子电池可显示出优异的钠储存性能。由于中空内部可以有效地适应在嵌钠和脱钠过程中的体积膨胀变化，而构造纳米立方体可以在电极和电解质之间扩大接触面积改善了电化学动力学性能，因而具有优异的钠存储性能。

Description

一种中空纳米硒化物及其制备方法和应用 技术领域
本发明涉及硒化物及钠离子电池技术领域，特别是涉及一种中空纳米硒化物及其制备方法和应用。
背景技术
钠离子工作电池与锂离子工作电池具有十分相似的储能理论，因为钠资源储量非常丰富并且价格也十分便宜，钠离子电池被认为是一种应用发展前景辽阔的能源储存技术，最根本的挑战是找到适合用于高效储能的钠离子电极材料。
虽然钠与锂具有相似的理化性质，但是由于钠离子有效半径大于锂离子有效半径，大部分适合于锂离子工作电池的材料不能直接推广应用在钠离子电池。迄今为止，在现有负极材料中，既能用于锂离子电池，又能直接被用于钠离子电池的高容量负极材料包括简单金属、合金、钴基金属氧化物和过渡金属硒元素化合物。钴基金属氧化物和过渡金属硒元素化合物因其结构坚固、成本低、制备简单和理论容量高等特点引起了极大的关注。然而，过渡金属硒化物在充放电过程中体积变化明显，反应动力学缓慢，导致容量迅速下降。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提供一种中空纳米硒化物及其制备方法和应用，该中空纳米硒化物可以提高电极材料的循环寿命和倍率性能。
为实现上述目的，本发明采用以下技术方案：
一种中空纳米硒化物，其化学式为M-CoSe 2，所述M为Cu、Ag、Au中的一种。
优选地，所述中空纳米硒化物的比表面积为42.5-46.5m 2/g。
一种中空纳米硒化物的制备方法，包括以下步骤：
(1)将钴盐、柠檬酸钠、六氰基钴酸盐在水存在下反应，固液分离，得到钴普鲁士蓝类似物Co-Co PBA纳米立方体；
(2)将所述钴普鲁士蓝类似物Co-Co PBA纳米立方体溶于有机溶剂中，再加入碱 液，沉淀反应，固液分离，得到钴普鲁士蓝类似物Co-Co PBA NFS纳米立方体；
(3)将所述钴普鲁士蓝类似物Co-Co PBA NFS纳米立方体和氢硒酸盐混合，再加入还原剂，进行水热反应，固液分离，得到CoSe 2纳米立方体；
(4)将所述CoSe 2纳米立方体和重金属盐溶于有机溶剂中，进行水热反应，固液分离，得到Cu-CoSe 2纳米立方体；所述重金属盐中的重金属为Cu、Ag、Au中的至少一种。
优选地，步骤(1)中，所述钴盐为乙酸钴、硝酸钴、碳酸钴或硫酸钴中的至少一种。
进一步优选地，所述钴盐为乙酸钴。
更优选地，所述乙酸钴的浓度为0.6-0.8mmol。
优选地，步骤(1)中，所述柠檬酸钠的浓度为0.9-1.0mmol。
优选地，步骤(1)中，所述钴盐和柠檬酸钠的质量比为(1-2)：3。
优选地，步骤(1)中，所述六氰基钴酸盐为六氰基钴酸钾、六氰基钴酸钠中的一种。
进一步优选地，所述六氰基钴酸盐为六氰基钴酸钾。
更优选地，所述六氰基钴酸钾的浓度为0.4-0.6mmol。
优选地，步骤(1)中，所述加入六氰基钴酸盐混合反应后还包括将反应所得沉淀物进行静置老化；所述静置时间为20-30h。
优选地，步骤(2)和步骤(4)中，所述有机溶剂为无水乙醇。
优选地，步骤(2)中，所述碱液为氨水、氢氧化钠溶液中的一种。
进一步优选地，所述碱液为氨水。
优选地，步骤(3)中，所述钴普鲁士蓝类似物Co-Co PBA NFS纳米立方体和氢硒酸盐的质量比为(1.5-2)：(6-8)。
优选地，步骤(3)中，所述还原剂为硼氢化钠、水合肼中的一种。
进一步优选地，所述还原剂为水合肼。
优选地，步骤(4)中，所述水热反应的温度为120-180℃，水热反应的时间为4-8h。
优选地，步骤(4)中，所述固液分离后还包括将固相进行干燥，所述干燥的温度 为60-80℃，干燥的时间为12-20h。
优选地，步骤(4)中，所述氢硒酸盐为硒化钠、硒化钾中的一种。
更优选地，所述氢硒酸盐为硒化钠。
