CN114927661B - Hierarchical hollow super-structure cobalt selenide nest-shaped composite material, and preparation and application thereof - Google Patents

Hierarchical hollow super-structure cobalt selenide nest-shaped composite material, and preparation and application thereof Download PDF

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CN114927661B
CN114927661B CN202210569174.4A CN202210569174A CN114927661B CN 114927661 B CN114927661 B CN 114927661B CN 202210569174 A CN202210569174 A CN 202210569174A CN 114927661 B CN114927661 B CN 114927661B
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严微微
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Abstract

The application discloses a hierarchical hollow super-structure cobalt selenide nest-shaped composite material, a preparation method thereof and application thereof in preparing a lithium ion battery cathode. The cobalt selenide nest-shaped composite material with the hierarchical hollow super structure adopts CoSe 2 The nanocrystalline and the CoSe nanocrystalline are assembled into nano hollow spheres as primary structural units, and the nano hollow spheres are assembled into nest-shaped hierarchical large hollow spheres with openings as secondary structural units; the spherical shell of the nest-shaped hierarchical large hollow sphere is a hierarchical porous super structure which is formed by assembling a plurality of nano hollow spheres and contains mesopores and micropores. The preparation method comprises the following steps: firstly synthesizing cobalt-glycol precursor in the shape of raspberry, and then carrying out selenization in a vacuum closed environment to form the hierarchical hollow super-structure cobalt selenide nest-shaped composite material. The material has unique structure, high specific capacity, high rate performance and excellent circulation performance.

Description

Hierarchical hollow super-structure cobalt selenide nest-shaped composite material, and preparation and application thereof
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a hierarchical hollow super-structure cobalt selenide nest-shaped composite material, a preparation method thereof and application thereof in preparation of a lithium ion battery cathode.
Background
Lithium ion batteries have become one of the important components of electric vehicles and electric tools because of high energy and power density, long life, and good safety. However, commercial graphite anodes have lower theoretical capacity (372 mAh/g), have potential safety hazards, and can not meet the requirements of high-performance lithium ion batteries, which motivates the wide exploration of novel high-performance anode materials.
The transition metal selenides have higher densities and higher conductivities than the corresponding oxides and sulfides. Lithium ions can be stored in large quantities by the conversion reaction. These characteristics allow for higher volumetric energy density, good rate capability and higher specific capacity of the transition metal selenide.
Cobalt selenide, an important member of the transition metal selenides, has received increasing attention due to its high capacity and excellent conductivity, including CoSe, coSe 2 Etc. However, cobalt selenide has the problems of large volume change in the charge and discharge process, slow electrochemical kinetics, serious material crushing during circulation, rapid capacity attenuation and low specific capacity.
To date, many strategies have been proposed to improve the cycling performance of cobalt selenide. One common strategy is to compound nanoscale cobalt selenide with various high-conductivity materials, for example, the application patent with publication number CN114229805A discloses a nitrogen-doped porous carbon-coated cobalt diselenide composite, the application with publication number CN113666344A discloses a transition metal selenide-carbon composite, the application with publication number CN112018361A discloses a carbon cloth-loaded carbon-coated cobalt selenide nano sheet anode material, and the application with publication number CN110492081A discloses a cobalt selenide/zinc selenide@nitrogen-doped porous carbon nano tube composite.
These techniques all have a problem in that the overall specific capacity of the composite material is lowered by compounding a large amount of highly conductive but low-capacity carbon material. In fact, the conductivity of cobalt selenide is not low and complex carbon is not necessary.
Therefore, the more effective utilization mode of the cobalt selenide is to engineer the nano structure of the cobalt selenide, and the cycle performance, specific capacity and multiplying power performance of the cobalt selenide are improved through the design of the material structure.
Disclosure of Invention
Aiming at the technical problems in the prior art, the application provides a hierarchical hollow super-structure cobalt selenide nest-shaped composite material and a preparation method thereof. The material has unique structure, high specific capacity, high rate performance and excellent circulation performance. In addition, the material has important application value as a lithium ion battery anode material.
A hierarchical hollow super-structure cobalt selenide nest-shaped composite material adopts CoSe 2 The nano-crystal and the CoSe nano-crystal are assembled into nano-hollow spheres by taking the nano-hollow spheres as primary structural units, and the nano-hollow spheres are assembled into nest-shaped hierarchical large hollow spheres with openings by taking the nano-hollow spheres as secondary structural units;
the spherical shell of the nest-shaped hierarchical large hollow sphere is a hierarchical porous super structure which is formed by assembling a plurality of nano hollow spheres and contains mesopores and micropores.
