CN113725432B - 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

Info

Publication number
CN113725432B
CN113725432B CN202110857324.7A CN202110857324A CN113725432B CN 113725432 B CN113725432 B CN 113725432B CN 202110857324 A CN202110857324 A CN 202110857324A CN 113725432 B CN113725432 B CN 113725432B
Authority
CN
China
Prior art keywords
zif
heating
cobalt selenide
koh
electrode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110857324.7A
Other languages
Chinese (zh)
Other versions
CN113725432A (en
Inventor
闻韬
朱学勇
张俊豪
薛艳春
沈克军
顾执明
杨茹
王鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
State Grid Zhenjiang Comprehensive Energy Service Co ltd
Original Assignee
State Grid Zhenjiang Comprehensive Energy Service Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by State Grid Zhenjiang Comprehensive Energy Service Co ltd filed Critical State Grid Zhenjiang Comprehensive Energy Service Co ltd
Priority to CN202110857324.7A priority Critical patent/CN113725432B/en
Publication of CN113725432A publication Critical patent/CN113725432A/en
Application granted granted Critical
Publication of CN113725432B publication Critical patent/CN113725432B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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 solution 3 ) 2 ·6H 2 Adding the solution of O to the obtained mixture, and stirring the mixture to obtain ZIF-67 powder. Among them, 2-methylimidazole and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 8: the mass concentration of 1,KOH substance 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 an aqueous solution, and the derived cobalt selenide/carbon composite material has excellent lithium storage performance. 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 simple synthetic strategy at low cost is crucial to accelerate 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 conversion reaction electrode material is widely concerned in the field of lithium ion batteries. One of the transition metal selenide-based materials is rich in resources, low in cost and large in theoretical lithium storage capacityThere is a wide range of interest in energy storage and conversion systems. For example, coSe 2 The 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 ·6H 2 Obtaining reaction liquid from the water solution of O, stirring the reaction liquid for 4-8 hours at room temperature, centrifuging, washing and drying to obtain ZIF-67 powder; the 2-methylimidazole and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 8:1,the mass concentration of KOH in the reaction solution is 0.1 to 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 -1 Raising 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 percent 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.
The preparation method of the ZIF-67 and the cobalt selenide/carbon electrode material derived from the ZIF-67 comprises the following steps: spreading selenium powder and the carbide obtained in the step 2) at two ends of the porcelain boat respectively 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 for selenizing in the atmosphere of inert gas, and heating the carbide at the 2 ℃ for min -1 Heating to 350 deg.C at heating rate, holding for 3 hr, and heating at 2 deg.C for min -1 Raising 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 results show that the reaction can be completed in 6 hours with a yield of 70 to 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 cobalt selenide and the carbon are uniformly compounded. 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 material at 100mA g prepared in examples 5 and 6 of the present invention -1 Cycling 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.
1. Preparation of ZIF-67 Material
Example 1:
firstly, sequentially adding KOH and 2-methylimidazole into deionized water, and performing ultrasonic stirring for 5 minutes and magnetic stirring for 10 minutes to obtain a mixed solution A; then adding Co (NO) 3 ) 2 ·6H 2 Solution 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 ·6H 2 The mass ratio of O is about 8:1,KOH in the reaction solution had a mass concentration of 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 1000nm.
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 -1 In the process, the morphology of the obtained product still takes a two-dimensional leaf-like structure as the main part, but the thickness of the sheet prepared by the method is larger than that of the sheet prepared 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 -1 KOH 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 showed that the resulting material was a three-dimensionally 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 -1 The KOH of (3) is more favorable for ZIF-67 to grow into a regular and uniform three-dimensional polyhedral structure.
2. Preparation of 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 -1 Raising the temperature to 500 ℃ at the heating rate, preserving the heat for 1 hour, and naturally cooling to obtain a carbonized product. And then sequentially adding the 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 20Drying to obtain Co 0.85 A Se/C composite material.
FIG. 7 shows the prepared polyhedral ZIF-67 derived high performance Co 0.85 The XRD spectrogram of the Se/C composite material shows that in the diffraction peaks of the composite material, a broad peak positioned at about 25 degrees corresponds to the characteristic peak of amorphous carbon, and peaks positioned at 33.15 degrees, 44.9 degrees and 50.5 degrees respectively correspond to Co 0.85 The (101), (102) and (110) crystal planes of Se (JCPDS No. 52-1008). The other impurity peaks are characteristic peaks of the Se simple substance, which shows that the hydrothermal selenization product is Co 0.85 Se/C composite material.