优选地，步骤(4)中，所述重金属盐为硝酸铜、硝酸银中的一种。
进一步优选地，所述重金属盐中的重金属为Cu。
本发明提供一种钠离子电池负极，包括所述的中空纳米硒化物。
本发明还提供一种钠离子电池，包括所述的钠离子电池负极。
反应方程式：
K 4[Co(CN) 6]+4Co(AC) 3→Co 4[Co(CN) 6] 3+4K(AC) 3；
Na 2SeO 3+N 2H 4·H 2O→N 2+Na 2Se+3H 2O；
Co 4[Co(CN) 6] 3+Na 2Se→CoSe 2+NaCN；
CoSe 2+Cu(NO 3) 2·3H 2O→Cu-CoSe 2+Co(NO 3) 2+3H 2O。
本发明的制备原理：
本发明通过模板法、刻蚀等方法制备具有可以控制形貌的中空结构的纳米材料，具体如下：首先，将Co类普鲁士蓝类似物反应后，静置老化，得到Co-Co PBA纳米立方体，再利用碱液(氨水)刻蚀，获得Co-Co NFS纳米立方体，之后与Se 2-离子进行阴离子交换反应，转变成分层中空的CoSe 2纳米立方体；最后利用金属离子(铜、金、银)的阳离子交换反应，在CoSe 2纳米立方体中掺入金属离子(铜、金、银)，得到M-CoSe 2纳米立方体。
本发明的有益效果如下：
(1)本发明制备的M-CoSe 2纳米立方体结合中空纳米结构和金属离子掺杂的优势，应用于钠离子电池可以增强的钠储存性能。由于中空内部可以有效地适应在嵌钠和脱钠过程中的体积膨胀变化，而构造纳米立方体可以在电极和电解质之间扩大接触面积改善了电化学动力学性能，因而具有优异的钠存储性能。本发明先制备中空纳米硒化物，再掺杂金属离子提高电极材料的循环寿命和倍率性能。电化学性能测试结果显示，在0.1A g -1的电流密度下，经过循环100圈后的比容量为450mA h g -1，其有效容量保持率为90.0％。
(2)本发明得到M-CoSe 2纳米立方体，其具有独特结构的中空纳米结构，表面积 可达42.5m 2g -1以上。
(3)本发明的制备方法简单(模板法、刻蚀、离子交换等)，原料易获得，通过控制刻蚀时间(刻蚀时间范围优选为5-30min)可以调控不同形貌的中空结构的纳米材料，所制备的形貌独特、新奇，具有很好的电化学性能。而且本发明采用的模板法不仅可以应用于硒基体系中，也能够应用于其它体系(S基体系)中，适用性十分广泛，因而对于钠离子电池负极材料的研究具有现实意义。
附图说明
图1为本发明实施例1的(a)Co-Co PBA和Co-Co PBA NFS纳米立方体的XRD图，(b-c)Co-Co PBA纳米立方体的SEM图，(d-g)Co-Co PBA NFS纳米立方体的SEM图，(h-k)Co-Co PBA NFS纳米立方体的TEM图；
图2为本发明实施例1的(a-b)CoSe 2纳米立方体的SEM图，(c-d)Cu-CoSe 2纳米立方体的SEM图，(e)CoSe 2纳米立方体的XRD图，(f)Cu-CoSe 2纳米立方体的XRD图；
图3为实施例1的(a-b)Cu-CoSe 2纳米立方体的TEM图，(c)实施例1的Cu-CoSe 2中Cu、Co和Se元素的mapping图；
图4的(a)为实施例1的Cu-CoSe 2纳米立方体材料和对比例1的CoSe 2纳米立方体材料在0.1Ag -1电流密度下充放电曲线；(b)为实施例1的Cu-CoSe 2纳米立方体材料和对比例1的CoSe 2纳米立方体材料在0.1-2A g -1电流密度下的倍率性能；(c)为实施例1的Cu-CoSe 2纳米立方体材料和对比例1的CoSe 2纳米立方体材料在0.1A g -1电流密度下循环稳定性。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1：中空纳米硒化物的制备
本实施例的中空纳米硒化物，其化学式为Cu-CoSe 2。
本实施例的中空纳米硒化物的制备方法，包括以下步骤：