Preferably, the CoSe 2 Nanocrystalline and CoSe NaThe diameter of the nanocrystals is 2-50 nm.
Preferably, the CoSe in each of the nano-hollow spheres 2 The total number of the nanocrystalline and the CoSe nanocrystalline is 3-10.
Preferably, the diameter of the nano hollow sphere is 30-150 nm.
Preferably, the nest-shaped graded large hollow sphere has a diameter of 100-2000 nm.
Preferably, the spherical shell thickness of the nest-shaped graded large hollow sphere is 50-500 nm.
Preferably, in the hierarchical hollow superstructure cobalt selenide nest-shaped composite material, the CoSe 2 The mass percentage of the nano-crystal is 30-90%, and the rest is CoSe nano-crystal.
The application also provides a preparation method of the hierarchical hollow super-structure cobalt selenide nest-shaped composite material, which comprises the following steps:
(1) Dissolving cobalt acetate in a mixed solution of ethylene glycol and ethanol to obtain a mixed solution in which the cobalt acetate is dissolved; transferring the obtained mixed solution dissolved with the cobalt acetate into a high-pressure reaction kettle, heating to 160-200 ℃ and reacting for 9-11 h; cooling, centrifugally separating a product, washing with ethanol, and drying to obtain a cobalt-ethylene glycol precursor;
(2) And (3) sealing the cobalt-glycol precursor obtained in the step (1) and selenium powder in a vacuum quartz test tube, heating to 500-700 ℃, and preserving heat for 9-11 h to obtain the hierarchical hollow super-structure cobalt selenide nest-shaped composite material.
The preparation method comprises the steps of firstly synthesizing cobalt-glycol precursor in a raspberry shape, and then carrying out selenization in a vacuum closed environment to form the hierarchical hollow super-structure cobalt selenide nest-shaped composite material.
Preferably, in the step (1), the volume ratio of the glycol to the ethanol in the mixed solution of the glycol and the ethanol is 14:16.
preferably, in the step (1), the ratio of the dosage of the cobalt acetate to the mixed solution of the ethylene glycol and the ethanol is 0.1-1.5 g:30mL.
Preferably, in the step (2), the mass ratio of the cobalt-ethylene glycol precursor to the selenium powder is 1:0.1 to 3.
The application also provides application of the hierarchical hollow super-structure cobalt selenide nest-shaped composite material in preparation of a lithium ion battery cathode.
The hierarchical hollow superstructure cobalt selenide nest-shaped composite material is adopted to manufacture the lithium ion battery cathode: the method comprises the steps of respectively weighing a hierarchical hollow super-structure cobalt selenide nest-shaped composite material, an acetylene black conductive agent and a sodium alginate binder according to the mass ratio of 7:1.5:1.5, dissolving sodium alginate in a proper amount of deionized water, stirring until the sodium alginate is completely dissolved, adding an active material and acetylene black which are uniformly ground into the solution, and continuously stirring to ensure uniform slurry mixing. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12 mm), drying at the temperature of 100 ℃ in a vacuum oven, and finally flattening by using the pressure of 10MPa on a tablet press to obtain the lithium ion battery negative plate.
And assembling the prepared electrode plate, the lithium plate and the diaphragm into the CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. Electrolyte is 1mol/L LiPF 6 The charge and discharge performance and the cycling stability of the lithium ion battery are tested by adopting a new-Wei battery test system.
The cobalt selenide material with high specific capacity, high rate performance and excellent cycle performance can be obtained by the application.
Compared with the prior art, the application has the following remarkable technical effects:
1) By CoSe 2 The nano crystal and the CoSe nano crystal are assembled into a hollow nano sphere by taking the hollow nano sphere as a secondary structural unit, the hollow nano sphere is further assembled into a porous super-structure spherical shell, and the prepared hierarchical hollow super-structure cobalt selenide nest-shaped composite material is provided with a large hole in the center, and the three structural characteristics are combined together to generate a strong and unique hierarchical multi-layer multi-pore synergistic effect, so that the CoSe is well buffered 2 And the volume change of CoSe in the charge and discharge process ensures the high cycle stability of the composite material. Wherein, especially the nest-shaped shell efficiently buffers the CoSe through a hierarchical porous super structure 2 And volume change of CoSe. Meanwhile, the hierarchical porous super-structure nest shell has a certain thicknessThe structural strength of the material is ensured.
2) For lithium ion transport: the hollow structure of the opening of the bird nest is beneficial to the permeation and storage of electrolyte; lithium ions can easily diffuse into the nest shell from two sides of the nest shell; lithium ions can be rapidly diffused and transmitted in the shell layer through the layered porous superstructure; coSe 2 And the ultra-small size of the CoSe nanocrystalline greatly shortens the solid-phase diffusion path of lithium ions; the hierarchical hollow super-structure cobalt selenide nest-shaped composite material has extremely large specific surface area and provides a large number of electrochemical active sites.
