CN109473651B - Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material - Google Patents
Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material Download PDFInfo
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Abstract
The invention discloses a method for synthesizing Co by deriving ZIF-67 polyhedron8FeS8A method of N-C polyhedral nano material. ZIF-67 is taken as a precursor, is derivatized into a hollow Co/N-C polyhedron, and then Fe grows on the inner surface of the hollow Co/N-C polyhedron3O4Nanoparticles, Co/N-C @ Fe forming polyhedral nanomaterials3O4Then the mixture is vulcanized and calcined at high temperature in inert gas to form Co8FeS8the/N-C polyhedral nano material. The method has simple and convenient process operation process, can effectively control the stoichiometric ratio of the multi-component material, obtains the nano composite material with uniform size, uniform distribution and good shape control, and obtains the Co8FeS8When the/N-C polyhedral nano material is used as a lithium ion battery cathode material, the nitrogen-doped amorphous carbon can improve the conductivity of the composite material, and Co8FeS8The confinement is in the nitrogen-doped carbon layer, and the volume effect in the charge and discharge process can be buffered, so that the composite material has better cycle stability and rate capability.
Description
Technical Field
The invention belongs to the technical field of production of lithium ion battery cathode materials, and particularly relates to a bimetallic sulfide Co8FeS8a/N-C polyhedral nano material and a synthetic method thereof.
Background
Metal organic framework Materials (MOFs) are coordination polymers which have been developed rapidly in recent decades, and refer to crystalline porous materials with periodic network structures formed by self-assembly of transition metal ions and organic ligands. It has high porosity, low density, large specific surface area and poresThe porous material has the advantages of regularity, adjustable pore diameter, diversity and tailorability of topological structures and the like, has a three-dimensional pore structure, generally takes metal ions as connecting points, is supported by organic ligands to form space 3D extension, is another important novel porous material except zeolite and carbon nano tubes, and is widely applied to catalysis, energy storage and separation. Currently, MOFs have become an important research direction for many chemical branches of inorganic chemistry, organic chemistry, and the like. The metal organic framework derivative has been used as a series of composite materials in the fields of electrocatalysis, photocatalysis, biological medicine carrying, lithium ion battery cathode materials and the like, and has the function of adjustable pore diameter controllability, so that the metal organic framework derivative is superior to the traditional porous material. Transition metal sulfides are an important class of functional materials that have emerged in recent years. The transition metal sulfide is considered to be an anode material with great application prospect in the lithium ion battery due to the advantages of high theoretical capacity, high natural abundance, low cost, easy synthesis and the like. To date, a large number of transition metal sulfides have included cobalt sulfides, iron sulfides, manganese sulfides, nickel sulfides, and the like. The metal sulfides have excellent electrochemical performance as anode materials of lithium ions. Among these transition metal sulfides, Co9S8It has received much attention because of its excellent electrochemical properties. And when the MOFs contain two different metal ions, the electrochemical performance can be effectively improved. The bimetallic sulfide can generate more redox reactions due to the increase of charge transfer of metal ions between binary ions, and shows more excellent electrochemical performance. In the invention, a bimetallic sulfide Co is synthesized8FeS8the/N-C polyhedral nano material shows excellent electrochemical performance through the synergistic effect of bimetallic ions of Co and Fe when being used as an anode material of a lithium ion battery.
Disclosure of Invention
The invention aims to provide Co synthesized by deriving ZIF-67 polyhedron8FeS8a/N-C polyhedral nano material and a method thereof.
The technical solution for realizing the purpose of the invention is as follows: co derivatized from ZIF-67 polyhedra8FeS8The method of the/N-C polyhedral nano material comprises the following steps:
1) preparation of hollow composite nano material of simple substance cobalt/nitrogen doped carbon (hollow Co/N-C polyhedron)
Co(NO3)2·6H2Dissolving O and 2-methylimidazole in a methanol solution respectively, stirring at room temperature, centrifugally washing after the reaction is finished, obtaining a solid phase, and drying to obtain a ZIF-67 polyhedral nano material;
calcining the obtained ZIF-67 polyhedral nano material at a certain temperature under the protection of inert gas to form a hollow Co/N-C polyhedral nano material.
