CN113725432A - ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67 - Google Patents

ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67 Download PDF

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CN113725432A
CN113725432A CN202110857324.7A CN202110857324A CN113725432A CN 113725432 A CN113725432 A CN 113725432A CN 202110857324 A CN202110857324 A CN 202110857324A CN 113725432 A CN113725432 A CN 113725432A
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zif
cobalt selenide
heating
koh
composite material
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CN113725432B (en
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闻韬
朱学勇
张俊豪
薛艳春
沈克军
顾执明
杨茹
王鑫
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State Grid Zhenjiang Comprehensive Energy Service Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method of ZIF-67 and a cobalt selenide/carbon electrode material derived from the ZIF-67, which comprises the steps of dissolving 2-methylimidazole and KOH in deionized water to obtain a transparent solution, and dissolving Co (NO) in the transparent solution3)2·6H2The solution was added to the O solution and stirred to obtain ZIF-67 powder. Among them, 2-methylimidazole and Co (NO)3)2·6H2The mass ratio of O is 8: 1, the mass concentration of KOH is 0.1-3mol L‑1. And then carbonizing the polyhedral ZIF-67 precursor, and preparing the cobalt selenide/carbon composite material by adopting different selenizing methods. In the invention, KOH is utilized for the first time to assist in synthesizing ZIF-67 with different shapes in aqueous solution, and the derived cobalt selenide/carbon composite material shows excellent performanceDifferent lithium storage properties. The method has the characteristics of green solvent, simple process, short reaction time, high yield and controllable product morphology.

Description

ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67
Technical Field
The invention relates to a preparation method of a ZIF-67 and a cobalt selenide/carbon electrode material derived from the ZIF-67, belonging to the technical field of new materials.
Background
With the increasing energy consumption and the rapid development of portable electronic products and electric vehicles, people are increasingly pursuing advanced rechargeable energy storage materials/devices with high efficiency and durability. The lithium ion battery has great development potential in the field of energy storage as a new generation of energy storage device. The exploration of the negative electrode material with high specific capacity and stability is of great significance. In recent years, transition metal selenides based on electrochemical conversion reactions have received much attention due to their high reversible capacity. However, transition metal selenides have problems of poor cycle performance and rate performance due to large volume change and low electrical conductivity. Therefore, designing a composite of transition metal selenides and carbon is an effective strategy to solve the above-mentioned problems.
In recent years, in the research of lithium ion battery negative electrode materials, the synthesis of porous carbon or metal compound/carbon material with high porosity by using Metal Organic Frameworks (MOFs) as precursors has become a research hotspot. The MOFs are organic-inorganic hybrid materials composed of organic ligands and inorganic metal ions or clusters, and generally, the metal ions are used as connecting points, and the organic ligands are used as connectors, and the MOFs are self-assembled to form a structure with a periodic net-shaped framework. During annealing, metal ions in the MOFs can be converted into active components for storing lithium, while organic ligands can be evolved into highly conductive carbon, and active defects can be generated during decomposition. Meanwhile, the derivative material also has rich and adjustable chemical components, an ordered multi-scale pore structure and uniformly and densely distributed active sites. However, the studies to control the shape of MOFs nanocrystals are not as sophisticated as metal nanoparticles; at present, the synthesis of many MOFs has the problems of low time efficiency, low yield, toxic solvent and the like; therefore, the development of a low-cost, simple synthetic strategy is crucial to accelerate the commercialization and industrialization of MOF-based anode materials.
Electrochemical energy storage of lithium ion batteries is mainly achieved by intercalation, conversion or alloying reactions taking place in the electrode material. Compared with an embedded reaction, the electrode can realize higher capacity by carrying out a conversion reaction, and compared with an alloying reaction, the conversion reaction type electrode has better circulation stability; therefore, the application of the conversion reaction electrode material in the field of lithium ion batteries is widely concerned. Transition metal selenide-based materials have gained wide attention in energy storage and conversion systems due to their abundant resources, low cost, and large theoretical lithium storage capacity. For example, CoSe2The electrode has larger interlayer spacing and narrow band gap, so that the electrode has higher lithium ion diffusion rate, higher electron transfer speed and lower energy barrier in the redox reaction.
