CN108190963B - Multistage hollow CoFe2O4Material, CoFe2O4Preparation method and application of/C composite material - Google Patents
Multistage hollow CoFe2O4Material, CoFe2O4Preparation method and application of/C composite material Download PDFInfo
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Abstract
The invention provides a method for preparing multi-stage hollow CoFe from coordination polymer2O4The method for preparing the material and the composite material thereof comprises the following steps: firstly, preparing a multi-stage hollow ferrocenyl coordination polymer (Co-Fc-Hcps) by using a cobalt salt and ferrocene dicarbamate through a solvothermal method; preparing multi-stage hollow CoFe by using high-temperature calcination method of prepared Co-Fc-Hcps coordination polymer in air atmosphere2O4A material; CoFe is obtained by stirring with dopamine hydrochloride and high-temperature calcination in nitrogen atmosphere2O4@ C multi-stage hollow composite material. The reaction steps of the invention are simple and convenient to operate and environment-friendly, and the equipment requirement is low. Compared with the prior report, the CoFe with the secondary nano rod-like structure2O4The @ C hollow sphere composite material has wide application prospect in the aspects of being used as a novel energy storage electrode material, magnetic application and the like.
Description
Technical Field
The invention relates to a multi-stage hollow CoFe2O4A preparation method of the composite material and application of the composite material in the electrode material of the lithium ion battery.
Background
With the widespread use of electronic devices, people have higher and higher requirements for energy storage of batteries. Therefore, a great deal of research workers have been devoted to research on electrode materials to improve the storage performance of batteries, and metal oxides and metal hydroxides are considered as significant electrode materials due to their high theoretical capacity. Research results show that cobalt ferrite and composite material thereof have higher specific capacity as lithium battery electrode material, and Hui et al prepared CoFe by adding cobalt nitrate and ferric nitrate into graphene solution through hydrothermal method2O4The specific capacity of the composite material with the graphene is 100 mA g-1At time of 910 mAhg-1（Hui X, Zhu D, Fu Y, et al. CoFe2O4-graphene nanocomposite as a high-capacity anode material for lithium-ion batteries[J]Electrochimica Acta,2012, 83(12): 166-174). The subject group of Guo utilizes Prussian blue to synthesize cobalt iron MOF, then synthesizes cubic cobalt ferrite material by a calcination conversion method, and under the long circulation of current density of 1.0C, the specific capacity is 1043 mAhg-1（Guo H, Li T, Chen W, et al. General design of hollow porous CoFe2O4nanocubes from metal-organic frameworks with extraordinary lithium storage[J]Nanoscale, 2014, 6(24): 15168). Ren and other composite materials of cobalt ferrite and carbon obtained by physical mixing and high-temperature calcination of ferrocene and cobaltocene at 100 mA g-1The lower specific capacity is 656 mAh g-1（Ren S, ZhaoX, Chen R, et al. A facile synthesis of encapsulated CoFe2O4, into carbonnanofibres and its application as conversion anodes for lithium ion batteries[J]Journal of Power Sources, 2014, 260(7): 205-210). Li's topic group prepared graded porous microsphere cobalt ferrite material by hydrothermal and calcination method using cobalt sulfate, ferric sulfate and sucrose, which is 2A g-1The lower energy can reach 406 mAh g-1（Shouli, Aihua, Ranran, et al. Hierarchical porous metal ferriteball-in-ball hollow spheres: General synthesis, formation mechanism, and highperformance as anode materials for Li-ion batteries[J]Nano-research (english edition), 2014, 7(8): 1116-1127.). Related reports show that the methods for synthesizing cobalt ferrite mainly comprise a hydrothermal method, a calcination method and an MOF (metal-organic framework) conversion method, but the synthesized material does not contain secondary nanostructures.
Disclosure of Invention
This patent first refers to Huo J et al (Huo J, Wang L, Irran E, et al, Synthesis, chromatography and magnetic properties of hollow microspheres with micro-meso shells assembled from cobalt-based coordination polymers [ J ]. Journal of Colloid & Interface Science, 2012, 367(1): 92-100.) to synthesize a multi-stage hollow cobalt-ferrocene coordination polymer (Co-Fc-Hcps) coordination polymer, which is then converted into a cobalt ferrite hollow sphere containing a secondary nanostructure by high temperature calcination, and further wrapped with a layer of carbon. The spherical shell has a unique secondary nano structure, so that the spherical shell has good electricity storage performance, and has important significance and application value for development and research of the spherical shell.