FIG. 9 shows the prepared polyhedral ZIF-67 derived Co 0.85 SEM image of Se/C composite material, the result shows that Co 0.85 The 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 Co 0.85 The result of the cyclic voltammetry curve of the Se/C electrode in the lithium ion battery shows that two reduction peak positions are respectively positioned at 0.36 and 0.94V in the first discharge process and correspond to reduction reaction, namely Co 0.85 Conversion of Se to Co and Li 2 Se, 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 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 Co 0.85 Se/C electrodes in LIBs at 0.1A g -1 The charge-discharge diagram at current density shows an inclined discharge curveThe charge and discharge platform of the material can be consistent with the position of the oxidation and reduction peak of the cyclic voltammetry curve, and the discharge specific capacity of the first circle can be found to be 1593.3mAh g -1 The 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 Co 0.85 Se/C composites in LIBs at 0.1A g -1 Cycling performance plot at current density. Co can be seen 0.85 The Se/C cycle shows higher specific capacity (765 mAh g) after 200 circles -1 ). In addition, co is recycled 0.85 The 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 discharge 0.85 The 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 Co 0.85 The rate performance graph of the Se/C composite material as the lithium ion battery cathode material can show that Co 0.85 The Se/C composite material shows excellent rate capability, and the electrode has the rate capability of being used in 0.1, 0.2, 0.5, 1, 2 and 5A g -1 Average capacities at bottom 1123, 1045, 932, 822, 632 and 293mAh g -1 . When the current returns to 0.1A g -1 When it is used, its specific capacity is 972mAh g -1 The capacity retention rate is close to 90%.
FIG. 15 shows the prepared polyhedral ZIF-67 derivatized Co 0.85 The 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 platforms gradually increases with increasing current, even at 5A g -1 Under the high current density, the stable charge-discharge platform still exists, which shows that Co has a stable charge-discharge platform 0.85 The Se/C composite material has good structural stability.
It can be seen from FIG. 16 that the prepared polyhedral ZIF-67-derived Co 0.85 Electrochemical impedance spectroscopy of Se/C composite materials in LIBsThe graph shows that the curve is composed of a semicircle of the high frequency region and a diagonal line of the low frequency region, the semicircle represents the charge transfer resistance, and the diagonal line represents the ion diffusion process, and the electrode resistance is related to the semicircle of the high frequency region. Co can be seen 0.85 The 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:
respectively placing selenium powder and carbonized product (with mass ratio of 2:1) at upstream and downstream of tube furnace, and heating at 2 deg.C for min under inert gas atmosphere -1 Heating to 350 deg.C, holding for 3 hr, holding at 500 deg.C for 1 hr, and naturally cooling to obtain black and gray CoSe 2 a/C composite material.
FIG. 8 is a polyhedral ZIF-67 derivatized CoSe prepared 2 The 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-CoSe 2 (ortho, pnm, JCPDS No. 53-0449) and c-CoSe 2 (Cubic, pa-3, JCPDS No. 09-0234). The characteristic peaks at 30.8 degrees, 34.5 degrees, 36.0 degrees, 47.7 degrees, 65.0 degrees and 63.3 degrees respectively correspond to o-CoSe 2 The (101), (111), (120), (211), (311) and (122) planes of (A) and (B), and the peaks at 34.2 °, 37.6 °, 51.8 °, 56.5 °, 58.8 ° and 74.0 ° respectively correspond to c-CoSe 2 The (210), (211), (311), (230), (321), and (421) crystal planes of (a). Evidence of CoSe 2 The cobalt selenide in the/C composite material is a biphase coexisting composite material and comprises cubic CoSe 2 And quadrature phase CoSe 2
FIG. 10 shows the prepared polyhedral ZIF-67 derived high performance CoSe 2 The 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 CoSe 2 The application of the/C composite material in the lithium ion battery cathode material is L0.1A g -1 Current densityCycle performance graph below. It can be seen that the CoSe is obtained after 200 cycles 2 the/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 -1 Better stability and o-CoSe 2 And c-CoSe 2 The 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 a ZIF-67 derived cobalt selenide/carbon electrode material 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 ·6H 2 Obtaining reaction liquid from the water solution of O, stirring the reaction liquid for 4-8 hours at room temperature, centrifuging, washing and drying to obtain ZIF-67 powder; the 2-methylimidazole and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 8:1,the mass concentration of KOH in the reaction solution was 3mol L -1 Obtaining ZIF-67 powder with a three-dimensional polyhedral structure;
2) Putting the ZIF-67 powder obtained in the step 1) into a tube furnace, and heating the tube furnace at 2 ℃ for min in a nitrogen or argon atmosphere -1 Heating to 500 ℃ at the heating rate, and keeping for 1 hour for carbonization;
3) Selenizing the carbide obtained in the step 2).
2. The preparation method of the ZIF-67 derived cobalt selenide/carbon electrode material of claim 1, wherein the selenization process of step 3) is hydrothermal selenization: sequentially adding the carbide obtained in the step 2), sodium selenite and hydrazine hydrate with the mass percent 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.
3. The method of claim 1, wherein the selenization process of step 3) is gas selenization: spreading selenium powder and the carbide obtained in the step 2) at two ends of the porcelain boat respectively 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 for selenizing in the atmosphere of inert gas, and heating the carbide at the 2 ℃ for min -1 Heating to 350 deg.C at heating rate, holding for 3 hr, and heating at 2 deg.C for min -1 Raising 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110857324.7A CN113725432B (en) 2021-07-28 2021-07-28 ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110857324.7A CN113725432B (en) 2021-07-28 2021-07-28 ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67