Disclosure of Invention
The invention aims to provide a preparation method of ZIF-67 and a cobalt selenide/carbon electrode material derived from the ZIF-67, wherein in a water system, the nucleation and growth of the ZIF-67 are regulated and controlled by changing the concentration of KOH so as to regulate and control the appearance and structure of a product, so that the appearance of the product is changed from a two-dimensional leaf shape into a three-dimensional polyhedral shape, and the synthesis efficiency and yield of the ZIF-67 are greatly improved. The cobalt selenide/carbon composite material is obtained by selenizing the polyhedral ZIF-67 serving as a precursor and is used as a lithium ion battery cathode material, so that the lithium storage performance is improved, and the conductivity of the electrode material is improved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of ZIF-67 and a cobalt selenide/carbon electrode material derived from the ZIF-67 comprises the following steps:
1) dissolving 2-methylimidazole and KOH in deionized water, ultrasonically dispersing for 5 minutes, stirring for 10 minutes to obtain a transparent solution, and adding Co (NO)3)2·6H2Obtaining a reaction solution from the water solution of O, stirring the reaction solution at room temperature for 4-8 hours, and then centrifuging, washing and drying to obtain ZIF-67 powder; the 2-methylimidazole and Co (NO)3)2·6H2The mass ratio of O is 8: 1, the mass concentration of KOH in the reaction solution is 0.1-3mol L-1
2) Putting the ZIF-67 powder obtained in the step 1) into a tube furnace, and heating at 2 ℃ for min in a nitrogen or argon atmosphere-1Raising the temperature to 500 ℃ at the temperature raising rate, keeping the temperature for 1 hour, and carbonizing;
3) selenizing the carbide obtained in the step 2).
The object of the invention can be further achieved by the following technical measures:
the preparation method of the ZIF-67 and the cobalt selenide/carbon electrode material derived from the ZIF-67 comprises the following steps: sequentially adding the carbide obtained in the step 2), sodium selenite and hydrazine hydrate with the mass percentage of 85% into deionized water, wherein the mass ratio of the carbide to the sodium selenite to the hydrazine hydrate to the deionized water is 20:60:0.62:16, uniformly stirring, transferring the mixture into a stainless steel reaction kettle, heating to 160 ℃, preserving heat for 8 hours, cooling, centrifuging, washing and drying to obtain the cobalt selenide/carbon composite material.
The preparation method of the ZIF-67 and the cobalt selenide/carbon electrode material derived from the ZIF-67 comprises the following steps: respectively spreading selenium powder and the carbide obtained in the step 2) at two ends of a porcelain boat in a mass ratio of 2:1, transferring the porcelain boat into a tube furnace, heating the selenium powder at the upstream and the carbide obtained in the step 2) at the downstream in an inert gas atmosphere for selenizing, and heating the carbide at the temperature of 2 ℃ for min-1Heating to 350 deg.C at a heating rate for 3 hr, and keeping at 2 deg.C for min-1Raising the temperature to 500 ℃ at the heating rate, preserving the heat for 1 hour, and cooling to obtain the cobalt selenide/carbon composite material.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the ZIF-67 with different morphologies is synthesized efficiently and massively under a water system condition by regulating the concentration of KOH. In the prior art, ZIF-67 with a polyhedral structure needs to be synthesized in methanol and grows for more than 24 hours, the method has the defects of time consumption, low yield and toxic solvent, and the product is charged with static electricity and is not beneficial to the next processing treatment. A two-dimensional structure is usually synthesized in a water system, ZIF-67 is difficult to grow in a multi-dimensional mode under the water system condition, a large amount of dimethyl imidazole ligand is needed to be added for realizing the growth, and the problems of non-uniform appearance, large particle size difference, time consumption and low yield exist. Compared with the existing ZIF-67 synthesis method, the method is more green, efficient and economical. The result shows that the reaction can be completed in 6 hours, and the yield is 70-80%. Meanwhile, compared with the existing method for regulating and controlling the ZIF-67 morphology by using surfactants such as CTAB or F127 and the like, the method is more economical and efficient, and the low-cost simple synthesis method has important significance for accelerating the commercialization and industrialization of the ZIF-67-based negative electrode material.
