CN110371936B - Preparation method and application of copper selenide nanosheet array for sodium-ion battery with adjustable interlayer spacing - Google Patents

Preparation method and application of copper selenide nanosheet array for sodium-ion battery with adjustable interlayer spacing Download PDF

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CN110371936B
CN110371936B CN201910694802.XA CN201910694802A CN110371936B CN 110371936 B CN110371936 B CN 110371936B CN 201910694802 A CN201910694802 A CN 201910694802A CN 110371936 B CN110371936 B CN 110371936B
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ion battery
copper selenide
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interlayer spacing
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CN110371936A (en
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肖元化
方少明
赵晓兵
王雪兆
周立明
吴诗德
张凯扬
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Zhengzhou University of Light Industry
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01—INORGANIC CHEMISTRY
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    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/04—Binary compounds including binary selenium-tellurium compounds
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    • 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
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    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method and application of a copper selenide nanosheet array for a sodium-ion battery with adjustable interlayer spacing, wherein the copper selenide nanosheet array takes high-purity copper foil, a selenium source, sodium hydroxide, a strong reducing agent and an intercalating agent as raw materials, takes water as a solvent, and reacts for 0.5-4 h at 20-80 ℃ to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing. The invention has the outstanding characteristics that the regulation and control of the spacing of the copper selenide layers are realized at lower temperature, and the material has simple preparation method, low energy consumption and easy industrialized large-scale production; and secondly, the copper selenide nanosheet array has good arrangement consistency, controllable morphology and higher specific surface area. When the material is used as a negative electrode material of a sodium ion battery, the material has the advantages of high specific capacity, good rate capability and excellent cycle performance. Therefore, the material is expected to be widely applied to the fields of sodium ion batteries, other alkali metal ion batteries, thermoelectric materials and the like.

Description

Preparation method and application of copper selenide nanosheet array for sodium-ion battery with adjustable interlayer spacing
Technical Field
The invention relates to the field of preparation of negative electrode materials of sodium-ion batteries, in particular to a preparation method and application of a copper selenide nanosheet array for a sodium-ion battery with adjustable interlayer spacing.
Background
Energy and environment are two major problems which need to be dealt with in the current human survival and social development, and with the exhaustion of stone resources such as coal and petroleum and the gradual deterioration of the environment, the development of renewable energy sources such as solar energy, wind energy, water energy and the like becomes a global trend. With the mass access of renewable energy sources and distributed energy sources to the power grid, the energy storage battery is widely applied to the fields of power generation, power transmission and distribution and power utilization in order to overcome the characteristics of irregular and intermittent output of wind energy or solar energy power generation.
Although the lithium ion battery has the advantages of high voltage, long cycle life, small self-discharge, no memory effect and the like, the lithium ion battery has high cost (the price of a positive electrode material, electrolyte and a diaphragm is high), and meanwhile, the lithium ion battery faces the problems of lithium resource shortage, difficult recovery and the like. From the economic aspect, the high cost lithium ion battery is not suitable for the application in the large scale energy storage field. The sodium element and the lithium element have similar physicochemical properties, and have wide sources and abundant reserves, and the secondary battery system taking the related compound of sodium as the raw material has great advantages in cost, so the sodium ion battery has great application potential in the field of large-scale energy storage.
As an important component of a battery, an anode material having a high specific capacity and a long life cycle characteristic is important to improve the overall energy storage density of the battery. Negative electrode materials based on electrochemical reaction mechanisms are classified into three categories: an intercalation type, an alloying type and a transformation type.
The conversion type anode material with multi-electron reaction can provide high specific capacity, which is a very promising material for sodium ion batteries. The transition metal compound can be completely reduced to a metallic state by a conversion reaction to give a material with a higher theoretical capacity than the insertion-type material. For example, Zhao Dong Yuan task group at the university of Compound Dan will highly crystallized mesoporous Fe3O4Encapsulated in N-doped hollow carbon nanospheres for high-capacity long-life sodium ion battery, and the material is at 160 mA g-1Has a current density of 372 mAh g-1And the material capacity is gradually increased and maintained at 522 mAh g after 800 cycles-1At 1200 mA g-1Capacity at current density of 196 mAh g-1And high coulombic efficiency (-100%), exhibiting excellent rate performance and cycling stability (Nano Energy, 2019, 56, 426). In addition, the reaction potential of the conversion-type anode material can be controlled by combining different transition metal cationsAnd an anionic species, which can effectively ensure the safety of the battery. At the same time, many conversion type anode materials such as Fe3O4And FeS2In its natural form, has extremely low production cost.