Publications (2)

Publication Number Publication Date
CN113725432A CN113725432A (en) 2021-11-30
CN113725432B true CN113725432B (en) 2022-11-11

Family

ID=78674181

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110857324.7A Active CN113725432B (en) 2021-07-28 2021-07-28 ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67

Country Status (1)

Country Link
CN (1) CN113725432B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114725372A (en) * 2022-04-24 2022-07-08 西安建筑科技大学 Nickel-cobalt bimetallic telluride electrode material for sodium-ion battery and preparation method and application thereof
CN115020661B (en) * 2022-05-18 2023-08-04 吉林大学 Co with selenium vacancies 0.85 Se@WSe 2 Preparation method and application of nitrogen-doped carbon polyhedral composite material
CN114920210B (en) * 2022-05-25 2023-05-23 芜湖天弋能源科技有限公司 Negative electrode material of sodium ion battery and preparation method thereof
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
CN115000421A (en) * 2022-07-14 2022-09-02 易航时代(北京)科技有限公司 N, Se doped carbon nanofiber loaded CoSe organic framework composite material as well as preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102731538A (en) * 2012-06-07 2012-10-17 中国石油大学(华东) Preparation method of nanometer-to-micrometer scale zeolitic imidazolate frameworks (ZIFs)
CN105609322A (en) * 2015-12-21 2016-05-25 中南大学 Cobalt selenide/nitrogen-doped carbon composite material and preparation method and application therefor
JP2018162515A (en) * 2017-03-24 2018-10-18 トヨタ自動車株式会社 Cobalt selenide/titanium mesh electrode for water-electrolyzing oxygen generation, and producing method and application thereof
CN109037617A (en) * 2018-07-10 2018-12-18 厦门理工学院 A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application
CN109585823A (en) * 2018-11-23 2019-04-05 重庆文理学院 A kind of preparation method of cobaltous selenide/graphite carbon composite
CN110400926A (en) * 2019-08-07 2019-11-01 福州大学 A kind of nitrogen-doped carbon cladding two-phase is interspersed type nickel cobalt bimetallic selenides electrode material and preparation method thereof
CN110465312A (en) * 2019-05-30 2019-11-19 华南理工大学 A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110729486A (en) * 2019-10-09 2020-01-24 齐鲁工业大学 Preparation method of elemental cobalt composite nitrogen-doped carbon high-efficiency oxygen reduction/oxygen precipitation catalyst
CN110853937A (en) * 2019-11-29 2020-02-28 江苏理工学院 Preparation method of nickel-cobalt bimetallic selenide/carbon composite for supercapacitor
CN111530409A (en) * 2020-05-12 2020-08-14 湖南垚恒环境科技有限公司 Nitrogen-doped porous carbon material derived from zeolite imidazole framework material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102731538A (en) * 2012-06-07 2012-10-17 中国石油大学(华东) Preparation method of nanometer-to-micrometer scale zeolitic imidazolate frameworks (ZIFs)
CN105609322A (en) * 2015-12-21 2016-05-25 中南大学 Cobalt selenide/nitrogen-doped carbon composite material and preparation method and application therefor
JP2018162515A (en) * 2017-03-24 2018-10-18 トヨタ自動車株式会社 Cobalt selenide/titanium mesh electrode for water-electrolyzing oxygen generation, and producing method and application thereof
CN109037617A (en) * 2018-07-10 2018-12-18 厦门理工学院 A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application
CN109585823A (en) * 2018-11-23 2019-04-05 重庆文理学院 A kind of preparation method of cobaltous selenide/graphite carbon composite
CN110465312A (en) * 2019-05-30 2019-11-19 华南理工大学 A kind of self-supporting carbon cloth load cobaltous selenide nickel nanowire preparation method and application
CN110400926A (en) * 2019-08-07 2019-11-01 福州大学 A kind of nitrogen-doped carbon cladding two-phase is interspersed type nickel cobalt bimetallic selenides electrode material and preparation method thereof