(2) According to the invention, polyhedral ZIF-67 is used as a precursor, and the cobalt selenide/carbon composite material is obtained through selenization. In the selenization process, metal ions in the ZIF-67 are converted into active components for storing lithium, and the organic ligand is converted into high-conductivity carbon, so that the uniform compounding of cobalt selenide and carbon is realized. The method can not only improve the conductivity of the electrode material, but also effectively relieve the volume expansion problem of the cobalt selenide. Meanwhile, the porous structure of the ZIF-67 can be reserved, which is beneficial to enlarging the contact area of the electrode/electrolyte and accelerating the high-efficiency transfer of ions. The result shows that the polyhedral ZIF-67 derivative material synthesized by KOH assistance shows excellent lithium storage performance. The preparation method adopted by the method is simple, efficient and high in yield, does not need harsh reaction conditions, and is convenient for large-scale production.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a ZIF-67 material prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Micrograph (SEM) of a ZIF-67 material prepared in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph (TEM image) of a ZIF-67 material prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a ZIF-67 material prepared in example 2 of the present invention;
FIG. 5 is an SEM image of a ZIF-67 material prepared in example 3 of the present invention;
FIG. 6 is an SEM image of a ZIF-67 material prepared in example 4 of the present invention;
FIG. 7 is an XRD spectrum of the polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 5 of the present invention;
FIG. 8 is an XRD spectrum of the polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 6 of the present invention;
FIG. 9 is an SEM image of a polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 5 of the present invention;
FIG. 10 is an SEM image of a polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 6 of the present invention;
FIG. 11 is a cyclic voltammogram of the polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 5 of the present invention;
FIG. 12 is a charge-discharge curve of the polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 5 of the present invention;
FIG. 13 is a graph of polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode materials at 100mA g prepared in examples 5 and 6 of the present invention-1Cycling performance at current density;
FIG. 14 is a graph of rate capability of polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode materials prepared in example 5 of the present invention;
FIG. 15 is a charge-discharge curve of the polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode material prepared in example 5 of the present invention at different current densities;
fig. 16 is an electrochemical impedance spectrum of polyhedral ZIF-67 derivatized cobalt selenide/carbon electrode materials prepared in examples 5 and 6 of the present invention in LIBs.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Preparation of ZIF-67 material
Example 1:
firstly, sequentially adding KOH and 2-methylimidazole into deionized water, and obtaining a mixed solution A after ultrasonic stirring for 5 minutes and magnetic stirring for 10 minutes; then adding Co (NO)3)2·6H2Solution B was prepared by dissolving O in deionized water. Adding the solution B into the solution A under the condition of stirring, continuously stirring for 6 hours, centrifuging, washing and drying to obtain the polyhedral ZIF-67 powder. The reaction temperature was 12 ℃. 2-methylimidazole and Co (NO)3)2·6H2The mass ratio of O is about 8: 1, the mass concentration of KOH in the reaction solution is 3mol L-1
As can be seen from FIG. 1, the XRD pattern of the prepared ZIF-67 material showed that the position of the characteristic peak of the material was consistent with that of the standard peak of ZIF-67, indicating that the synthesized product was ZIF-67.
As can be seen from fig. 2, the SEM image of the prepared ZIF-67 material showed a three-dimensional polyhedral structure, was uniformly dispersed, had no agglomeration phenomenon, and had a diameter of about 1000 nm.
It can be seen from fig. 3 that the TEM image of the prepared ZIF-67 material shows that the three-dimensional polyhedron is a solid structure.