In order to achieve the purpose, the invention adopts the technical scheme that:
multistage hollow CoFe2O4The preparation method of the material comprises the following steps:
firstly, preparing a precursor which is a multi-stage hollow Co-Fc-Hcps coordination polymer;
secondly, calcining the multistage hollow Co-Fc-Hcps coordination polymer prepared in the first step in air atmosphere to obtain multistage hollow CoFe2O4A material.
Preferably, the calcination condition in the second step is calcination at 350-550 ℃ for 3h, and the heating rate is 3 ℃/min.
Preferably, the specific process for preparing the precursor in the first step is as follows: respectively dissolving 1,1 '-ferrocene dicarboxylic acid and a cobalt salt compound in DMF (dimethyl formamide) or DMF (dimethyl formamide) aqueous solution, uniformly stirring, then adding the cobalt salt solution into the 1, 1' -ferrocene dicarboxylic acid solution, uniformly stirring, transferring the mixed solution into a reaction kettle, reacting the reaction kettle at 125 ℃ for 12-20 h, centrifuging after the reaction is finished, cleaning with the DMF or DMF aqueous solution until the solution is clear, and drying to obtain the Co-Fc-Hcps coordination polymer.
Preferably, in the specific process of preparing the precursor in the first step, the aqueous solution of DMF is obtained by mixing DMF and water according to a volume ratio of 1: 1.
Preferably, in the specific process of preparing the precursor in the first step, the cobalt salt compound is one of cobalt nitrate hexahydrate, cobalt chloride hexahydrate, cobalt sulfate and cobalt acetate.
Preferably, the mass ratio of the 1, 1' -ferrocene bibenzoic acid to the cobalt salt compound in the specific process of preparing the precursor in the first step is (0.5-1): 1.
Multistage hollow CoFe2O4The preparation method of the @ C composite material comprises the following steps:
adding dopamine hydrochloride and CoFe prepared in the way into tris (hydroxymethyl) aminomethane buffer solution2O4Continuously stirring for 3h, centrifuging, washing the solid with distilled water and ethanol respectively, drying at 65 ℃ for 12h, and calcining the dried solid in nitrogen atmosphere to obtain the multilevel hollow CoFe2O4@ C composite material.
Preferably, the calcination condition is calcination at 350-550 ℃ for 3h, and the heating rate is 3 ℃/min. In the embodiment of the invention, the calcination is carried out at 450 ℃, but the calcination temperature in the range of 350-550 ℃ is within the protection range of the invention.
Preferably, the dopamine hydrochloride and CoFe2O4The mass ratio of (1) to (0.2). Further preferably, the dopamine hydrochloride and CoFe2O4The mass ratio of (1: 2) and the concentration of dopamine hydrochloride in the mixed solution before centrifugation is 0.4g/L, and the ratio of CoFe2O4The concentration of (B) was 0.8 g/L.
Preferably, the concentration of the tris (hydroxymethyl) aminomethane buffer solution is 0.1 mol/L.
The multi-stage hollow CoFe2O4Material, CoFe2O4The application of the @ C composite material as an electrode material in a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a multi-stage hollow CoFe2O4The preparation method of the sphere is obtained by taking the cobalt-ferrocene coordination polymer as a precursor and calcining at high temperature, the process is simple, the whole reaction process of the preparation of the precursor is carried out in DMF, other additives are not required to be added, and the calcining method has simple process and low cost and is easy for industrial production; in addition, the preparation method can obtain different cobalt ferrite three-dimensional composite materials by regulating and controlling process conditions.
Drawings
FIG. 1 shows a two-stage nanostructure prepared in example 4 of the present inventionCoFe2O4Scanning electron microscope images of the hollow materials;
FIG. 2 shows CoFe with two-stage nanorod structure obtained in example 5 of the present invention2O4Scanning electron microscope images of @ C hollow composite materials;
FIG. 3 shows CoFe with two-stage nanorod structure obtained in example 5 of the present invention2O4X-ray diffraction patterns for @ C hollow composites;
FIG. 4 shows CoFe with two-stage nanorod structure obtained in example 5 of the present invention2O4@ C hollow composite material cyclic voltammogram;
FIG. 5 shows CoFe with two-stage nanorod structure obtained in example 5 of the present invention2O4The charging and discharging graphs of the @ C hollow composite material under different multiplying factors.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
This example for the preparation of CoFe2O4Comprises the following steps:
(1) synthesizing a precursor multistage hollow Co-Fc-Hcps coordination polymer: 0.2000g (1.1mmol) of 1, 1' -ferrocene dicarboxylic acid and 0.2124g (1.1mmol) of cobalt nitrate hexahydrate are weighed out and dissolved in 18mL of DMF/H respectively2And (3) adding a cobalt nitrate solution into the 1, 1' -ferrocene biscarboxylic acid solution dropwise after uniformly stirring the mixture in the O (the volume ratio of the two is 1: 1). The mixed solution is stirred evenly and transferred to a 50mL reaction kettle to react for 20H at 125 ℃, centrifuged and added with DMF/H2Cleaning O (the volume ratio of the two is 1:1) until the O is clear, and blowing and drying the O for 15 hours at the temperature of 80 ℃ to obtain a Co-Fc-Hcps coordination polymer;
(2) calcining the obtained Co-Fc-Hcps coordination polymer in a tubular furnace at 350 ℃ for 3h (3 ℃/min) to obtain CoFe2O4A material.
Example 2
This example for the preparation of CoFe2O4Comprises the following steps:
(1) synthesizing a precursor multistage hollow Co-Fc-Hcps coordination polymer: 0.5086g (A) are weighed1.8mmol) of 1, 1' -ferrocene biscarboxylic acid and 0.4326g (1.8mmol) of cobalt nitrate hexahydrate were dissolved in 18mL of DMF/H, respectively2And (3) adding a cobalt nitrate solution into the 1, 1' -ferrocene biscarboxylic acid solution dropwise after uniformly stirring the mixture in the O (the volume ratio of the two is 1: 1). The mixed solution is stirred evenly and then transferred to a 50mL reaction kettle to react for 20H at 125 ℃, centrifuged and added with DMF/H2Cleaning O (the volume ratio of the two is 1:1) until the O is clear, and blowing and drying the O for 15 hours at the temperature of 80 ℃ to obtain a Co-Fc-Hcps coordination polymer;
(2) calcining the obtained Co-Fc-Hcps coordination polymer in a tubular furnace at 450 ℃ for 3h (3 ℃/min) to obtain CoFe2O4A material.
Example 3
This example for the preparation of CoFe2O4Comprises the following steps:
(1) synthesizing a precursor multistage hollow Co-Fc-Hcps coordination polymer: 0.5086g (1.8mmol) of 1,1 '-ferrocene dicarboxylic acid and 0.4326g (1.8mmol) of cobalt chloride hexahydrate are weighed out and respectively dissolved in 18mL of DMF, and after uniform stirring, the cobalt chloride solution is added dropwise into the 1, 1' -ferrocene dicarboxylic acid solution. Uniformly stirring the mixed solution, transferring the mixed solution to a 50mL reaction kettle, reacting for 12h at 125 ℃, centrifuging, cleaning with DMF (dimethyl formamide) to be clear, and drying by blowing at 80 ℃ for 15h to obtain a Co-Fc-Hcps coordination polymer;
(2) calcining the obtained Co-Fc-Hcps coordination polymer in a tubular furnace at 550 ℃ for 3h (3 ℃/min) to obtain hollow CoFe2O4A material.
Example 4
This example for the preparation of CoFe2O4Comprises the following steps:
(1) synthesizing a precursor multistage hollow Co-Fc-Hcps coordination polymer: 0.5086g (1.8mmol) of 1,1 '-ferrocene dicarboxylic acid and 0.4326g (1.8mmol) of cobalt chloride hexahydrate are weighed out and respectively dissolved in 18mL of DMF, and after uniform stirring, the cobalt chloride solution is added dropwise into the 1, 1' -ferrocene dicarboxylic acid solution. Uniformly stirring the mixed solution, transferring the mixed solution to a 50mL reaction kettle, reacting for 12h at 125 ℃, centrifuging, cleaning with DMF (dimethyl formamide) to be clear, and drying by blowing at 80 ℃ for 15h to obtain a Co-Fc-Hcps coordination polymer;
(2) the obtained Co-FcCalcining the-Hcps coordination polymer in a tubular furnace at 450 ℃ for 3h (3 ℃/min) to obtain hollow CoFe with a secondary nanostructure2O4A material.
Secondary nanostructured hollow CoFe prepared in this example2O4The scanning electron micrograph of the material is shown in FIG. 1, and the CoFe prepared is seen from FIG. 12O4The hollow sphere is a hollow shell composed of nano sheets.
Example 5
This example for the preparation of CoFe2O4The process of @ C composite includes the steps of:
(1) to 100mL of tris (hydroxymethyl) aminomethane buffer solution (10 mmol) were added 40mg of dopamine hydrochloride and 80mg of CoFe2O4Stirring for 3h, centrifuging to obtain black solid, washing with distilled water and ethanol for 3 times, and drying at 65 deg.C for 12 h.
(2) The obtained CoFe2O4Calcining the compound with dopamine hydrochloride at 450 ℃ for 3h (3 ℃/min) in a tubular furnace under the protection of nitrogen to prepare the hollow CoFe with the secondary nanostructure2O4@ C composite material.
Secondary nanostructured hollow CoFe prepared in this example2O4As shown in FIG. 2, the scanning electron micrograph of the @ C composite material shows that the unique hollow structure of the material is not significantly changed when the material is coated with carbon in FIG. 2.
Hollow CoFe prepared by the invention2O4The composite material has a two-stage nano structure, shows excellent electrochemical capacity performance, rate capability and cycle performance when being used as an electrode material of a lithium ion battery, and has wide application prospect in the aspects of synthesizing a multi-stage structure and storing energy.
FIG. 3 shows the CoFe with two-stage nano structure2O4And CoFe2O4The X-ray diffraction pattern of @ C hollow three-dimensional composite material is compared with standard card, and the material prepared by said invention is just CoFe2O4And CoFe2O4@ C. FIG. 4 shows CoFe with two-stage nanorod structure prepared according to the present invention2O4@ C hollow composite material cyclic voltammogram; FIG. 5 shows the CoFe with two-stage nanorod structure2O4The charging and discharging graphs of the @ C hollow composite material under different multiplying factors. The experimental results of fig. 4 and 5 show that CoFe with two-stage nanorod structure prepared by the invention2O4The @ C hollow composite material has excellent electrochemical performance in the aspect of preparing electrode materials of lithium ion batteries.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. Hollow CoFe with two-stage nano rod-like structure for lithium ion battery electrode material2O4The preparation method of the @ C composite material is characterized by comprising the following steps of:
(1) synthesizing a precursor multistage hollow Co-Fc-Hcps coordination polymer: weighing 1.8mmol of 1,1 '-ferrocene dicarboxylic acid and 1.8mmol of cobalt chloride hexahydrate, respectively dissolving in 18mL of DMF, stirring uniformly, and then dropwise adding the cobalt chloride solution into the 1, 1' -ferrocene dicarboxylic acid solution; uniformly stirring the mixed solution, transferring the mixed solution to a 50mL reaction kettle, reacting for 12h at 125 ℃, centrifuging, cleaning with DMF (dimethyl formamide) to be clear, and drying by blowing at 80 ℃ for 15h to obtain a Co-Fc-Hcps coordination polymer;
(2) heating the obtained Co-Fc-Hcps coordination polymer to 450 ℃ at the speed of 3 ℃/min in a tubular furnace, and preserving heat for 3h to obtain hollow CoFe with a two-stage nano rod-like structure2O4A material;
(3) 40mg of dopamine hydrochloride and 80mg of CoFe are added to 100mL of 0.1mol/L tris (hydroxymethyl) aminomethane buffer solution2O4Continuously stirring for 3h, centrifuging to obtain black solid, washing with distilled water and ethanol for 3 times, and drying at 65 deg.C for 12 h;
(4) the obtained CoFe2O4And dopa hydrochlorideHeating the amine compound to 450 ℃ at the speed of 3 ℃/min under the protection of nitrogen in a tube furnace, calcining for 3h to obtain the hollow CoFe with the two-stage nano rod-like structure2O4@ C composite material.
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| CN109449379B (en) * | 2018-09-12 | 2021-05-11 | 华南师范大学 | Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof |
| CN112151804B (en) * | 2020-09-27 | 2022-10-04 | 广州大学 | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof |
| CN112599743B (en) * | 2020-12-15 | 2022-06-07 | 西安交通大学 | Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof |
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