Although conversion-type negative electrode materials have many advantages, practical application of this type of materials still presents many challenges due to their low ion/electron conductivity, relatively large volume change of the materials during charge and discharge, and electrolyte decomposition. Low conductivity will lead to poor kinetics and reduced rate capability of the material. The large volume expansion crushes the electrode material, resulting in rapid decay of the battery capacity. In addition, electrolyte decomposition may cause an increase in the resistance of the electrode, affecting the electrochemical performance of the electrode material. Therefore, many efforts are still needed to make the conversion-type anode material a practical alternative to the sodium ion battery.
To overcome the inherent disadvantages of the conversion-type materials, researchers have adopted various optimization strategies to improve the sodium storage performance of the conversion-type cathode materials, including nanostructure design, carbon material recombination, and molecular intercalation. Hollow/pore nanostructures have proven to be a promising strategy to improve the sodium storage performance of electrodes. Li et al report mesoporous CoS @ C composites with core-shell hollow microsphere structures, with unoptimized CoS (5 cycles to 55 mAh g capacity)-1) In contrast, the CoS @ C composite was at 0.2A g-1The product still has 532 mAh g after being circulated for 100 times-1The high specific capacity of the CoS @ C composite material, the excellent electrochemical performance of the CoS @ C composite material benefits from the synergistic effect of the mesoporous CoS core and the alveolar carbon shell structure (Nano Energy, 2017, 41, 109). Carbon material compounding is another effective method for improving the electrical conductivity and mechanical stability of the electrode, and improving the rate characteristic and cycle life of the electrode. Ren et al reported the preparation of ultra-thin MoS on flexible carbon cloth2N-doped carbon nanowall composite materials derived from nanosheet @ Metal Organic Framework (MOF) and used as anode materials of sodium ion batteries show high specific capacity (at 200 mA g)-1653.9 mA h g at lower-1619.2 mA h g after 100 cycles-1) Excellent rate capability and long cycle lifeStability (at 1A g)-1After 1000 cycles, the time is 265 mA h g-1) (adv. funct. Mater, 2017, 27, 1702116). The intercalation of the surfactant can increase the interlayer spacing of the material to buffer the volume expansion of the material in the charging and discharging processes, and the larger interlayer spacing is favorable for the rapid transmission of sodium ions, so that the rate capability of the material is improved; finally, the surfactant prevents further growth of the metal particles in the conversion reaction and ensures a high cycling stability of the electrode.
Copper selenides exist in different stoichiometric forms, and their complex structure and valence states result in several unique optical and electrical properties. Copper selenide is an important p-type semiconductor and has wide potential application in the fields of solar cells, catalysis, energy storage, optical filters, nano switches, thermoelectric and photoelectric transformers, superconductors and the like. For example, research groups of Chongqing palace and Kombuxing of chemical institute of Chinese academy of sciences find that the copper selenide nano-catalyst has excellent performance in the process of producing methanol by using a carbon dioxide electrochemical reduction method, and the current density can reach 41.5 mA cm under the low overvoltage of 285 mV-2And the faraday efficiency is 77.6% (Nature Communications, 2019, 10, 677). Jiang et al used copper selenide for the first time as the cathode of an aluminum ion battery, and the copper selenide electrode showed high reversible capacity and excellent cycle stability at 200 mA g-1At a high current density, the specific discharge capacity in the initial cycle is 241 mA h g-1And maintained at 100 mA hr g after 100 cycles-1The coulombic efficiency was 96.1%, showing a good capacity retention (ACS appl. mater. Interfaces, 2018, 10, 21, 17942-17949). The problem group of professor Chen Li Dong successfully realizes the in-situ growth of Cu on the surface of CNTs by utilizing the special chemical interaction force between metallic Cu and multi-wall CNTs2Se nano crystal and assembling into a series of Cu2Se/CNTs hybrid material. Cu2The molecular CNTs highly monodisperse inside Se grain boundaries greatly reduce the lattice thermal conductivity and the carrier concentration, so that the thermoelectric figure of merit is as high as 2.4 at 1000 k (Energ. environ. Sci., 2017, 10(9): 1928-.
In addition, there are similar patents as follows: hu zhi et al (CN103449385A) synthesized cuprous selenide powder by vacuum calcination. Plum brilliant and the like (CN104016313A) adopts a hydrothermal method, and a hexagonal copper selenide nanosheet is synthesized at the hydrothermal temperature of 100-160 ℃ and the reaction time of 1-4 h. Chengang et al (CN103879974A) prepared copper selenide nanowires by microwave hydrothermal method using copper acetate, sodium selenite and the like as raw materials. Schlemmi et al (CN1889291) produced cuprous selenide thin films by reactive pulsed laser deposition and used as lithium ion battery cathodes. The preparation processes of the similar materials all involve a large amount of complex equipment with high energy consumption, have high production cost and long period and are not suitable for large-scale production. Therefore, the synthetic method which is simple and easy to implement, green and environment-friendly and can be produced in a large scale is significant to find.
Disclosure of Invention
The invention provides a preparation method of a copper selenide nanosheet array for a sodium-ion battery with adjustable interlayer spacing, which is simple in synthesis method and low in cost and can be used for large-scale industrial production. The prepared copper selenide nanosheet array for the sodium ion battery with adjustable interlayer spacing is a sodium ion battery cathode material which is stable in structure, high in specific capacity, excellent in cycling stability and high in rate capability.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a copper selenide nanosheet array for a sodium ion battery with adjustable interlayer spacing comprises the following steps:
(1) respectively treating high-purity copper foil with acetone and 1 mol L of acetone-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) Dissolving a certain amount of sodium hydroxide in an intercalation agent aqueous solution, then sequentially adding a selenium source and a strong reducing agent, and rapidly stirring at 20-80 ℃ for 10-120 min to completely dissolve the raw materials to obtain a solution A.
(3) And (2) placing the copper foil treated in the step (1) in the solution A, reacting for 0.5-4 h at the temperature of 20-80 ℃, taking out the copper foil, washing with deionized water and ethanol for multiple times, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
Further, the selenium source in the step (2) is elemental selenium powder, selenium dioxide, sodium selenite, selenious acid, selenic acid, and selenium tetrachloride.
Further, the strong reducing agent in the step (2) is hydrazine hydrate, sodium borohydride, potassium borohydride.
Further, the intercalation agent in the step (2) is cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, dodecyl dimethyl benzyl ammonium chloride or cetyl trimethyl ammonium chloride.
Further, the mass concentration of the intercalation agent molecular water solution in the step (2) is 0.001-0.05 mol L-1The amount concentration of sodium hydroxide in the mixed solution is 1-5 mol L-1The solubility of the strong reducing agent is 0.05-0.2 mol L-1The solubility of the selenium source is 0.01-0.05 mol L-1。
The copper selenide nanosheets prepared by the method are consistent in array arrangement and controllable in appearance; the thickness of the nano-sheet is 20-40 nm, and the array height is 1-4 μm.
The copper selenide nanosheet array for the sodium ion battery with the adjustable interlayer spacing, which is prepared by the preparation method, is applied to the cathode material of the sodium ion battery.
The invention has the beneficial effects that: 1. according to the invention, a copper selenide material with excellent electronic conductivity is used as a sodium ion battery cathode material, and the specific surface area and the interlayer spacing of the material are improved by combining two means of nanostructure design and intercalation of intercalation agent molecules so as to buffer the volume expansion of the material in the charging and discharging processes, and finally the sodium ion battery cathode material with excellent performance is obtained.
2. The copper selenide nanosheets have the advantages of good array consistency, controllable appearance, higher specific surface area, high electrochemical activity, contribution to embedding and removing of sodium ions, direct growth on the surface of the copper foil, no need of coating and capability of well reducing the production cost.
3. The method realizes the in-situ growth of the copper foil of the copper selenide nanosheet array and the regulation and control of the interlayer spacing at normal temperature, does not need high-temperature and high-pressure equipment of conventional hydrothermal reaction, has simple preparation method, short reaction time and almost no energy consumption, is easy for industrial large-scale production, and has the advantages of relative greenness and economy.
4. The preparation process of the copper selenide nanosheet array is simple to operate, high in yield, low in cost, environment-friendly, high in charging and discharging specific capacity of the sodium ion battery, good in cycling stability and excellent in rate capability. The obtained sodium ion battery was used as a negative electrode material of a sodium ion battery, and the obtained sodium ion battery was rated at 0.1A g-1、0.2 A g-1、0.4 A g-1、0.8 A g-1、1.0 A g-1、2.0 A g-1、5.0 A g-1、10.0 A g-1The specific capacities of the current densities of the three-phase current sensors are 432.76, 421.62, 420.37, 407.49, 403.82, 387.48, 358.74 and 320.36 mAh g-1And the high-rate performance is shown. At 2A g-1The specific capacity retention rate is 88.70 percent when the current density is tested for 500 times of cycling stability, and the excellent cycling stability is shown.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is an XRD spectrum of the copper selenide nanosheet array of example 1 of the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) of an array of copper selenide nanoplates of example 1 of the invention.
Fig. 3 is a constant current charge and discharge curve of the copper selenide nanosheet array of example 1 at different current densities.
Fig. 4 is a rate performance curve for the copper selenide nanosheet array of example 1.
Fig. 5 is a cycle stability curve for the copper selenide nanosheet array of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the copper selenide nanosheet array for the sodium-ion battery with the adjustable interlayer spacing comprises the following steps:
(1) cutting high-purity copper foil into 1 cm × 1 cm size, respectively treating with acetone and 1 mol L-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) 4 g of sodium hydroxide are dissolved in 100 ml of 0.001 mol L-1Then 0.110 g (0.001 mol) of selenium dioxide and 0.189 g (0.005 mol) of sodium borohydride are added in turn to the aqueous solution of sodium dodecyl sulfate, and the mixture is rapidly stirred at 20 ℃ for 10 min to completely dissolve the raw materials to obtain solution A.
(3) And (2) placing the copper foil treated in the step (1) in the solution A, reacting for 4 h at the temperature of 20 ℃, taking out the copper foil, washing for multiple times by using deionized water and ethanol, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
As can be seen from fig. 1, the XRD pattern of the copper selenide nanosheet array is consistent with that of standard card PDF #29-0575, and the pattern has a diffraction peak appearing at 7.6 °, and the (111) crystal plane is shifted by 5.4 ° toward a small angle direction, which is caused by the interlayer spacing expansion of the material due to intercalation of the intercalator molecules, and is the diffraction peak of the copper (PDF # 04-0836) substrate.
As can be seen in FIG. 2, the copper selenide nanosheet array is composed of 40-100 nm of sheets and is arranged in order.
From right to left in FIG. 3, 0.1A g-1、0.2 A g-1、0.4 A g-1、0.8 A g-1、1.0 A g-1、2.0 A g-1、5.0 A g-1、10.0 A g-1The charge-discharge curve was measured at the current density of (2). In the process, the charging and discharging curve is not obviously changed, which shows that the copper selenide nanosheet array has excellent stability in the application of the sodium ion battery cathode material.
Fig. 4 is a rate performance curve for the copper selenide nanosheet array of example 1. From left to right, the current density is 0.1A g-1、0.2 A g-1、0.4 A g-1、0.8 A g-1、1.0 A g-1、2.0 A g-1、5.0 A g-1、10.0 A g-1Under the condition, the measured specific discharge capacity data is 0.1A g-1Specific capacity of 432.75 mAh g under current density-1When the current density was increased to 10A g-1The specific capacity is still 320.64 mAh g-1. And at 10A g-1After five cycles at current density, when the current density was changed to 0.1A g-1And in addition, the specific capacity is hardly attenuated, and the high-power-factor high-voltage power supply has high rate performance and cycling stability.
FIG. 5 is a schematic representation at 2A g-1The initial specific capacity is 372.69 mAh g-1After 500 charge-discharge cycles, the attenuation is 329.96 mAh g-1The specific capacity retention rate was 88.53%. Exhibits ultra-long cycling stability.
The prepared copper selenide nanosheet array is used as a negative electrode material of a sodium ion battery, and 1 mol L of electrolyte-1Sodium trifluoromethanesulfonate (CF)3SO3Na) and the solvent is diethylene glycol dimethyl ether (DEGDME).
Example 2
The preparation method of the copper selenide nano-array for the sodium-ion battery with the adjustable interlayer spacing comprises the following steps:
(1) cutting high-purity copper foil into 1 cm × 1 cm size, respectively treating with acetone and 1 mol L-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) Will be provided with8 g of sodium hydroxide are dissolved in 100 ml of 0.005 mol L-1Then 0.346 g (0.002 mol) of sodium selenite and 0.378 g (0.01 mol) of sodium borohydride are added into the polyvinylpyrrolidone aqueous solution in sequence, and the mixture is rapidly stirred for 30 min at 30 ℃ to completely dissolve the raw materials to obtain solution A.