Example 2:
the difference from example 1 is that the KOH concentration is 0.1mol L-1. The SEM image in FIG. 4 shows that when the concentration of KOH was 0.1mol L-1In the meantime, the morphology of the obtained product still predominates in a two-dimensional leaf-like structure, but the thickness of the sheet produced by this method is greater than that of the sheet produced in the reported aqueous solution; in addition, a three-dimensional carambola-like structure is also found in the picture, which shows that the appearance of the product tends to be changed from a two-dimensional structure to a three-dimensional structure with the addition of KOH.
Example 3:
the difference from example 1 is that the KOH concentration is 1mol L-1. As shown in fig. 5, SEM showed that the resulting material was mainly a three-dimensional granular structure with only a small amount of two-dimensional structure. As compared with example 2, it is found that 2mol L-1KOH further induced the ZIF-67 crystals to transition from predominantly two-dimensional growth to three-dimensional growth, and it can be seen that the addition of KOH at high concentrations accelerates the change in the direction of crystal growth.
Example 4:
the difference from example 1 is that the KOH concentration is 2mol L-1. Basic parameters: as shown in FIG. 6, SEM showsThe resulting material is a three-dimensional structured particle. It can be seen from comparison with case 3 that the two-dimensional morphology is completely converted into the three-dimensional morphology with an increase in the amount of KOH added. As compared with case 1, 3mol L-1The KOH of (3) is more favorable for ZIF-67 to grow into a regular and uniform three-dimensional polyhedral structure.
Secondly, preparing a ZIF-67 derived cobalt selenide/carbon electrode material
Example 5:
the product of example 1 was placed in a tube furnace under an inert gas atmosphere at 2 ℃ for min-1Raising the temperature to 500 ℃ at the heating rate, preserving the heat for 1 hour, and naturally cooling to obtain a carbonized product. Then sequentially adding carbide, sodium selenite and hydrazine hydrate (85%) into deionized water, wherein the mass ratio of the carbide to the sodium selenite to the hydrazine hydrate to the deionized water is 20:60:0.62:16, uniformly stirring, transferring the mixture into a stainless steel reaction kettle, heating to 160 ℃, preserving heat for 8 hours, naturally cooling, centrifuging, washing and drying to obtain Co0.85Se/C composite material.
FIG. 7 shows the prepared polyhedral ZIF-67 derived high performance Co0.85The XRD spectrum of the Se/C composite material shows that in the diffraction peaks of the composite material, the broad peak positioned at about 25 degrees corresponds to the characteristic peak of amorphous carbon, and the peaks positioned at 33.15 degrees, 44.9 degrees and 50.5 degrees respectively correspond to the peaks of Co0.85Se's (101), (102) and (110) crystal planes (JCPDS No. 52-1008). The other impurity peaks are characteristic peaks of the Se simple substance, which shows that the hydrothermal selenization product is Co0.85Se/C composite material.
FIG. 9 shows the prepared polyhedral ZIF-67 derived Co0.85SEM image of Se/C composite material, the result shows that Co0.85The Se/C composite material is in a three-dimensional polyhedral structure, a nano flaky structure is attached to the surface of the Se/C composite material, and nano fragments are scattered among gaps of the polyhedron, which is attributed to the fact that in the hydrothermal selenization process, cobalt ions on the surface enter a solvent and react with sodium selenite under the action of hydrazine hydrate, so that the Se/C composite material shows a phenomenon of stripping/falling off the flaky structure.
FIG. 11 shows the prepared polyhedral ZIF-67 derived high performance Co0.85Cycling of Se/C electrodes in lithium ion batteriesThe results of the cyclic voltammetry curve show that two reduction peak positions, which are respectively at 0.36 and 0.94V and correspond to the reduction reaction, namely Co0.85Conversion of Se to Co and Li2Se, and formation of a solid electrolyte interfacial layer. The subsequent anode scan showed two peaks at 1.38V and 2.56V, which were caused by the oxidation of cobalt metal to cobalt ions. In the second cycle, the reduction peak in the cyclic voltammogram was shifted to 0.65, 1.12 and 1.66V, which is similar to other similar conversion negative electrode materials, and the structure was changed due to the first lithiation/delithiation. The other cyclic voltammograms except the first two cycles were highly overlapping, indicating good reversibility of the electrode.