Also Published As

Publication number Publication date
CN113725432A (en) 2021-11-30

Similar Documents

Publication Publication Date Title
CN113725432B (en) ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67
CN110364693B (en) Nano three-dimensional conductive framework/MnO 2 Preparation method of composite structure material and application of composite structure material in zinc battery anode
CN111952572B (en) Cobalt-nickel bimetallic nitrogen-doped carbon composite material containing single-atom active sites
Alsamet et al. Synthesis and characterization of nano-sized LiFePO4 by using consecutive combination of sol-gel and hydrothermal methods
CN106654221A (en) Three-dimensional porous carbon-coated zinc selenide material for lithium ion battery anodes and preparation method of material
CN108314092B (en) Foam nickel loaded nano rod-shaped cobalt molybdate and preparation method and application thereof
CN106887575A (en) A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery
CN112290022B (en) Lithium ion battery anode lithium supplement additive and preparation method and application thereof
CN109817962A (en) A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method of phenolic resin modification
CN103400980A (en) Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof
CN113793932B (en) Double-layer carbon-coated cobalt-based/cobalt-based chalcogen composite electrode material, preparation method and application
CN113809323A (en) Hollow carbon shell embedded with metal sulfide and preparation method and application thereof
CN111463406B (en) Preparation method of cobalt-doped zinc-based metal selenide composite electrode for lithium ion battery
CN116936771A (en) Hollow spherical shell structure ferric sodium sulfate composite positive electrode material, preparation method and sodium ion battery
CN115036505B (en) Carbon-coated germanium composite anode material for lithium ion battery and preparation method and application thereof
CN110600710A (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN113851620B (en) Potassium ion battery cathode composite material with multi-stage heterostructure and preparation method thereof
CN114695861B (en) Preparation method of sulfur and nitrogen co-doped porous carbon material, prepared carbon material and application thereof
Yanan et al. Co0. 85Se nanosheet anchored on carbon fibers as anode materials for high-performance flexible Li-ion batteries
CN110931789A (en) Preparation method of carbon nanosheet, positive electrode material and preparation method thereof
CN113745475B (en) Graphene/iron diselenide composite material for lithium ion battery cathode material and preparation method thereof
CN115490213B (en) VSe derived from metal-organic frameworks 2 Material, preparation method and application thereof
CN116779831B (en) Sea urchin structure electrode material, preparation method and application thereof in battery
CN113675384B (en) Nano titanium dioxide/graphene negative electrode material and preparation method thereof
CN106450268A (en) Porous trimanganese tetraoxide/graphene composite material and preparation method therefor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant