CN110342585B - Four-side hollowed-out CoFe2O4Nano material and preparation method and application thereof - Google Patents
Four-side hollowed-out CoFe2O4Nano material and preparation method and application thereof Download PDFInfo
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Abstract
Four-side hollowed-out CoFe2O4A nano material and a preparation method and application thereof belong to the field of materials, and in order to solve the problem that the volume of a cobalt ferrite material is expanded in the charge-discharge process to cause serious reduction of the cycle performance, the key point is that under the magnetic stirring, a solution A is added into a solution B within 10-30s, and then the stirring is continued for 1-3 min; s4, standing the obtained solution at 80-100 ℃ for 2-4h, centrifuging, drying and calcining to obtain the nano material with hollowed four surfaces.
Description
Technical Field
The invention belongs to the field of materials, and relates to four-side hollow CoFe2O4A nano material and a preparation method and application thereof.
Background
Spinel type binary iron oxides, e.g. CoFe2O4Can be applied in many research fields, such as: information storage, photocatalysis, electrocatalysis, food safety detection, magnetic fluid, lithium batteries and the like. For different fields of application, CoFe is required2O4Have different structures and excellent performance. For example, CoFe for use in food safety inspection2O4Small size, biocompatibility, non-toxicity, etc. are required. In addition to the above requirements, the materials are required to have specific structural characteristics for the field of electrocatalytic water splitting.
Nai et al use the raw materials cobalt acetate, sodium citrate and potassium ferricyanide, standing the liquid at 80 ℃ for 6h to synthesize Co-Fe PBA NFs, standing the liquid at 35 ℃ for 36h to synthesize Co-Fe PBA NAFs, calcining the two products at 350 ℃ for 2h to obtain Co-Fe oxide, and applying the Co-Fe oxide to the field of electrocatalytic water cracking.
King Wei and the like prepare the titanium dioxide/cobalt ferrite nanometer negative electrode material and research the electrochemical performance of the titanium dioxide/cobalt ferrite nanometer negative electrode material. The text is that the structure of cobalt ferrite is stabilized by composite titanium dioxide nano particles. In the process of charging and discharging, the titanium dioxide is stable in structure, and the titanium dioxide are compounded to have a synergistic effect, so that the volume expansion of the titanium dioxide is reduced, and the electrical property is improved. The first discharge specific capacity of the composite material is 623mAh/g, the discharge specific capacity after 200-week circulation is kept at 516mAh/g, and the capacity retention rate is up to 83%.
The lithium ion battery has the advantages of long service life, high energy density, low self-discharge rate, light weight and the like, so the application field is wider. Currently, the negative electrode material of commercial lithium ion batteries is graphite, and graphite has a lower theoretical capacity (372 mAh/g). With the progress of technology, people have higher and higher capacity requirements on lithium batteries, and obviously, graphite cathode materials cannot meet the development requirements of lithium ion batteries. Spinel type binary iron oxides, such as cobalt ferrite, of the general formula AFe in recent years2O4(a ═ Zn, Ni, Co, Mn) has been a research hotspot in the field of lithium batteries, and cobalt ferrite has a high theoretical capacity (916mAh/g), but it expands in volume during charge and discharge, causing structural destruction of its material, resulting in severe degradation of cycle performance. Therefore, the invention aims to synthesize the cobalt ferrite with the special four-side hollow structure, so that the volume expansion of the cobalt ferrite is relieved, and the cycle performance of the cobalt ferrite is improved.
Disclosure of Invention
In order to solve the problem that the volume of the cobalt ferrite material is expanded in the charge and discharge process to cause serious reduction of the cycle performance, the invention provides the following technical scheme: four-side hollow CoFe2O4The preparation method of the nano material comprises the following steps:
s1, dissolving cobalt nitrate hexahydrate and sodium dodecyl benzene sulfonate in deionized water to form a solution A;
s2, dissolving potassium ferricyanide in deionized water to form a solution B;
s3, adding the solution A into the solution B within 10-30s under magnetic stirring, and then continuing stirring for 1-3 min;
s4, standing the obtained solution at 80-100 ℃ for 2-4h, centrifuging, drying and calcining to obtain the CoFe with hollowed four surfaces2O4And (3) nano materials.