3) For electron conduction: in the nest-shaped hierarchical porous super-structure spherical shell, hollow nanospheres are tightly assembled together as secondary structural units. In the hollow nanospheres, coSe 2 The nanocrystals are also tightly coupled with the CoSe nanocrystals. The multi-layer close coupling relation constructs a high-efficiency conductive network, so that the composite material has extremely high conductivity.
4)CoSe 2 And two different selenides of CoSe are combined in the same hollow nanosphere assembly to form a heterostructure, so that the heterostructure has a synergistic effect on electrochemical lithium storage reaction, can accelerate electrochemical reaction kinetics, and has a special composite effect which is not possessed by a single cobalt selenide material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a cobalt-ethylene glycol precursor prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the cobalt-ethylene glycol precursor prepared in example 1;
FIG. 3 is an SEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite prepared according to example 1;
FIG. 4 is a TEM photograph of the hierarchical hollow superstructure cobalt selenide bird nest composite prepared in example 1;
FIG. 5 is a partial TEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite prepared in example 1;
FIG. 6 is a partially enlarged TEM photograph of the hierarchical hollow superstructure cobalt selenide bird nest composite prepared in example 1;
FIG. 7 is a High Resolution TEM (HRTEM) photograph of the hierarchical hollow superstructure cobalt selenide bird nest composite prepared in example 1;
FIG. 8 is an XRD pattern of the hierarchical hollow superstructure cobalt selenide bird nest composite prepared in example 1;
FIG. 9 is a graph of the cycling performance at a current density of 1A/g of the hierarchical hollow superstructure cobalt selenide bird nest composite prepared in example 1.
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
(1) 0.5g of cobalt acetate was dissolved in a mixed solution of 14ml of ethylene glycol and 16ml of ethanol. The prepared mixed solution was sealed in a 50ml autoclave, heated to 180℃and subjected to solvothermal reaction for 10 hours. After the autoclave was naturally cooled, the product was centrifuged, washed with ethanol several times and dried at 70 ℃. Obtaining a cobalt-ethylene glycol precursor;
(2) And (3) sealing the cobalt-glycol precursor obtained in the step (1) and selenium powder in a vacuum quartz test tube according to a mass ratio of 1:1, heating to 600 ℃, and preserving heat for 10 hours to obtain the hierarchical hollow super-structure cobalt selenide nest-shaped composite material.
Fig. 1 is an SEM photograph of a prepared cobalt-ethylene glycol precursor, which is a hollow sphere with an opening, in the shape of a raspberry. These cobalt-ethylene glycol precursors are rough in surface and exhibit particle assembly characteristics.
Fig. 2 is a TEM photograph of the prepared cobalt-ethylene glycol precursor, and it was confirmed that small particles were assembled with a diameter of about 50nm, particles were tightly coupled, and no pores were present between particles and within particles. The shell thickness of the cobalt-glycol precursor is 120-180 nm measured through the opening.
Fig. 3 is an SEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite, with the hollow spheres intact after selenization, but the surface particles becoming sharper.
Fig. 4 is a TEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite, confirming that the bird nest composite is hollow, having only one opening at one end, the particles on the surface of the pellets being finer after selenization, a large number of micropores being present on the surface of the pellets, and the overall structure being bird nest-shaped. The diameter of the bird nest is about 600-800 nm, and the shell thickness is about 110-170 nm.
FIG. 5 is a partial TEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite, with the understanding that there are many hollow nanospheres within the bird nest shell, which are tightly packed together to form a hierarchical porous superstructure sphere.
FIG. 6 is a partially enlarged TEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite, having at least 4 nanocrystals within one hollow nanosphere, the nanocrystals being closely connected. The diameter of the nanocrystals was about 20nm. The outer diameter of the nano hollow sphere is about 50nm. The center of the nano hollow sphere is provided with a hole with the diameter of about 7nm, which proves that the nano hollow sphere is of a hollow structure.
FIG. 7 is a HRTEM photograph of a hierarchical hollow superstructure cobalt selenide bird nest composite, two of the four particles exhibiting two different crystal grains with interplanar spacings of 0.290nm and 0.314nm, respectively, good CoSe anastomosis 2 (101) crystal plane of (a) and (100) crystal plane of CoSe.