(1)Co-Co PBA纳米立方体的制备：将0.6mmol的乙酸钴与0.9mmol的柠檬酸钠溶解在20mL的去离子水里，作为A化学溶液，再将0.4mmol的六氰基钴酸钾溶解在 20mL的去离子水里，作为B化学溶液，把A化学溶液和B化学溶液混合磁力搅拌3min，并在室温下静置20h，离心，收集沉淀物，用去离子水与乙醇洗涤，在真空烘箱里于60℃干燥24h，得到Co-Co PBA纳米立方体。
(2)Co-Co PBA NFS纳米立方体的制备：将20mg的Co-Co PBA粉末溶于10mL的无水乙醇中得到A化学溶液，并且将20mL的去离子水倒入5mL的质量分数为28％氨水得到B化学溶液，把化学溶液A与化学溶液B混合，并在磁力搅拌下混合10min，离心，收集沉淀物，用去离子水与无水乙醇洗涤，再在真空烘箱60℃真空干燥24h，得到Co-Co PBA NFS纳米立方体。
(3)CoSe 2纳米立方体的制备：称量7.5mgCo-Co PBA NFs粉末溶于10mL去离子水中得到A溶液，然后称重30mg硒化钠并溶于且溶于10mL去离子水得到B化学溶液，把A化学溶液和B化学溶液混合，再加入0.8mL水合肼(N 2H 4·2H 2O)搅拌10min后转移到水热反应釜里，并且置于120℃的水热反应炉里放置加热处理4h，反应结束完成后用去离子水与乙醇洗涤，离心收集整理黑色沉淀物，最终在60℃真空干燥12h，得到CoSe 2纳米立方体。
(4)Cu-CoSe 2纳米立方体的制备：称量15mgCoSe 2和50mg三水硝酸铜溶于20mL无水乙醇后，转移到水热反应釜里，并且置于120℃的水热反应炉里并且加热处理4h，用乙醇与去离子水洗涤，离心收集沉淀物，最后置于60℃的真空干燥箱中并真空干燥12h，得到Cu-CoSe 2纳米立方体。
本实施例制备的Cu-CoSe 2纳米立方体的比表面积为45.2m 2g -1。
实施例2：中空纳米硒化物的制备
本实施例的中空纳米硒化物，其化学式为Cu-CoSe 2。
本实施例的中空纳米硒化物的制备方法，包括以下步骤：
(1)Co-Co PBA纳米立方体的制备：将0.6mmol的乙酸钴与0.9mmol的柠檬酸钠溶解在20mL的去离子水里，作为A化学溶液，再将0.4mmol的六氰基钴酸钾溶解在20mL的去离子水里，作为B化学溶液，把A化学溶液和B化学溶液混合磁力搅拌3min，并在室温下静置20h，离心，收集沉淀物，用去离子水与乙醇洗涤，在真空烘箱里于60℃干燥24h，得到Co-Co PBA纳米立方体。
(2)Co-Co PBA NFS纳米立方体的制备：将20mg的Co-Co PBA粉末溶于10mL的无水乙醇中得到A化学溶液，并且将20mL的去离子水倒入5mL的质量分数为30％ 氨水得到B化学溶液，把化学溶液A与化学溶液B混合，并在磁力搅拌下混合10min，离心，收集沉淀物，用去离子水与无水乙醇洗涤，再在真空烘箱60℃真空干燥24h，得到Co-Co PBA NFS纳米立方体。
(3)CoSe 2纳米立方体的制备：称量7.5mgCo-Co PBA NFs粉末溶于10mL去离子水中得到A溶液，然后称重30mg硒化钠并溶于且溶于10mL去离子水得到B化学溶液，把A化学溶液和B化学溶液混合，再加入0.8mL水合肼(N 2H 4·2H 2O)搅拌10min后转移到水热反应釜里，并且置于120℃的水热反应炉里放置加热处理4h，反应结束完成后用去离子水与乙醇洗涤，离心收集整理黑色沉淀物，最终在60℃真空干燥12h，得到CoSe 2纳米立方体。
(4)Cu-CoSe 2纳米立方体的制备：称量15mgCoSe 2和40mg三水硝酸铜溶于20mL无水乙醇后，转移到水热反应釜里，并且置于120℃的水热反应炉里并且加热处理4h，用乙醇与去离子水洗涤，离心收集沉淀物，最后置于60℃的真空干燥箱中并真空干燥12h，得到Cu-CoSe 2纳米立方体。
本实施例制备的Cu-CoSe 2纳米立方体的比表面积为42.5m 2g -1。
实施例3：中空纳米硒化物的制备
本实施例的中空纳米硒化物，其化学式为Cu-CoSe 2。
本实施例的中空纳米硒化物的制备方法，包括以下步骤：
(1)Co-Co PBA纳米立方体的制备：将0.6mmol的乙酸钴与0.9mmol的柠檬酸钠溶解在20mL的去离子水里，作为A化学溶液，再将0.4mmol的六氰基钴酸钾溶解在20mL的去离子水里，作为B化学溶液，把A化学溶液和B化学溶液混合磁力搅拌3min，并在室温下静置20h，离心，收集沉淀物，用去离子水与乙醇洗涤，在真空烘箱里于60℃干燥24h，得到Co-Co PBA纳米立方体。
(2)Co-Co PBA NFS纳米立方体的制备：将20mg的Co-Co PBA粉末溶于10mL的无水乙醇中得到A化学溶液，并且将20mL的去离子水倒入5mL的质量分数为30％氨水得到B化学溶液，把化学溶液A与化学溶液B混合，并在磁力搅拌下混合10min，离心，收集沉淀物，用去离子水与无水乙醇洗涤，再在真空烘箱60℃真空干燥24h，得到Co-Co PBA NFS纳米立方体。
(3)CoSe 2纳米立方体的制备：称量7.5mgCo-Co PBA NFs粉末溶于10mL去离子水中得到A溶液，然后称重30mg硒化钠并溶于且溶于10mL去离子水得到B化学溶 液，把A化学溶液和B化学溶液混合，再加入0.8mL水合肼(N 2H 4·2H 2O)搅拌10min后转移到水热反应釜里，并且置于120℃的水热反应炉里放置加热处理4h，反应结束完成后用去离子水与乙醇洗涤，离心收集整理黑色沉淀物，最终在60℃真空干燥12h，得到CoSe 2纳米立方体。
(4)Cu-CoSe 2纳米立方体的制备：称量15mg CoSe 2和30mg三水硝酸铜溶于20mL无水乙醇后，转移到水热反应釜里，并且置于140℃的水热反应炉里并且加热处理4h，用乙醇与去离子水洗涤，离心收集沉淀物，最后置于60℃的真空干燥箱中并真空干燥12h，得到Cu-CoSe 2纳米立方体。
本实施例制备的Cu-CoSe 2纳米立方体的比表面积为43.7m 2g -1。
实施例4：中空纳米硒化物的制备
本实施例的中空纳米硒化物，其化学式为Ag-CoSe 2。
本实施例的中空纳米硒化物的制备方法，包括以下步骤：
(1)Co-Co PBA纳米立方体的制备：将0.6mmol的乙酸钴与0.9mmol的柠檬酸钠溶解在20mL的去离子水里，作为A化学溶液，再将0.4mmol的六氰基钴酸钾溶解在20mL的去离子水里，作为B化学溶液，把A化学溶液和B化学溶液混合磁力搅拌3min，并在室温下静置20h，离心，收集沉淀物，用去离子水与乙醇洗涤，在真空烘箱里于60℃干燥24h，得到Co-Co PBA纳米立方体。
(2)Co-Co PBA NFS纳米立方体的制备：将20mg的Co-Co PBA粉末溶于10mL的无水乙醇中得到A化学溶液，并且将20mL的去离子水倒入5mL的质量分数为30％氨水得到B化学溶液，把化学溶液A与化学溶液B混合，并在磁力搅拌下混合10min，离心，收集沉淀物，用去离子水与无水乙醇洗涤，再在真空烘箱60℃真空干燥24h，得到Co-Co PBA NFS纳米立方体。
(3)CoSe 2纳米立方体的制备：称量7.5mgCo-Co PBA NFs粉末溶于10mL去离子水中得到A溶液，然后称重30mg硒化钠并溶于且溶于10mL去离子水得到B化学溶液，把A化学溶液和B化学溶液混合，再加入0.8mL水合肼(N 2H 4·2H 2O)搅拌10min后转移到水热反应釜里，并且置于120℃的水热反应炉里放置加热处理4h，反应结束完成后用去离子水与乙醇洗涤，离心收集整理黑色沉淀物，最终在60℃真空干燥12h，得到CoSe 2纳米立方体。
(4)Ag-CoSe 2纳米立方体的制备：称量15mgCoSe 2和50mg硝酸银溶于20mL无 水乙醇后，转移到水热反应釜里，并且置于120℃的水热反应炉里并且加热处理4h，用乙醇与去离子水洗涤，离心收集沉淀物，最后置于60℃的真空干燥箱中并真空干燥12h，得到Ag-CoSe 2纳米立方体。
本实施例制备的Ag-CoSe 2纳米立方体的比表面积为44.9m 2g -1。
对比例1
本对比例中空纳米硒化物的制备方法，包括以下步骤：