FIG. 12 shows that the prepared polyhedral ZIF-67-derived high-performance Co0.85Se/C electrodes in LIBs at 0.1A g-1The charge-discharge diagram under the current density shows an inclined discharge curve, the charge-discharge platform of the material can be seen to be consistent with the position of the oxidation-reduction peak of the cyclic voltammetry curve, and the first-circle specific discharge capacity can be seen to be 1593.3mAh g-1The higher first-turn specific discharge capacity is attributed to the increase of the electrochemical reaction active sites by Se doping. The discharge curve overlap ratio was good for the next 4 cycles, indicating good initial cycle stability.
FIG. 13 shows that the prepared polyhedral ZIF-67-derived Co0.85Se/C composites in LIBs at 0.1A g-1Cycling performance plot at current density. It can be seen that Co0.85The Se/C cycle shows higher specific capacity (765mAh g) after 200 circles-1). In addition, Co is recycled0.85The capacity of Se/C shows a tendency to decay first and then rise back, with the first 100 cycles being a slow decay of capacity due to the change in volume. In the last 100 cycles, Co is caused by the volume expansion due to repeated charge and discharge0.85The Se/C composite material is subjected to particle nanocrystallization, active sites are increased, and therefore the capacity is increased.
FIG. 14 shows the prepared polyhedral ZIF-67 derived Co0.85The rate performance graph of the Se/C composite material as the lithium ion battery cathode material can show that Co0.85Se/C complexThe composite material shows excellent rate performance, and the electrode has the rate performance of 0.1, 0.2, 0.5, 1, 2 and 5A g-1Average capacities at bottom 1123, 1045, 932, 822, 632 and 293mAh g-1. When the current returns to 0.1A g-1When it is used, its specific capacity is 972mAh g-1The capacity retention rate is close to 90%.
FIG. 15 shows the prepared polyhedral ZIF-67 derivatized Co0.85The Se/C composite material is used as a charge-discharge curve of the lithium ion battery cathode material under different current densities. It can be seen that the potential difference of the charge and discharge platform gradually increases with increasing current, even at 5A g-1Under the high current density, the stable charge-discharge platform still exists, which shows that Co has a stable charge-discharge platform0.85The Se/C composite material has good structural stability.
It can be seen from FIG. 16 that the prepared polyhedral ZIF-67-derived Co0.85The electrochemical impedance spectrogram of the Se/C composite material in the LIBs shows that a curve is composed of a semicircle of a high-frequency region and a slash of a low-frequency region, the semicircle represents a charge transfer resistance, the slash represents an ion diffusion process, and the electrode resistance is related to the semicircle of the high-frequency region. It can be seen that Co0.85The Se/C composite exhibits a relatively small semicircle, indicating that the charge transfer resistance is small, which can suppress the formation of an excessively thick solid electrolyte membrane, facilitating the electron transfer.
Example 6:
placing selenium powder and carbonized product (mass ratio of 2:1) at upstream and downstream of tube furnace respectively, and heating at 2 deg.C for min under inert gas atmosphere-1The temperature rising rate is increased to 350 ℃ and is kept for 3 hours, the temperature is kept for 1 hour at 500 ℃, and the black and gray CoSe is obtained after natural cooling2a/C composite material.