FIG. 8 is an XRD pattern of a hierarchical hollow superstructure cobalt selenide bird nest composite with diffraction peaks at 30.7, 34.5, 35.9, 37, 47.8, 56.9, 59.2, 63.3 corresponding to CoSe 2 The (101), (111), (120), (200), (211), (131), (310), (122) crystal planes at 33.1 °,44.9 ° and 50.4 ° diffraction peaks correspond to the (101), (102) and (110) crystal planes of CoSe, proving CoSe 2 And CoSe coexist. Low diffraction peak intensity, indicating CoSe 2 The grain sizes of the nanocrystals and the CoSe nanocrystals are fine. There were no diffraction peaks for the cobalt-ethylene glycol precursor, indicating that it was completely selenized. Through EDS analysis, the atomic percentage contents of cobalt and selenium in the hierarchical hollow super-structure cobalt selenide nest-shaped composite material are 16.15 percent and 26.47 percent respectively, thereby obtaining CoSe 2 And the mass percentages of CoSe are 73.57% and 26.43%, respectively.
The hierarchical hollow superstructure cobalt selenide nest-shaped composite material of the embodiment is adopted to manufacture the lithium ion battery cathode: the method comprises the steps of respectively weighing a hierarchical hollow super-structure cobalt selenide nest-shaped composite material, an acetylene black conductive agent and a sodium alginate binder according to the mass ratio of 7:1.5:1.5, dissolving sodium alginate in a proper amount of deionized water, stirring until the sodium alginate is completely dissolved, adding an active material and acetylene black which are uniformly ground into the solution, and continuously stirring to ensure uniform slurry mixing. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12 mm), drying at the temperature of 100 ℃ in a vacuum oven, and finally flattening by using the pressure of 10MPa on a tabletting machine to obtain the electrode slice.
And assembling the prepared electrode plate, the lithium plate and the diaphragm into the CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. Electrolyte is 1mol/L LiPF 6 The charge and discharge performance and the cycling stability of the lithium ion battery are tested by adopting a new-Wei battery test system.
FIG. 9 is a graph of the cycling performance of a hierarchical hollow superstructure cobalt selenide bird nest composite at a current density of 1A/g. In the first 75 cycles, the discharge capacity was stabilized at 612mAh/g. After that, the discharge capacity was slowly increased. At 880 th cycle, the maximum was as high as 1623mAh/g. At cycle 1000, the discharge capacity still reached 1361mAh/g.
The lithium battery performance of the graded hollow super-structure cobalt selenide nest-shaped composite material is superior to that of the application patent of publication No. CN113666344A, namely a transition metal selenide-carbon composite material (the 170 th cycle discharge capacity is about 150mAh/g when the current density is 0.05A/g), the nitrogen doped porous carbon coated cobalt diselenide composite material is superior to that of the application patent of publication No. CN114229805A (the discharge capacity after 300 cycles is 644mAh/g when the current is 0.2A/g), the molybdenum doped flaky cobalt diselenide/graphene composite electrode material is superior to that of the application patent of publication No. CN109962229A (the discharge capacity is 996 mAh/g), and the cobalt diselenide/carbon nano material is superior to that of the application patent of publication No. CN105428647A (the 50 th cycle discharge capacity is 500 mAh/g).
Example 2
(1) 0.5g of cobalt acetate was dissolved in a mixed solution of 14ml of ethylene glycol and 16ml of ethanol. The prepared mixed solution was sealed in a 50ml autoclave, and heated to 190 ℃ for solvothermal reaction for 10h. After the autoclave was naturally cooled, the product was centrifuged, washed with ethanol several times and dried at 70 ℃. Obtaining a cobalt-ethylene glycol precursor;
the subsequent steps are the same as in example 1.
The structure of the product-graded hollow superstructure cobalt selenide nest-shaped composite material is similar to that of example 1, and the main difference is CoSe 2 The sizes of the nanocrystals and the CoSe nanocrystals were changed to about 26nm, and the diameters of the constituent hollow nanospheres were about 65nm; the size of the bird nest becomes 750-950 nm, and the shell thickness of the bird nest becomes 150-220 nm.
The same process as in example 1 was used to fabricate a lithium ion battery negative electrode, assembled into a lithium ion battery, and subjected to cyclic charge and discharge test at a current density of 1A/g and a voltage range of 0.01 to 3.0V. The discharge capacity of the hierarchical hollow super-structure cobalt selenide nest-shaped composite material is stabilized at 520mAh/g in the first 70 cycles. After that, the discharge capacity was slowly increased. At cycle 810, the maximum value is as high as 1362mAh/g. At cycle 1000, the discharge capacity still reached 1136mAh/g.
