CN111816867A - Sea urchin-shaped NiCo with mesoporous structure2O4Preparation method and application of three-dimensional construction graphene microsphere composite material - Google Patents
Sea urchin-shaped NiCo with mesoporous structure2O4Preparation method and application of three-dimensional construction graphene microsphere composite material Download PDFInfo
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Abstract
Sea urchin-shaped NiCo with mesoporous structure2O4The preparation method and the application of the three-dimensional construction graphene microsphere composite material comprise the following steps: (1) firstly, treating the three-dimensional constructed graphene with oxidizing acid in a high-pressure reaction kettle, washing with water, and drying to obtain hydrophilic three-dimensional constructed graphene; (2) dispersing hydrophilic three-dimensional structure graphene in water by an ultrasonic method, then adding cobalt salt, nickel salt, a surfactant and a precipitator, and fully stirring to form a uniform solution; (3) the mixed solution is subjected to hydrothermal reaction to obtainTo nickel cobaltate precursor; (4) calcining the nickel cobaltate precursor in air atmosphere to obtain the mesoporous NiCo2O4A three-dimensional structure graphene microsphere compound. The preparation method has the advantages of simple preparation process, environmental protection, wide raw material source and electrochemical performance of the product. The specific capacity of the lithium ion battery cathode material prepared by the material in the first discharge is up to 1403mA h g‑1. When the material is used as a negative electrode material of a sodium ion battery, the first discharge specific capacity is up to 818.4mA h g‑1。
Description
Technical Field
The invention relates to a mesoporous NiCo structure2O4A stereo-structure graphene microsphere, in particular to sea urchin-shaped NiCo with a mesoporous structure2O4Preparation method and application of stereo-structure graphene microsphere composite material.
Background
A graphite sheet having 10 or less layers is called graphene, which is a conductive material having a hexagonal network two-dimensional space structure. The nano-composite material has the advantages of super large specific surface area, good conductivity and super high chemical stability, and has excellent application potential in the fields of super capacitors, luminescent materials and the like. However, when the graphene with the two-dimensional space structure is independently used as a negative electrode material of a lithium ion battery or a sodium ion battery, the problems of low discharge capacity and coulombic efficiency, fast capacity fading and the like exist. However, the graphene with a two-dimensional space structure is used as a coating layer of a negative electrode material or a positive electrode material of a lithium ion battery, and plays a positive role in improving the cycle stability of the battery (Hsu T H, Liu W R, Polymers,2020,12(5): 1162; Yang X F, Qiu J Y and the like, J.alloys Compad., 2020,824: 153945; Zhang J F, Ji G J and the like, appl.Surf.Sci.,2020,513: 145854). However, the two-dimensional graphene is easy to agglomerate and agglomerate, and has the defects of difficult storage and use and the like. In addition, the ion transmission channel of the two-dimensional graphene is small, so that the two-dimensional graphene is not suitable for serving as a negative electrode material of a sodium ion battery or a coating layer of a positive electrode material and a negative electrode material. At present, the construction of graphene with a three-dimensional (3D) structure has proven to be a strategy capable of effectively providing a self-supporting structure, preventing graphene nanoplatelets from aggregating, and improving the energy storage performance of graphene-based materials, and a unique 3D structure provides channels capable of satisfying sodium ion transport (Li Y Y, Li Z S, etc., adv.Mater.,2013,25(17): 2474-.
NiCo2O4Is a composite metal oxide with a spinel structure and a composite valence state, wherein nickel ions occupy octahedral sites in the spinel structure, and cobalt ions occupy tetrahedral sites. In the solid state NiCo2O4In the electrochemical reaction of (2), Ni is present3 +/Ni2+And Co3+/Co2+Two redox couples provide two active centers for the pseudocapacitance. With a single component metal oxide Co3O4Binary metal oxide NiCo, in contrast to NiO2O4Has high conductivity, mechanical stability, theoretical capacity and low cost. To improve NiCo2O4Many efforts have been made to improve the electrochemical properties of NiCo2O4Surface modification, nanocrystallization and mixing with various carbons to form a composite material (Wuhongying, Wang Huan Shang Wen, Proc. physicochemical science, 2013,29(7), 1501-1506). Nickel nitrate hexahydrate, cobalt nitrate hexahydrate and NH4F. Urea and activated carbon fiber cloth are used as raw materials, and nickel cobaltate nanoflowers successfully grow on the activated carbon fiber support through a hydrothermal method and subsequent heat treatment. (Fu F, Li J D, Yao Y Z et al, ACS appl. Mater. Interf.,2017,9: 16194-2O4Micro rod at 100mA g-1When the micro-rod material is used as a lithium ion negative electrode material, the discharge capacity after 50 cycles is about 1000mA h g-1(ii) a The initial charge capacity of the lithium ion battery cathode material is 431.1mAh g-1. (the square of the plum square,rod-shaped NiCo is synthesized by a one-step hydrothermal method through Ronghoubin, Ronghuiwei and the like, chemical journal of higher schools, 2017,38(11): 1913-1920)2O4@ C Complex at 100mA g-1At current density of NiCo2O4The discharge capacities of the @ C compound as the lithium ion battery negative electrode material after the initial time and the 5-time circulation are 767.2mA h g-1And 650.1mA h g-1. (Zhangming Mei, Li Yuan, Xijimin, etc., Chinese patent CN 106169384A discloses a three-dimensional mesoporous NiCo2O4The preparation method of the/nitrogen-doped graphene composite electrode material comprises the steps of using graphene oxide as a carbon source and acetonitrile as a solvent, treating the graphene oxide by a hydrothermal method, mixing the obtained graphene with nickel nitrate hexahydrate, cobalt nitrate hexahydrate and hexamethylenetetramine, carrying out hydrothermal reaction, and calcining the obtained precursor in an air atmosphere to obtain the three-dimensional mesoporous NiCo2O4The nitrogen-doped graphene composite electrode material. Chinese patent CN 104882298A discloses a microwave method for preparing NiCo2O4A method for preparing a graphene super-capacitor material comprises the steps of synthesizing a precursor by a microwave heating method by taking graphene oxide obtained by processing natural graphene through a Hummers method as a carbon source, taking nickel chloride and cobalt chloride as a nickel source and a cobalt source respectively and taking urea as a precipitator, calcining the precursor in an air atmosphere to obtain porous flaky NiCo2O4A graphene supercapacitor material.
Disclosure of Invention
The invention aims to provide a sea urchin-shaped NiCo with a mesoporous structure, which is simple to operate and can be prepared2O4Preparation method of stereo-structure graphene microsphere composite material, wherein the obtained material is 100mA g-1The lithium ion battery and the sodium ion battery are respectively used as cathode materials under current density, and the first discharge specific capacity is 1403mA h g-1And 818.4mA h g-1The material has good rate capability and cycling stability.
The invention realizes the purpose through the following technical scheme: sea urchin-shaped NiCo with mesoporous structure2O4The preparation method of the three-dimensional structure graphene microsphere composite material comprises the following steps:
(1) placing the three-dimensional structure graphene powder into a hydrothermal kettle lined with polytetrafluoroethylene, adding 68 wt% of nitric acid, heating the hydrothermal kettle at a constant temperature, naturally cooling the hydrothermal kettle to room temperature after the reaction is finished, filtering, collecting and precipitating to obtain hydrophilic three-dimensional structure graphene powder, wherein when the hydrophilic three-dimensional structure graphene powder is prepared, the dosage ratio of the three-dimensional structure graphene to the nitric acid is 1 g: 25-70 mL of the graphene powder, the reaction temperature of 80-160 ℃, the reaction time of 10-36 h, and the temperature for drying the three-dimensional structure graphene powder of 50-90 ℃;
(2) ultrasonically dispersing the hydrophilic three-dimensional structure graphene powder obtained in the step (1) into deionized water to obtain a uniformly dispersed hydrophilic three-dimensional structure graphene solution A, wherein the dosage ratio of the hydrophilic three-dimensional structure graphene powder to the deionized water is 0.1 g: 20-50 mL, and 5-40 min of ultrasonic time;
(3) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea and polyethylene glycol-400 by using deionized water to obtain a solution B, wherein the dosage ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate, the urea and the polyethylene glycol-400 is 0.003-0.009 mol: 0.006-0.018 mol: 0.036-0.108 mol: 2-4 ml;
(4) mixing the solution A and the solution B to obtain a solution C, and preparing the mixed solution C by using hydrophilic three-dimensional construction graphene and NiCo2O4The dosage ratio of the components is 0.1 g: 0.3-1.2 g;
(5) transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene, carrying out constant-temperature thermal reaction, filtering and washing to obtain a three-dimensional constructed graphene-coated nickel cobaltate precursor D, wherein the constant-temperature reaction temperature is 85-160 ℃ and the reaction time is 4-20 h when the three-dimensional constructed graphene-coated nickel cobaltate precursor D is prepared;
(6) placing the precursor D in a muffle furnace for calcining at the temperature of 280-360 ℃ for 1-4 h to obtain the mesoporous NiCo2O4A three-dimensional structure graphene microsphere compound.