FIG. 8 is a preparation of polyhedral ZIF-67 derivatized CoSe2The XRD spectrogram of the/C composite material shows that the position of the characteristic peak of the composite material is corresponding to the position of o-CoSe2(ortho, Pnm, JCPDS No.53-0449) and c-CoSe2(Cubic, Pa-3, JCPDS No. 09-0234). The characteristic peaks at 30.8 °, 34.5 °, 36.0 °, 47.7 °, 65.0 ° and 63.3 ° correspond to o-CoSe2The (101), (111), (120), (211), (311) and (122) crystal planes of (A) and (B) are located inThe peaks at 34.2 °, 37.6 °, 51.8 °, 56.5 °, 58.8 ° and 74.0 ° correspond to the c-CoSe2The (210), (211), (311), (230), (321), and (421) crystal planes of (a). Evidence of CoSe2The cobalt selenide in the/C composite material is a biphase coexisting composite material and comprises cubic CoSe2And quadrature phase CoSe2
FIG. 10 shows the prepared polyhedral ZIF-67 derived high performance CoSe2The result of an SEM image of the electrode material shows that after calcination and selenization, the polyhedral ZIF-67 is shrunk in shape, and blocky bulges appear on the surface, which are caused by decomposition of a ligand on the surface at high temperature, outward escape of metal ions and combination of selenium ions, and the bulges are cobalt selenide crystal clusters.
FIG. 13 shows the prepared polyhedral ZIF-67 derived high performance CoSe2The application of the/C composite material in the negative electrode material of the lithium ion battery is L0.1A g-1Cycling performance plot at current density. It can be seen that CoSe was present after 200 cycles2the/C composite material shows better cycling stability, and the specific capacity of the composite material is still kept 489.6mAh g after 200 cycles of cycling-1Better stability and o-CoSe2And c-CoSe2The synergistic effect is related.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.

Claims (3)

1. A preparation method of ZIF-67 and a cobalt selenide/carbon electrode material derived from the ZIF-67 is characterized by comprising the following steps:
1) dissolving 2-methylimidazole and KOH in deionized water, ultrasonically dispersing for 5 minutes, stirring for 10 minutes to obtain a transparent solution, and adding Co (NO)3)2·6H2Obtaining a reaction solution from the water solution of O, stirring the reaction solution at room temperature for 4-8 hours, and then centrifuging, washing and drying to obtain ZIF-67 powder; the 2-methylimidazole and Co (NO)3)2·6H2The mass ratio of O is 8: 1, the mass concentration of KOH in the reaction solution is 0.1-3mol L-1
2) Putting the ZIF-67 powder obtained in the step 1) into a tube furnace, and heating at 2 ℃ for min in a nitrogen or argon atmosphere-1Raising the temperature to 500 ℃ at the temperature raising rate, keeping the temperature for 1 hour, and carbonizing;
3) selenizing the carbide obtained in the step 2).
2. The preparation method of ZIF-67 and cobalt selenide/carbon electrode materials derived therefrom as claimed in claim 1, wherein the selenization method of step 3) is hydrothermal selenization: sequentially adding the carbide obtained in the step 2), sodium selenite and hydrazine hydrate with the mass percentage of 85% into deionized water, wherein the mass ratio of the carbide to the sodium selenite to the hydrazine hydrate to the deionized water is 20:60:0.62:16, uniformly stirring, transferring the mixture into a stainless steel reaction kettle, heating to 160 ℃, preserving heat for 8 hours, cooling, centrifuging, washing and drying to obtain the cobalt selenide/carbon composite material.
3. The preparation method of ZIF-67 and cobalt selenide/carbon electrode materials derived therefrom as claimed in claim 1, wherein the selenization method of step 3) is gas selenization: respectively spreading selenium powder and the carbide obtained in the step 2) at two ends of a porcelain boat in a mass ratio of 2:1, transferring the porcelain boat into a tube furnace, heating the selenium powder at the upstream and the carbide obtained in the step 2) at the downstream in an inert gas atmosphere for selenizing, and heating the carbide at the temperature of 2 ℃ for min-1Heating to 350 deg.C at a heating rate for 3 hr, and keeping at 2 deg.C for min-1Raising the temperature to 500 ℃ at the heating rate, preserving the heat for 1 hour, and cooling to obtain the cobalt selenide/carbon composite material.
CN202110857324.7A 2021-07-28 2021-07-28 ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67 Active CN113725432B (en)

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CN114937764A (en) * 2022-05-27 2022-08-23 江苏科技大学 Cobalt disulfide composite material protected by double carbon layers and preparation method and application thereof
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