Example 3
(1) 0.7g of cobalt acetate was dissolved in a mixed solution of 14ml of ethylene glycol and 16ml of ethanol. The prepared mixed solution was sealed in a 50ml autoclave, heated to 180℃and subjected to solvothermal reaction for 10 hours. After the autoclave was naturally cooled, the product was centrifuged, washed with ethanol several times and dried at 70 ℃. Obtaining a cobalt-ethylene glycol precursor;
the subsequent procedure was the same as in example 1.
The structure of the product-graded hollow superstructure cobalt selenide nest-shaped composite material is similar to that of example 1, and the main difference is CoSe 2 The sizes of the nanocrystals and the CoSe nanocrystals were changed to 30nm, and the diameters of the hollow nanospheres composed of the nanocrystals were about 75nm; the size of the bird nest becomes 900-1100 nm, and the shell thickness of the bird nest becomes 160-230 nm.
The same process as in example 1 was used to fabricate a lithium ion battery negative electrode, assembled into a lithium ion battery, and subjected to cyclic charge and discharge test at a current density of 1A/g and a voltage range of 0.01 to 3.0V. The discharge capacity of the hierarchical hollow super-structure cobalt selenide nest-shaped composite material is stabilized at 495mAh/g in the first 70 cycles. After that, the discharge capacity was slowly increased. At cycle 800, the maximum value is as high as 1258mAh/g. At cycle 1000, the discharge capacity still reached 1048mAh/g.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.

Claims (8)

1. A hierarchical hollow super-structure cobalt selenide nest-shaped composite material is characterized in that the hierarchical hollow super-structure cobalt selenide nest-shaped composite material adopts CoSe 2 The nano-crystal and the CoSe nano-crystal are assembled into nano-hollow spheres by taking the nano-hollow spheres as primary structural units, and the nano-hollow spheres are assembled into nest-shaped hierarchical large hollow spheres with openings by taking the nano-hollow spheres as secondary structural units;
the spherical shell of the nest-shaped hierarchical large hollow sphere is a hierarchical porous super structure which is formed by assembling a plurality of nano hollow spheres and contains mesopores and micropores.
2. The hierarchical hollow superstructure cobalt selenide nest composite of claim 1, wherein:
the CoSe 2 The diameters of the nanocrystals and the CoSe nanocrystals are 2-50 nm;
CoSe in each of the nano hollow spheres 2 The total number of the nanocrystalline and the CoSe nanocrystalline is 3-10;
the diameter of the nano hollow sphere is 30-150 nm;
the diameter of the nest-shaped grading large hollow sphere is 100-2000 nm;
the thickness of the spherical shell of the nest-shaped grading large hollow sphere is 50-500 nm.
3. The hierarchical hollow superstructure cobalt selenide bird nest composite of claim 1, wherein the hierarchical hollow superstructure cobalt selenide bird nest compositeIn the CoSe 2 The mass percentage of the nano-crystal is 30-90%, and the rest is CoSe nano-crystal.
4. The method for preparing the hierarchical hollow super-structure cobalt selenide nest-shaped composite material according to claim 1, comprising the steps of:
(1) Dissolving cobalt acetate in a mixed solution of ethylene glycol and ethanol to obtain a mixed solution in which the cobalt acetate is dissolved; transferring the obtained mixed solution dissolved with the cobalt acetate into a high-pressure reaction kettle, heating to 160-200 ℃ and reacting for 9-11 h; cooling, centrifugally separating a product, washing with ethanol, and drying to obtain a cobalt-ethylene glycol precursor;
(2) And (3) sealing the cobalt-glycol precursor obtained in the step (1) and selenium powder in a vacuum quartz test tube, heating to 500-700 ℃, and preserving heat for 9-11 h to obtain the hierarchical hollow super-structure cobalt selenide nest-shaped composite material.
5. The method for preparing the hierarchical hollow super-structure cobalt selenide nest-shaped composite material according to claim 4, wherein in the step (1), the volume ratio of the glycol and the ethanol in the mixed solution of the glycol and the ethanol is 14:16.
6. the method for preparing the hierarchical hollow super-structure cobalt selenide nest-shaped composite material according to claim 4, wherein in the step (1), the ratio of the amount of the cobalt acetate to the amount of the mixed solution of ethylene glycol and ethanol is 0.1-1.5 g:30mL.
7. The method for preparing a hierarchical hollow superstructure cobalt selenide nest-shaped composite material according to claim 4, wherein in the step (2), the mass ratio of the cobalt-ethylene glycol precursor to the selenium powder is 1:0.1 to 3.
8. Use of the hierarchical hollow superstructure cobalt selenide bird nest composite material according to any one of claims 1 to 3 in the preparation of a lithium ion battery negative electrode.
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