2) Preparation of Co8FeS8N-C polyhedral nano material
Dispersing the obtained hollow Co/N-C polyhedral nano material in oleylamine and dibenzyl ether, and carrying out high-temperature liquid phase reaction for a period of time under the protection of inert gas to obtain Co/N-C @ Fe3O4A polyhedral nano-material;
the obtained Co/N-C @ Fe3O4Adding sulfur powder into polyhedral nano material under inert gas and calcining to obtain Co8FeS8the/N-C polyhedral nano material.
Preferably, in the step 1), the prepared hollow Co/N-C polyhedron has uniform appearance and stable structure, and Co/N-C @ Fe with good appearance is prepared for subsequent process3O4Polyhedral nanomaterials provide advantages.
Preferably, in the step 1), Co (NO)3)2·6H2The ratio of the amounts of O and 2-methylimidazole substances is 1: 4. under the condition, the ZIF-67 polyhedral nano material with uniform appearance can be obtained.
Preferably, in the step 1), Co (NO)3)2·6H2The reaction time of O and 2-methylimidazole is 24h, and the size of ZIF-67 is mainly adjusted.
Preferably, in the step 1), the calcining temperature for preparing the hollow Co/N-C is 500-900 ℃, and the reaction time is 0.5-5 h. Is used for adjusting the crystal form and the graphitization degree of the hollow Co/N-C polyhedron and the integrity of the polyhedron structure.
Preferably, in the step 2), the mass ratio of the hollow Co/N-C polyhedron to the iron acetylacetonate is 1: 0.1-1, and the volume ratio of the dibenzyl ether to the oleylamine is 1: 0.1-10. Mainly for regulating Fe3O4Amount of nanoparticles grown in situ on hollow Co/N-C polyhedra and Fe3O4And (4) morphology.
Preferably, in the step 2), the reaction temperature of the hollow Co/N-C polyhedron and the iron acetylacetonate in the mixed solvent of the oleylamine and the dibenzyl ether is 200-350 ℃. Mainly for regulating Fe3O4The reaction rate of the nano particles growing in situ on the hollow Co/N-C polyhedron and the size of the ferroferric oxide nano particles. The reaction time is 30 min-24 h. Mainly to adjust the completeness of the reaction and the size of the nanoparticles.
Preferably, in the step 2), the structure is kept intact, and a good structure is presented, Fe3O4The nano-particles grow on the inner and outer surfaces of the hollow Co/N-C polyhedron.
Preferably, in the step 2), the obtained Co/N-C @ Fe3O4The mass ratio of the polyhedral nano material to the S powder is 1: 0.5-5, the temperature is 500-900 ℃, the calcining time is 0.5-5 h, and the heating rate is 1-10 ℃ per minute-1Heating under argon. Cooling at room temperature to obtain Co8FeS8the/N-C polyhedral nano material. Co8FeS8the/N-C polyhedral structure can form a carbon layer with excellent conductivity, namely Co with uniform appearance can be obtained8FeS8the/N-C polyhedral nano material.
Compared with the prior art, the invention has the following remarkable advantages: (1) the preparation cost is low, the operation process is simple and convenient, and the materials required in the reaction process are low in toxicity and harmless: (2) co8FeS8The structure of the/N-C polyhedral nano material enables the volume effect generated in the lithiation/delithiation process of the material to be effectively relieved, and the active material to be effectively protected in large current and long circulation.
Drawings
FIG. 1 is a transmission electron microscope image of a ZIF-67 polyhedron of different magnification prepared in the first embodiment of the present invention.
FIG. 2 is a transmission electron microscope image of hollow Co/N-C polyhedrons of different magnifications prepared in the first embodiment of the invention.
FIG. 3 shows Co prepared in the first embodiment of the present invention with different magnification8FeS8Transmission electron microscope picture of/N-C polyhedral nano material.
FIG. 4 shows Co prepared in the first embodiment of the present invention8FeS8XRD pattern of/N-C polyhedral nano material.
FIG. 5 shows Co prepared in the first embodiment of the present invention8FeS8Performance diagrams of lithium ion batteries of the N-C polyhedral nano materials under different multiplying powers.
FIG. 6 shows the preparation of Co in the first embodiment of the present invention8FeS8The current density of the lithium ion battery made of the/N-C polyhedral nano material is 1A g-1Long cycle performance plot below.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail below with reference to the accompanying drawings and embodiments.