Further, solution a was added to solution B over 15s, after which stirring was continued for 1 min.
Further, the solution in the step S4 is kept standing for 2-4h at 80 ℃ or 90 ℃.
Further, the solution in the step S4 is kept standing for 2 hours at 80 ℃ or 90 ℃.
The invention also relates to four-side hollowed-out CoFe2O4The nano material is prepared by the preparation method.
The invention also relates to four-side hollowed-out CoFe2O4The application of the nano material as a negative electrode material of a lithium ion battery in improving the cycle performance.
Has the advantages that: four-side hollowed-out CoFe is synthesized by a template-free method2O4The method is simple and convenient, and is suitable for industrial production. The material synthesized by the method has higher specific capacity (four-side hollow CoFe)2O4-90: 675mAh/g) and with solid CoFe2O4(solid CoFe)2O4-30) four-sided openwork CoFe compared to2O4Has excellent cycle performance. The reason for this is that the hollow structure makes lithium ions more easily inserted and extracted, and thus the expansion rate of the material becomes small, while solid CoFe2O4CoFe with hollow four sides is difficult to remove and embed and has larger expansion rate of material2O4The cycle performance is good.
Drawings
FIG. 1 is solid CoFe of example 12O4-a TEM photograph of 30;
FIG. 2 is solid CoFe of example 22O4-a TEM photograph of 50;
FIG. 3 is a partially hollowed-out CoFe of example 32O4-a TEM photograph of 60;
FIG. 4 is semi-hollow CoFe of example 42O4-a TEM photograph of 70;
FIG. 5 is the four-sided openwork CoFe of example 52O4-TEM photograph of 80;
FIG. 6 is the four-sided openwork CoFe of example 62O4-TEM photograph of 90;
FIG. 7 is the four-sided openwork CoFe of example 72O4-TEM photograph of 100;
FIG. 8 shows crushed CoFe of example 82O4-TEM photograph of 110;
FIG. 9 is solid CoFe2O4-30, four-sided openwork CoFe2O4-80, four-sided openwork CoFe2O4-90, four-sided hollowed-out CoFe2O4-100 cycle performance versus graph.
Detailed Description
Example 1: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 30 ℃ for 2h, centrifuging, washing a sample with deionized water and ethanol, drying the sample in an oven at 60 ℃ for 12h to obtain solid Co-Fe Prussian blue, then placing the sample in a muffle furnace, and calcining at 350 ℃ for 2h to obtain solid CoFe2O4Nano material (named solid CoFe2O4-30). The results obtained by TEM observation are shown in FIG. 1.
Example 2: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 50 deg.C for 2h, centrifuging,washing a sample with deionized water and ethanol, placing the sample in an oven at 60 ℃ for drying for 12h to obtain solid Co-Fe Prussian blue, placing the sample in a muffle furnace, calcining at 350 ℃ for 2h to obtain solid CoFe2O4Nano material (named solid CoFe2O4-50). The results obtained by TEM observation are shown in FIG. 2.
Example 3: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 60 ℃ for 2h, centrifuging, washing the sample with deionized water and ethanol, drying the sample in an oven at 60 ℃ for 12h to obtain solid Co-Fe Prussian blue, then placing the sample in a muffle furnace, and calcining at 350 ℃ for 2h to obtain solid CoFe2O4Nano material (named semi-hollow CoFe)2O4-60). The results obtained by TEM observation are shown in FIG. 3.
Example 4: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 70 ℃ for 2h, centrifuging, washing a sample with deionized water and ethanol, drying the sample in an oven at 60 ℃ for 12h to obtain semi-hollow Co-Fe Prussian blue, then placing the sample in a muffle furnace, calcining at 350 ℃ for 2h to obtain semi-hollow CoFe2O4Nano material (named semi-hollow CoFe)2O4-70). The results obtained by TEM observation are shown in FIG. 4.
Example 5: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution A was added to solution B over 15s under magnetic stirring, after which timeStirring was continued for 1 min. Standing the obtained solution at 80 ℃ for 2h, centrifuging, washing a sample with deionized water and ethanol, drying the sample in a 60 ℃ oven for 12h to obtain Co-Fe Prussian blue with hollowed four sides, then placing the sample in a muffle furnace, and calcining at 350 ℃ for 2h to obtain CoFe with hollowed four sides2O4Nano material (named four-side hollow CoFe)2O4-80). The results obtained by TEM observation are shown in FIG. 5.
Example 6: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 90 ℃ for 2h, centrifuging, washing a sample with deionized water and ethanol, drying the sample in a 60 ℃ oven for 12h to obtain Co-Fe Prussian blue with hollowed four sides, then placing the sample in a muffle furnace, and calcining at 350 ℃ for 2h to obtain CoFe with hollowed four sides2O4Nano material (named four-side hollow CoFe)2O4-90). The results obtained by TEM observation are shown in FIG. 6.
Example 7: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a; dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 100 ℃ for 2h, centrifuging, washing a sample with deionized water and ethanol, placing the sample in a 60 ℃ oven for drying for 12h to obtain Co-Fe Prussian blue with hollowed four sides, placing the sample in a muffle furnace for calcining at 350 ℃ for 2h to obtain CoFe with hollowed four sides2O4Nano material (named four-side hollow CoFe)2O4-100). The results obtained by TEM observation are shown in FIG. 7.
Example 8: in this example, first 0.291g of cobalt nitrate hexahydrate and 0.348g of sodium dodecylbenzenesulfonate were dissolved in 30ml of deionized water to form a solution a;dissolving potassium ferricyanide in 30ml of deionized water to form a solution B; solution a was added to solution B over 15s with magnetic stirring, after which stirring was continued for 1 min. Standing the obtained solution at 110 ℃ for 2h, centrifuging, washing the sample with deionized water and ethanol, drying the sample in an oven at 60 ℃ for 12h to obtain crushed Co-Fe Prussian blue, then placing the sample in a muffle furnace, and calcining at 350 ℃ for 2h to obtain crushed CoFe2O4Nano material (named as broken CoFe2O4-110). The results obtained by TEM observation are shown in FIG. 8.
Example 9: for each embodiment, the solution A is added into the solution B within 10-30s, then the stirring is continued for 1-3min, the standing time is 2-4h, and the materials can reach the basically similar hollow degree.
Example 10: the invention adopts a template-free method to control the synthesis of CoFe with different morphologies2O4Nanomaterial (solid CoFe)2O4Nano material and four-side hollowed-out CoFe2O4Nano-materials). Firstly, dissolving cobalt nitrate hexahydrate and sodium dodecyl benzene sulfonate in deionized water to form a solution A; dissolving potassium ferricyanide in deionized water to form a solution B; adding the solution A into the solution B within 10-30s under magnetic stirring, and then continuing stirring for 1-3 min. CoFe is then controlled by controlling the reaction temperature2O4The growth process of (1). Standing the obtained solution at 30-50 ℃ for 2-4h, centrifuging, drying and calcining to obtain solid CoFe2O4And (3) nano materials. If the obtained solution is kept stand for 2-4h at the temperature of 60-70 ℃, semi-hollow CoFe can be obtained after centrifugation, drying and calcination2O4And (3) nano materials. If the obtained solution is kept stand for 2-4h at 80-100 ℃, the CoFe with hollow four sides can be obtained after centrifugation, drying and calcination2O4And (3) nano materials. If the obtained solution is kept stand for 2-4h at the temperature of more than 100 ℃, the solution is centrifuged, dried and calcined, and then the CoFe with hollow four sides is obtained2O4And (4) crushing the nano material.