Furthermore, the hydrothermal reaction temperature/time is 95-110 ℃/8-4 h.
Furthermore, the calcination temperature is controlled to be 300-335 ℃.
The mesoporous NiCo2O4The preparation method of the three-dimensional structure graphene microsphere compound comprises the following steps:
(1) placing the three-dimensional structure graphene powder into a hydrothermal kettle lined with polytetrafluoroethylene, adding 68 wt% of nitric acid, heating the hydrothermal kettle at a constant temperature, naturally cooling the hydrothermal kettle to room temperature after the reaction is finished, filtering, collecting and precipitating to obtain hydrophilic three-dimensional structure graphene powder, wherein when the hydrophilic three-dimensional structure graphene powder is prepared, the dosage ratio of the three-dimensional structure graphene to the nitric acid is 1 g: 40mL, the reaction temperature is 120 ℃, the reaction time is 24 hours, and the temperature for drying the three-dimensional graphene powder is 60 ℃;
(2) ultrasonically dispersing the hydrophilic three-dimensional structure graphene powder obtained in the step (1) into deionized water to obtain a uniformly dispersed hydrophilic three-dimensional structure graphene solution A, wherein the dosage ratio of the hydrophilic three-dimensional structure graphene powder to the deionized water is 0.1 g: 30mL, and the ultrasonic time is 30 min;
(3) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea and polyethylene glycol-400 by using deionized water to obtain a solution B, wherein when a mixed solution B is prepared, the dosage ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate, the urea and the polyethylene glycol-400 is 0.003 mol: 0.006 mol: 0.036 mol: 2 ml;
(4) mixing the solution A and the solution B to obtain a solution C, and preparing the mixed solution C by using the hydrophilic three-dimensional structure graphene and NiCo2O4The dosage ratio of the components is 0.1 g: 0.72 g;
(5) transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene, carrying out constant-temperature thermal reaction, filtering and washing to obtain a three-dimensional constructed graphene-coated nickel cobaltate precursor D, wherein the constant-temperature reaction temperature is 95 ℃ and the reaction time is 8 hours when the three-dimensional constructed graphene-coated nickel cobaltate precursor D is prepared;
(6) placing the precursor D in a muffle furnace for calcining at the calcining temperature of 300 ℃ for 2h to obtain the mesoporous NiCo2O4A three-dimensional structure graphene microsphere compound.
The prepared mesoporous NiCo2O4Application of the three-dimensional structure graphene microsphere compound in a lithium ion battery cathode material.
The prepared mesoporous NiCo2O4Application of the three-dimensional structure graphene microsphere compound in a sodium ion battery cathode material.
The material is characterized by an X-ray diffractometer (XRD), a Scanning Electron Microscope (SEM), a thermogravimetric analyzer (TG), a nitrogen adsorption-desorption analyzer and an X-ray photoelectron spectrometer (XPS), and the electrochemical performance of the material as the lithium/sodium battery cathode material is tested by an electrochemical workstation and a battery test system.