Cobalt sulfide and iron sulfide both have higher theoretical lithium intercalation specific capacity. Co8FeS8When the/N-C polyhedral nano material is used as a lithium ion battery cathode material, the nitrogen-doped amorphous carbon can improve the conductivity of the composite material, and Co8FeS8The confinement is in the nitrogen-doped carbon layer, so that the volume effect in the charge-discharge process can be buffered, and the composite material has better cycle stability and rate capability. Thus, Co was derivatized from ZIF-67 polyhedra8FeS8the/N-C polyhedral nano material is a lithium ion negative electrode material with application prospect. Hollow Co/N-C polyhedron is used as raw material and template for subsequent reaction, or other shape and different nanometer material can be used as template, such as Zn/N-C polyhedron structure obtained by calcining ZIF-8.
Example 1:
1) synthesis of elemental cobalt/Nitrogen-doped carbon hollow composite nanomaterial (hollow Co/N-C polyhedron)
Co(NO3)2·6H2And respectively dissolving 291 mg of O and 328 mg of 2-methylimidazole in 25 ml of methanol solution, mixing, stirring at room temperature for 24h, centrifuging at 6000 rpm for 5 min after the reaction is finished, washing with ethanol for 4 times, obtaining a solid phase, and drying at 60 ℃ for 6h to form the ZIF-67 polyhedral nano material.
And putting the ZIF-67 polyhedral nano material into a tubular furnace, calcining for 0.5h at 900 ℃ in argon, and heating at the rate of 1 ℃/min to obtain a hollow Co/N-C polyhedron.
2) Synthesis of Co/N-C @ Fe3O4Polyhedral nano material
Dispersing 100mg of the obtained hollow Co/N-C polyhedron nano material and 10mg of iron acetylacetonate (the mass ratio of the hollow Co/N-C polyhedron to the iron acetylacetonate is 1: 0.1) in 1ml of dibenzyl ether and 10ml of oleylamine, introducing argon, maintaining the temperature at 120 ℃ for removing water for 1h, then introducing the argon, heating to 200 ℃, maintaining the temperature at 200 ℃ and reacting for 24 h. After the reaction is finished, cooling to room temperature. Centrifuging at 5000 rpm for 5 min, washing with ethanol for 3 times, collecting solid phase, and drying at 60 deg.C for 6 hr. Thus obtaining Co/N-C @ Fe3O4Polyhedral nano materials.
3) Synthesis of Co8FeS8N-C polyhedral nano material
The obtained Co/N-C @ Fe3O4Placing 100mg of polyhedral nano material and 50mg of S powder on two different positions of quartz boat respectively, placing the quartz boat containing S powder on the upstream of furnace, calcining at 900 deg.C for 0.5h, and heating at 1 deg.C/min-1Heating under argon. Cooling at room temperature to obtain Co8FeS8the/N-C polyhedral nano material.
Example 2:
1) synthesis of elemental cobalt/Nitrogen-doped carbon hollow composite nanomaterial (hollow Co/N-C polyhedron)
Co(NO3)2·6H2Dissolving O291 mg and 2-methylimidazole 328 mg in 25 ml methanol solution respectively, mixing, stirring at room temperature for 24h, centrifuging at 6000 rpm for 5 min after reaction, washing with ethanol for 4 times, drying at 60 deg.C for 6h to obtain ZIF-67 polyvidoneA nano-material of a body.
And (3) putting the ZIF-67 polyhedral nano material into a tube furnace, calcining for 2h at 800 ℃ in argon at the heating rate of 2 ℃/min, and obtaining the hollow Co/N-C polyhedron.
2) Synthesis of Co/N-C @ Fe3O4Polyhedral nano material
Dispersing 100mg of the obtained hollow Co/N-C polyhedron nano material and 50mg of iron acetylacetonate (the mass ratio of the hollow Co/N-C polyhedron to the iron acetylacetonate is 1: 0.5) in 5ml of dibenzyl ether and 5ml of oleylamine, introducing argon, maintaining the temperature at 120 ℃ for removing water for 1h, then introducing the argon, heating to 300 ℃, and keeping the temperature at 300 ℃ for reacting for 1 h. After the reaction is finished, cooling to room temperature. Centrifuging at 5000 rpm for 5 min, washing with ethanol for 3 times, collecting solid phase, and drying at 60 deg.C for 6 hr. Thus obtaining hollow Co/N-C @ Fe3O4Polyhedral nano materials.
3) Synthesis of Co8FeS8N-C polyhedral nano material
The obtained Co/N-C @ Fe3O4Placing 100mg of polyhedral nano material and 100mg of S powder on two different positions of quartz boat respectively, placing the quartz boat containing S powder on the upstream of furnace, heating at 800 deg.C for 2 hr, and heating at 2 deg.C/min-1Heating under argon. Cooling at room temperature to obtain Co8FeS8the/N-C polyhedral nano material.
Example 3:
1) synthesis of elemental cobalt/Nitrogen-doped carbon hollow composite nanomaterial (hollow Co/N-C polyhedron)
Co(NO3)2·6H2And respectively dissolving 291 mg of O and 328 mg of 2-methylimidazole in 25 ml of methanol solution, mixing, stirring at room temperature for 24h, centrifuging at 6000 rpm for 5 min after the reaction is finished, washing with ethanol for 4 times, obtaining a solid phase, and drying at 60 ℃ for 6h to form the ZIF-67 polyhedral nano material.
And (3) putting the ZIF-67 polyhedral nano material into a tube furnace, calcining for 5h at 500 ℃ in argon at a heating rate of 10 ℃/min to obtain a hollow Co/N-C polyhedron.
2) Synthesis of Co/N-C @ Fe3O4Polyhedral nano material
Dispersing 100mg of the obtained hollow Co/N-C polyhedral nano material and 100mg of iron acetylacetonate (the mass ratio of the hollow Co/N-C polyhedral to the iron acetylacetonate is 1: 1) in 10ml of dibenzyl ether and 1ml of oleylamine, introducing argon, maintaining the temperature of 120 ℃ for removing water for 1h, then introducing the argon, heating to 350 ℃, and keeping the temperature at 350 ℃ for reacting for 0.5 h. After the reaction is finished, cooling to room temperature. Centrifuging at 5000 rpm for 5 min, washing with ethanol for 3 times, collecting solid phase, and drying at 60 deg.C for 6 hr. Thus obtaining hollow Co/N-C @ Fe3O4Polyhedral nano materials.
3) Synthesis of Co8FeS8N-C polyhedral nano material
The obtained hollow Co/N-C @ Fe3O4Placing 100mg of polyhedral nano material and 500mg of S powder on two different positions of quartz boat respectively, placing the quartz boat containing S powder on the upstream of furnace, heating at 500 deg.C for 5 hr, and heating at 10 deg.C/min-1Heating under argon. Cooling at room temperature to obtain Co8FeS8the/N-C polyhedral nano material.
And (3) product verification:
the hollow Co/N-C polyhedron prepared by the embodiment has the advantages that the particle size is about 300-500 nm, the wall thickness is about 40nm, a large number of mesopores are contained, and the structure has a very large specific surface area.
FIG. 1 is a transmission electron microscope image of a ZIF-67 polyhedron at different magnifications prepared by the method of the present invention. It can be seen from the figure that: the prepared product has the particle size of about 300-500 nm and a smooth surface.
FIG. 2 is a transmission electron microscope image of a hollow Co/N-C polyhedron prepared by the method of the present invention under different magnifications. It can be seen from the figure that: the prepared product has the particle size of about 300-500 nm and generates cobalt simple substance particles in a polyhedral way.
FIG. 3 shows Co prepared by the method of the present invention8FeS8Transmission electron microscope picture of/N-C polyhedral nano material. It can be seen from the figure that: the appearance is uniform, and the nano particles growing on the polyhedral structure can be clearly seen to be obviously enlarged.
FIG. 4 shows a schematic diagram of a method for manufacturing a semiconductor deviceCo prepared by the method8FeS8XRD pattern of/N-C polyhedral nano material. It can be seen from the figure that: co8FeS8The crystal form of the/N-C polyhedral nano material is good. Illustrating the successful recombination of our composite nanomaterials.
FIG. 5 shows the prepared Co8FeS8Performance diagrams of lithium ion batteries of the N-C polyhedral nano materials under different multiplying powers. Co8FeS8The current density of the negative electrode of the lithium ion battery made of the/N-C polyhedral nano material is respectively 0.1A g-1，0.2 A g-1，0.5 A g-1，1 A g-1，2 A g-1，5 A g-1，0.1 A g-1The specific capacity of the mass at 5A g can be seen from the figure-1While the temperature can still be kept at 390 mAh g-1Specific capacity of from 5A g-1To 0.1A g-1Can still return to 700 mAh g-1Thus Co8FeS8the/N-C polyhedral nano material has good rate capability when being used as a lithium ion battery cathode material.
