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 PDFInfo
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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
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.
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| 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 |
| CN114937764B (en) * | 2022-05-27 | 2024-03-15 | 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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