As shown in FIGS. 1 to 8, it is apparent from the TEM photographs that CoFe was synthesized at a reaction temperature of 30 to 50 deg.C2O4Is of solid structure, andthe temperature is 60-70 ℃, and the synthesized CoFe2O4Is in a semi-hollow structure, and the reaction temperature is 80-100 ℃, the synthesized CoFe2O4Is a four-side hollow structure, and the reaction temperature is 110 ℃, the synthesized CoFe2O4The four-sided hollowed-out structure is destroyed. The reaction mechanism is as follows: when the two reaction solutions are mixed, cubic Co-Fe Prussian blue is quickly formed, and more energy is provided at a higher reaction temperature (80-100 ℃) to drive the particle ripening and crystal regrowth processes of the Co-Fe Prussian blue. Specifically, after the cube is rapidly formed, the sodium dodecyl benzene sulfonate plays a role of a surfactant and a structure directing agent, the Co-Fe Prussian blue takes the Co-Fe Prussian blue as a template, the core of the Co-Fe Prussian blue is gradually dissolved along with the reaction, a cavity is formed in the core of the cube, the surface of the Co-Fe Prussian blue is gradually dissolved along with the further reaction, and the nano-framework structure is finally formed. If the reaction temperature is too low (30-50 ℃), there is not enough energy to drive particle ripening and crystal growth of Co-Fe prussian blue. If the reaction temperature is too high (> 100 ℃), excessive energy will over-mature the particles of Co-Fe prussian blue, resulting in the destruction of the tetrahedral hollowed-out structure.
As shown in FIG. 9, solid CoFe after 20 cycles2O4-30, four-sided openwork CoFe2O4-80, four-sided openwork CoFe2O4-90, four-sided hollowed-out CoFe2O4The retention ratios of discharge capacities of-100 were 83.8%, 87.9%, 89.9%, 88.5%, respectively; obviously showing CoFe with hollowed four sides2O4Solid CoFe in cycle performance ratio2O4Is excellent and is four-side hollowed-out CoFe2O4The cycle performance of-90 is optimal. The reason for this is that lithium ions are in solid CoFe2O4The polymer is difficult to remove and the material has larger volume expansion, so the cycle performance is poorer. The hollow structure can enable lithium ions to be more easily inserted and extracted, and the volume expansion of the material is reduced, so that the CoFe with hollowed four surfaces2O4The cycle performance is good. Four-side hollowed-out CoFe2O480, incomplete hollow structure, firmer nano-frame, smaller specific surface area and large expansion rate. Four-side hollowed-out CoFe2O4The-100 hollow structure is too complete, and the nano-frame is easy to damage. And four sides hollowed out CoFe2O4The-90 is completely hollow, and the nano-frame is not easy to damage, so that the performance is optimal. That is, the solution is preferably allowed to stand at 80 ℃ in view of the frame stability, and at 90 ℃ in view of the cycle performance, and it is needless to say that the temperature values in this interval are preferably 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ and 100 ℃.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (4)
1. Four-side hollow CoFe2O4The preparation method of the nano material is characterized by comprising the following steps:
s1, dissolving cobalt nitrate hexahydrate and sodium dodecyl benzene sulfonate in deionized water to form a solution A;
s2, dissolving potassium ferricyanide in deionized water to form a solution B;
s3, adding the solution A into the solution B within 10-30s under magnetic stirring, and then continuing stirring for 1-3 min;
s4, standing the obtained solution at 80-100 ℃ for 2-4h, centrifuging, drying and calcining to obtain the CoFe with hollowed four surfaces2O4And (3) nano materials.
2. The four-sided openwork CoFe of claim 12O4The preparation method of the nano material is characterized in that the solution A is added into the solution B within 15s, and then the stirring is continued for 1 min.
3. The four-sided openwork CoFe of claim 1 or said2O4The preparation method of the nano material is characterized in that the solution in the step S4 is kept stand for 2-4h at 80 ℃ or 90 ℃.
4. The four-sided openwork CoFe of claim 3 or claim2O4The preparation method of the nano material is characterized in that the solution in the step S4 is kept stand for 2 hours at 80 ℃ or 90 ℃.
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