Except for other descriptions, the percentages are mass percentages, and the sum of the content percentages of all the components is 100%. The invention has the beneficial effects that:
the sea urchin-shaped NiCo with the mesoporous structure prepared by the method2O4The three-dimensional construction graphene microsphere composite electrode material has controllable microsphere size and controllable size of a nanorod forming a sea urchin-shaped microsphere, the diameter of the sea urchin-shaped microsphere is 1.9-4.5 mu m, the diameter of the nanorod forming the sea urchin-shaped microsphere is about 60nm, and the pore diameter and the specific surface area of the material are respectively 4.45nm and 138.81m2g–1. When the prepared material is used as a negative electrode material of a lithium ion battery and a sodium ion battery, the amount of the prepared material is 100mA g-1The first discharge specific capacity is respectively up to 1403mA h g-1And 818.4mA h g-1. In addition, the material has good rate capability and cycling stability. The preparation method has the advantages of simple operation, easy control of reaction conditions, low cost and excellent lithium/sodium storage performance of the obtained material.
Drawings
Fig. 1 is an SEM image of the three-dimensional structure graphene.
FIG. 2 shows a sea urchin-like NiCo with mesoporous structure2O4An XRD diffraction pattern of the three-dimensional constructed graphene microsphere composite material shows characteristic diffraction peaks of graphene and nickel cobaltate.
FIG. 3 shows a sea urchin-like NiCo with mesoporous structure2O4SEM image of stereo-structured graphene.
FIG. 4 shows a sea urchin-like NiCo with mesoporous structure2O4A nitrogen adsorption-desorption curve chart of the three-dimensional constructed graphene.
FIG. 5 shows sea urchin-like (a) NiCo2O4And (b) NiCo2O4The stereo-structure graphene microsphere is used as the cathode material of the lithium ion battery at 0.1A g-1Cycling performance at current density.
FIG. 6 shows sea urchin-like (a) NiCo2O4And (b) NiCo2O4The stereo-structure graphene microsphere is used as the negative electrode material of the sodium-ion battery at 0.1A g-1Cycling performance at current density.
Detailed Description
The technical solution of the present invention is further described below with reference to the following embodiment examples.
Example 1
And preparing hydrophilic three-dimensional construction graphene. 1g of stereostructured graphene is put into a 80mL hydrothermal reaction kettle lined with polytetrafluoroethylene, 40mL of nitric acid with the concentration of 68 wt% is added, and the mixture is reacted for 24 hours at the temperature of 120 ℃. And naturally cooling to room temperature after the reaction is finished, performing suction filtration on the obtained product by using a No. 6 sand core funnel, alternately washing the product for 6 times by using deionized water and absolute ethyl alcohol, and then drying the product for 5 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the hydrophilic three-dimensional construction graphene powder. SEM analysis of the product proves that the structure of the product is a three-dimensional structure; XPS analysis showed that sp was present in the product2C; water dispersibility experiments are carried out on the product, and the hydrophilicity of the product is obviously improved compared with that of the stereo-structure graphene which is not treated by 68 wt% of nitric acid. The prepared product is hydrophilic three-dimensional structure graphene. As shown in fig. 1 and 2.
Example 2
Preparation of sea urchin-shaped NiCo with mesoporous structure2O4. 0.8724g of 0.003mol of nickel nitrate hexahydrate, 1.7462g of 0.006mol of cobalt nitrate hexahydrate, 2.1622g of 0.036mol of urea and 2mL of polyethylene glycol-400 were dissolved in 60mL of deionized water. The resulting solution was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8 h. After cooling to room temperature, the mixture was passed through a funnel with a No. 6 sand coreAnd (4) carrying out suction filtration, collecting the precipitate, and alternately washing the precipitate for 3 times by using deionized water and absolute ethyl alcohol. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4And (3) precursor. Mixing NiCo2O4Precursor in air for 2min-1Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure2O4Sea urchin shaped NiCo2O4Has a pore diameter and a specific surface area of 3.98nm and 125.71m2g–1. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4Used as the negative electrode material of lithium ion battery, is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 1409.6mA h g respectively at a current density-1And 610.7mA h g–1As shown in fig. 5 a. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4Used as the negative electrode material of sodium-ion battery, is 0.1A g-1At a current density, the first discharge capacity and the 50 th-cycle discharge capacity were 638mA h g-1And 214.6mA hr g–1As shown in fig. 6 a.