FIG. 6 shows the prepared Co8FeS8Current density of the lithium ion battery made of the/N-C polyhedral nano material is 1A g-1Long cycle performance plot below. After circulating for 400 circles, 570 mAh g can be still maintained-1To illustrate, Co8FeS8the/N-C polyhedral nano material has good long-cycle performance when being used as a lithium ion battery cathode material. The reason for this may be due to unique Co8FeS8the/N-C polyhedral nano material is Co8FeS8The volume effect generated by the/N-C material in the process of lithium ion intercalation and deintercalation provides an effective buffer space.
The invention takes a hollow Co/N-C polyhedron obtained by ZIF-67 derivatization as a carrier, and carries out Fe on the inner and outer surfaces of the polyhedron template through the high-temperature pyrolysis of iron acetylacetonate in a high-temperature environment3O4In-situ growth of nano particles, high-temperature heating of sulfur powder in argon and calcination to form Co8FeS8the/N-C polyhedral nano material. The results show that unique Co8FeS8a/N-C polyhedral nanomaterial not only Co8FeS8The volume effect generated by the/N-C material in the lithium ion intercalation and deintercalation process provides effective buffer space, the specific surface area is improved, and Co is enabled to be8FeS8A large number of active sites of the/N-C are exposed, so that the rapid transmission of lithium ions is facilitated; Co/N-C @ Fe3O4The transition metal sulfide Co is obtained after the polyhedral material is added with sulfur and calcined8FeS8 The transition bimetal Fe and Co has higher specific capacity and rate capability and excellent cycling stability due to the synergistic effect of the/N-C polyhedral nano material and the transition bimetal Fe and Co; and Co8FeS8The structure of the/N-C polyhedral nano material enables the volume effect generated in the lithiation/delithiation process of the material to be effectively relieved, and the active material to be effectively protected in large current and long circulation. Thus, Co8FeS8the/N-C polyhedral nano material is a lithium ion battery cathode material with excellent performance and great application prospect.
Claims (10)
1. Synthesis of bimetallic sulfide Co8FeS8The method for preparing the/N-C polyhedral nano material is characterized by comprising the following steps:
1) calcining ZIF-67 at a certain temperature under the protection of inert gas to form a hollow Co/N-C polyhedral material;
2) dispersing the hollow Co/N-C polyhedral material and ferric acetylacetonate in a mixed solution of oleylamine and dibenzyl ether, and carrying out high-temperature liquid phase reaction on the obtained dispersion to obtain Co/N-C @ Fe3O4A step of polyhedral nano materials;
3) mixing Co/N-C @ Fe3O4Calcining the polyhedral nano material in inert gas in the presence of sulfur powder to obtain the Co8FeS8And a step of N-C polyhedral nano material.
2. The method of claim 1, wherein the ZIF-67 is obtained by dissolving cobalt nitrate and 2-methylimidazole in methanol, respectively, mixing and stirring at room temperature for reaction, centrifuging and washing after the reaction is completed, and drying the obtained solid phase.
3. The method of claim 2, wherein the ratio of the amounts of cobalt nitrate and 2-methylimidazole species is 1: 4 to 8.
4. The method of claim 1, wherein in step 1), the ZIF-67 is calcined at 500 to 900 ℃ for 0.5 to 5 hours in argon.
5. The method according to claim 1, wherein in the step 2), the mass ratio of the hollow Co/N-C polyhedral material to the iron acetylacetonate is 1: 0.1-1.
6. The method of claim 1, wherein in step 2), the volume ratio of the dibenzyl ether to the oleylamine is 1:0.1 to 10.
7. The method of claim 1, wherein in the step 2), the high temperature liquid phase reaction temperature is 200 to 350 ℃ and the reaction time is 30 min to 24 h.
8. The method of claim 1 wherein in step 3), Co/N-C @ Fe3O4The mass ratio of the polyhedral nano material to the sulfur powder is 1: 0.5-5.
9. The method according to claim 1, wherein in the step 3), the calcination temperature is 500 to 900 ℃ and the calcination time is 0.5 to 5 hours.
10. The method according to claim 1 or 9, wherein in the step 3), the temperature rise rate during the calcination is 1 to 10 ℃/min.
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