本对比例1与实施例1的区别在于，没有步骤(4)的金属离子掺杂。
电化学性能：
图1为本发明实施例1的(a)Co-Co PBA和Co-Co PBA NFS纳米立方体的XRD图，(b-c)Co-Co PBA纳米立方体的SEM图，(d-g)Co-Co PBA NFS纳米立方体的SEM图，(h-k)Co-Co PBA NFS纳米立方体的TEM图；从图1可得出的信息:首先通过对Co-Co PBA纳米立方体和Co-Co PBA NFS纳米立方体的晶体结构材料进行XRD表征测试，如图1(a)对应的所有衍射峰均与标准卡片Co 3[Co(CN) 6] 2(JCPDS no 77-1161)的衍射峰相同，可以得出此材料合成是成功的。用扫描电子显微镜和透射电镜研究了样品的形貌特征以及微观特征，如图1(b-c)所示，扫描电子显微镜对Co-Co PBA纳米立方体材料进行表征，结果显示Co-Co PBA纳米立方体具有高度均一性，平均尺寸约为350nm。在随后的化学蚀刻步骤中，它们被转化为Co-Co PBA NFS纳米立方体，SEM成像如图1(d-g)所示，Co-Co PBA NFS纳米立方体也显示出了均一性和独特的中空结构，纳米框架均匀分布且具有光滑的表面，纳米立方体的角要比平面暴露出更多的缺陷，所以在这种结构中，Co-Co PBA NFS纳米立方体首先在八个角处被刻蚀。Co-Co PBA NFS的纳米立方体形态也通过TEM成像得到鉴定，如图1(h-k)所示，Co-Co PBA NFS纳米立方体边缘的厚度为约80nm，Co-Co PBA NFS纳米立方体的XRD图谱显示的峰与Co-Co PBA纳米立方体的峰相同，证明了在化学蚀刻步骤中结晶相没有变化。
图2为本发明实施例1的(a-b)CoSe 2纳米立方体的SEM图，(c-d)Cu-CoSe 2纳米立方体的SEM图，(e)CoSe 2纳米立方体的XRD图，(f)Cu-CoSe 2纳米立方体的XRD图；从图2中可得出的信息：所获得CoSe 2纳米立方体产品的典型SEM图像如图2(a)所示，仍然保留了Co-Co PBA前驱体的立方体形态和尺寸，但表面非常粗糙，并出现了许多小的纳米颗粒，这可能是有些杂质残留。单个CoSe 2纳米立方体放大SEM图像如图2(b)所示，壳由随机组装的超薄纳米片组成。Cu-CoSe 2纳米立方体SEM图像如图 2(c-d)所示，掺杂Cu 2+离子后CoSe 2纳米立方体的结构形态得到了很好的维护，可以从破裂的立方体中识别出中空内部，中空结构可以使得有足够的体积支撑钠离子嵌入/脱出过程中引起的体积膨胀。Cu-CoSe 2纳米立方体和CoSe 2纳米立方体XRD表征测试如图2(e-f)所示，在水热条件下与适量的Cu 2+离子反应后，与CoSe 2纳米立方体的衍射峰相比，衍射峰变化不大。CoSe 2和Cu-CoSe 2纳米立方体的XRD精修结果表明，与CoSe 2纳米立方体相比，Cu-CoSe 2纳米立方体表现出较小的晶格膨胀，小的晶格扩展膨胀可能会导致更高的迁移率和缺陷结构，从而导致更高的电导率。
图3为实施例1的(a-b)Cu-CoSe 2纳米立方体的TEM图，(c)实施例1的Cu-CoSe 2中Cu、Co和Se元素的mapping图；从图3可得出的信息:Cu-CoSe 2纳米立方体TEM图像如图3(a-b)所示，Cu-CoSe 2纳米立方体继承了CoSe 2纳米立方体的分层空心结构，从单个Cu-CoSe 2纳米立方体的放大TEM图像(图3a)中可以观察到厚度约250nm，从TEM图像可以清楚地在纳米立方体识别出具有内部中空的结构。中空结构的演变可以归因于扩散效应具体而言，在硒化过程中，Se 2-离子首先与钴离子反应形成CoSe 2薄层，这相当于是一种物理屏障，阻碍了外部Se 2-离子与内部钴离子之间的化学反应。由于钴离子的尺寸较小，与Se 2-离子的向内扩散相比，钴离子的向外扩散占主导地位。结果就是硒化反应主要发生在预成型的CoSe 2壳上，最终形成内部中空结构。如图3(c)所示证实了Cu、Co和Se元素的均匀分布。