(3) And (2) placing the copper foil treated in the step (1) in the solution A, reacting for 4 h at the temperature of 30 ℃, taking out the copper foil, washing for multiple times by using deionized water and ethanol, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
In this example, the XRD pattern showed Cu2The Se (111) crystal plane is shifted by 5.6 deg. toward a small angle direction from 13.0 deg. to 7.4 deg., resulting from the expansion of the interlayer distance by surfactant intercalation, when the interlayer distance is expanded from the initial 0.68 nm to 1.2 nm. Cell assembly procedure as in example 1, at 0.1A g-1Has a specific discharge capacity of 410.68 mAh g-1At 2A g-1The capacity retention ratio was 89.2% when 500 charge-discharge cycles were performed at the current density of (1).
Example 3
The preparation method of the copper selenide nano-array for the sodium-ion battery with the adjustable interlayer spacing comprises the following steps:
(1) cutting high-purity copper foil into 1 cm × 1 cm size, respectively treating with acetone and 1 mol L-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) 10 g of sodium hydroxide are dissolved in 100 ml of 0.01 mol L-1Then 0.237 g (0.003 mol) selenium powder and 0.81 g (0.015 mol) potassium borohydride are added in sequence into the aqueous solution of sodium dodecyl benzene sulfonate, and the mixture is rapidly stirred at 40 ℃ for 60 min to completely dissolve the raw materials to obtain solution A.
(3) And (2) placing the copper foil treated in the step (1) in the solution A, reacting for 3 h at the temperature of 40 ℃, taking out the copper foil, washing for multiple times by using deionized water and ethanol, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
In this example, the XRD pattern showedCu2The Se (111) crystal plane is shifted by 5.1 deg. toward a small angle direction from 13.0 deg. to 7.9 deg., resulting from the expansion of the interlayer distance by surfactant intercalation, when the interlayer distance is expanded from the initial 0.68 nm to 1.12 nm. Cell assembly procedure as in example 1, at 0.1A g-1Has a specific discharge capacity of 422.74 mAh g-1At 2A g-1The capacity retention ratio was 85.4% when 500 charge-discharge cycles were performed at the current density of (1).
Example 4
The preparation method of the copper selenide nano-array for the sodium-ion battery with the adjustable interlayer spacing comprises the following steps:
(1) cutting high-purity copper foil into 1 cm × 1 cm size, respectively treating with acetone and 1 mol L-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) 12 g of sodium hydroxide are dissolved in 100 ml of 0.02 mol L-1Adding 0.516 g (0.004 mol) of selenious acid and 1.08 g (0.02 mol) of potassium borohydride into the dodecyl dimethyl benzyl ammonium chloride aqueous solution in sequence, and rapidly stirring the mixture at 50 ℃ for 60 min to completely dissolve the raw materials to obtain a solution A.
(3) And (2) placing the copper foil treated in the step (1) in the solution A, reacting for 2 h at the temperature of 50 ℃, taking out the copper foil, washing for multiple times by using deionized water and ethanol, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
In this example, the XRD pattern showed Cu2The Se (111) crystal plane is shifted by 4.7 deg. toward a small angle direction, from 13.0 deg. to 8.3 deg., due to the expansion of the interlayer distance caused by surfactant intercalation, when the interlayer distance is expanded from the initial 0.68 nm to 1.06 nm. Cell assembly procedure as in example 1, at 0.1A g-1Has a specific discharge capacity of 397.92 mAh g-1At 2A g-1The capacity retention ratio was 83.9% when 500 charge-discharge cycles were carried out at the current density of (1).
Example 5
(1) Cutting high-purity copper foil into 1 cm × 1 cm size, respectively treating with acetone and 1 mol L-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) 16 g of sodium hydroxide are dissolved in 100 ml of 0.05 mol L-10.725 g (0.001 mol) selenic acid and 8 ml hydrazine hydrate are added in turn into the hexadecyl trimethyl ammonium bromide aqueous solution, and the mixture is rapidly stirred for 90 min at the temperature of 60 ℃ to ensure that the raw materials are completely dissolved to obtain a solution A.
(3) And (2) placing the copper foil treated in the step (1) into the solution A, reacting for 1 h at the temperature of 60 ℃, taking out the copper foil, washing for multiple times by using deionized water and ethanol, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
In this example, the XRD pattern showed Cu2The Se (111) crystal plane is shifted by 5.5 DEG in the small angle direction from 13.0 DEG to 7.5 DEG, resulting from the expansion of the interlayer distance caused by surfactant intercalation, when the interlayer distance is expanded from the initial 0.68 nm to 1.17 nm. Cell assembly procedure as in example 1, at 0.1A g-1Has a specific discharge capacity of 427.25 mAh g-1At 2A g-1The capacity retention ratio was 87.5% when 500 charge-discharge cycles were carried out at the current density of (1).