电化学性能图如图4((a)为实施例1的Cu-CoSe 2纳米立方体材料和对比例1的CoSe 2纳米立方体材料在0.1Ag -1电流密度下充放电曲线；(b)实施例1的Cu-CoSe 2纳米立方体材料和对比例1的CoSe 2纳米立方体材料在0.1-2A g -1电流密度下的倍率性能；(c)实施例1的Cu-CoSe 2纳米立方体材料和对比例1的CoSe 2纳米立方体材料在0.1A g -1电流密度下循环稳定性)所示，实施例1的电化学性能测试在0.1A g -1电流密度下经过100个循环后的比容量为450mA h g -1，当电流密度为0.1A g -1时，在100个循环后观察到容量保持率为90％。倍率性能则是在当电流密度分别为0.1、0.2、0.5、和1A g -1时，Cu-CoSe 2纳米立方体的放电容量分别为470、464、448和407mAh g -1。即使在2A g -1的大电流密度下，Cu-CoSe 2纳米立方体仍可提供387mA h g -1的出色比容量，这表明Cu-CoSe 2纳米立方体电极具有出色的比容量。与之形成鲜明对比的是，对比例1中无Cu掺杂的CoSe 2纳米立方体的比容量在高电流密度下会迅速下降，无Cu掺杂的CoSe 2纳米立方体的经过80个循环后容量迅速下降。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所 属技术领域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。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种中空纳米硒化物，其特征在于，所述中空纳米硒化物的化学式为M-CoSe 2，所述M为Cu、Ag、Au中的至少一种。
  2. 权利要求1所述的中空纳米硒化物的制备方法，其特征在于，包括以下步骤：
    (1)将钴盐、柠檬酸钠、六氰基钴酸盐在水存在下反应，固液分离，得到钴普鲁士蓝类似物Co-Co PBA纳米立方体；
    (2)将所述Co-Co PBA纳米立方体溶于有机溶剂中，再加入碱液，沉淀反应，固液分离，得到钴普鲁士蓝类似物Co-Co PBA NFS纳米立方体；
    (3)将所述钴普鲁士蓝类似物Co-Co PBA NFS纳米立方体和氢硒酸盐混合，再加入还原剂，进行水热反应，固液分离，得到CoSe 2纳米立方体；
    (4)将所述CoSe 2纳米立方体和重金属盐溶于有机溶剂中，进行水热反应，固液分离，得到Cu-CoSe 2纳米立方体；所述重金属盐中的重金属为Cu、Ag、Au中的至少一种。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述钴盐为乙酸钴、硝酸钴、碳酸钴或硫酸钴中的至少一种。
  4. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述钴盐和柠檬酸钠的摩尔比为(1-2)：3；进一步地，步骤(3)中，所述钴普鲁士蓝类似物Co-Co PBA NFS纳米立方体和氢硒酸盐的质量比为(1.5-2)：(6-8)。
  5. 根据权利要求2所述的制备方法，其特征在于，步骤(1)中，所述六氰基钴酸盐为六氰基钴酸钾、六氰基钴酸钠中的一种。
  6. 根据权利要求2所述的制备方法，其特征在于，步骤(2)中，所述碱液为氨水、氢氧化钠溶液中的一种。
  7. 根据权利要求2所述的制备方法，其特征在于，步骤(3)中，所述还原剂为硼氢化钠、水合肼中的一种。
  8. 根据权利要求2所述的制备方法，其特征在于，步骤(4)中，所述氢硒酸盐为硒化钠、硒化钾中的一种或两种。
  9. 一种钠离子电池负极，其特征在于，包括要求1所述的中空纳米硒化物。
  10. 一种钠离子电池，其特征在于，包括要求9所述的钠离子电池负极。
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