Example 6
The preparation method of the copper selenide nano array for the sodium-ion battery with the adjustable interlayer spacing comprises the following steps:
(1) cutting high-purity copper foil into 1 cm × 1 cm size, respectively treating with acetone and 1 mol L-1And ultrasonically washing the copper foil by using a hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying the copper foil for 5 hours at the temperature of 60 ℃ in vacuum.
(2) 20 g of sodium hydroxide are dissolved in 100 ml of 0.01 mol L-1Then 1.100 g (0.005 mol) of selenium tetrachloride and 8 ml of hydrazine hydrate are added in turn, and the mixture is rapidly stirred at 60 ℃ for 120 min to completely dissolve the raw materials to obtain a solution A.
(3) And (2) placing the copper foil treated in the step (1) into the solution A, reacting for 1 h at the temperature of 60 ℃, taking out the copper foil, washing for multiple times by using deionized water and ethanol, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain the copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing.
In this example, the XRD pattern showed Cu2The Se (111) crystal plane is shifted by 5.3 deg. toward a small angle direction from 13.0 deg. to 7.7 deg., resulting from the expansion of the interlayer distance by surfactant intercalation, when the interlayer distance is expanded from the initial 0.68 nm to 1.15 nm. Cell assembly procedure as in example 1, at 0.1A g-1Has a specific discharge capacity of 415.03 mAh g-1At 2A g-1The capacity retention ratio was 86.8% when 500 charge-discharge cycles were carried out at the current density of (1).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. A preparation method of a copper selenide nanosheet array for a sodium ion battery with adjustable interlayer spacing is characterized by comprising the following steps:
(1) respectively treating high-purity copper foil with acetone and 1 mol L of acetone-1Ultrasonically washing with hydrochloric acid solution and deionized water to remove organic matters and oxides on the surface of the copper foil, and then drying for 5 hours at the temperature of 60 ℃ in vacuum;
(2) dissolving a certain amount of sodium hydroxide in an intercalation agent molecular aqueous solution, then sequentially adding a selenium source and a strong reducing agent, and rapidly stirring at 20-80 ℃ for 10-120 min to completely dissolve the raw materials to obtain a mixed solution;
(3) placing the copper foil treated in the step (1) in a mixed solution, reacting for 0.5-4 h at the temperature of 20-80 ℃, taking out the copper foil, washing with deionized water and ethanol for multiple times, and then drying for 10 h at the temperature of 60 ℃ in vacuum to obtain a copper selenide nanosheet array for the sodium-ion battery with adjustable interlayer spacing;
the intercalation agent in the step (2) is cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, dodecyl dimethyl benzyl ammonium chloride or cetyl trimethyl ammonium chloride;
the mass concentration of the intercalation agent molecular water solution in the step (2) is 0.001-0.05 mol L-1The amount concentration of sodium hydroxide in the mixed solution is 1-5 mol L-1The concentration of the strong reducing agent is 0.05-0.2 mol L-1The concentration of the selenium source is 0.01-0.05 mol L-1。
2. The method for preparing the copper selenide nano-array for the sodium-ion battery with the adjustable interlayer spacing according to claim 1, wherein the method comprises the following steps: the selenium source in the step (2) is elemental selenium powder, selenium dioxide, sodium selenite, selenious acid, selenic acid or selenium tetrachloride.
3. The preparation method of the copper selenide nanosheet array for the sodium-ion battery with the adjustable interlayer spacing according to claim 1, wherein the preparation method comprises the following steps: the strong reducing agent in the step (2) is hydrazine hydrate, sodium borohydride and potassium borohydride.
4. The preparation method of the copper selenide nanosheet array for the sodium-ion battery with the adjustable interlayer spacing according to claim 1, wherein the preparation method comprises the following steps: the prepared copper selenide nanosheets are consistent in array arrangement and controllable in appearance; the thickness of the nano-sheet is 20-40 nm, and the array height is 1-4 μm.
5. The application of the copper selenide nanosheet array for the sodium-ion battery with the adjustable interlayer spacing, which is prepared by the preparation method according to any one of claims 1 to 4, in the cathode material of the sodium-ion battery.
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