Example 3
Preparation of sea urchin-shaped NiCo with mesoporous structure2O4A stereo-structure graphene microsphere. 0.8724g of 0.003mol of nickel nitrate hexahydrate, 1.7462g of 0.006mol of cobalt nitrate hexahydrate, 2.1622g of 0.036mol of urea, 100mg of hydrophilic stereo-structure graphene and 2mL of polyethylene glycol-400 are ultrasonically dispersed in 60mL of deionized water. The resulting mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8 h. After cooling to room temperature, the precipitate was collected by suction filtration through a No. 6 sand core funnel and washed alternately with deionized water and anhydrous ethanol 3 times. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4A precursor of the stereostructured graphene. Mixing NiCo2O4The precursor of the stereo-structured graphene is in the air atmosphere for 2min-1Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is shown in figure 2 and figure 3, and the pore diameter and the specific surface area of the composite material are dividedRespectively 4.45nm and 138.81m2g–1As shown in FIG. 4, the pore size and specific surface area of the composite material are both greater than those of a single NiCo2O4The sample was improved. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is used as the cathode material of the lithium ion battery and is 0.1A g-1At a current density, the first discharge capacity and the 50 th-cycle discharge capacity were 1403mA h g and g, respectively-1And 1027mA h g–1As shown in fig. 5 b. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 819mA h g, respectively, at a current density-1And 314mAh g–1As shown in fig. 6 b. Shows NiCo2O4NiCo obtained by coating surface of graphene through three-dimensional construction2O4Single NiCo prepared under the same technical condition of lithium/sodium storage performance ratio of three-dimensional structure graphene composite2O4Are all obviously improved.
Example 4
Preparation of sea urchin-shaped NiCo with mesoporous structure2O4A stereo-structure graphene microsphere.
1.7448g of 0.006mol of nickel nitrate hexahydrate, 3.4924g of 0.012mol of cobalt nitrate hexahydrate, 4.3244g of 0.072mol of urea, 200mg of hydrophilic stereo-structure graphene and 3mL of polyethylene glycol-400 are ultrasonically dispersed in 60mL of deionized water. The resulting mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8 h. After cooling to room temperature, the precipitate was collected by suction filtration through a No. 6 sand core funnel and washed alternately with deionized water and anhydrous ethanol 3 times. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4A precursor of the stereostructured graphene. Mixing NiCo2O4The precursor of the stereo-structured graphene is in the air atmosphere for 2min-1Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure2O4The aperture and the specific surface area of the composite material are respectively4.40nm and 129.03m2g–1The pore size and specific surface area of the composite material are slightly reduced compared with the sample obtained under the technical conditions of the example 3. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is used as the cathode material of the lithium ion battery and is 0.1A g-1At a current density, the first discharge capacity and the 50 th-cycle discharge capacity were 1370 mA hg, respectively-1And 1001mA h g–1. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 810mA h g and g, respectively, at a current density-1And 310mA h g–1. Shows the resulting NiCo2O4The lithium/sodium storage performance of the stereostructured graphene composite is reduced compared with that of the sample obtained in the example 3.
Example 5
Prepared sea urchin-shaped NiCo with mesoporous structure2O4A stereo-structure graphene microsphere.
2.6172g of 0.009mol of nickel nitrate hexahydrate, 5.2386g of 0.018mol of cobalt nitrate hexahydrate, 6.4866g of 0.108mol of urea, 300mg of hydrophilic stereo-structure graphene and 6mL of polyethylene glycol-400 were ultrasonically dispersed in 60mL of deionized water. The resulting mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8 h. After cooling to room temperature, the precipitate was collected by suction filtration through a No. 6 sand core funnel and washed alternately with deionized water and anhydrous ethanol 3 times. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4A precursor of the stereostructured graphene. Mixing NiCo2O4The precursor of the stereo-structured graphene is in the air atmosphere for 2min-1Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure2O4The aperture and the specific surface area of the composite material are respectively 4.25nm and 126.7m2g–1The pore diameter and the specific surface area of the composite material are both larger than those of single NiCo2O4The sample was improved but less than example 3 and practiceThe sample of example 4. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is used as the cathode material of the lithium ion battery and is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 1365mA h g and g, respectively, at current density-1And 995mA h g–1. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 800mA h g and g, respectively, at a current density-1And 300.4mA hr g–1. Shows NiCo2O4NiCo obtained by coating surface of graphene through three-dimensional construction2O4Stereo-structure graphene composite lithium/sodium storage performance ratio single NiCo2O4Both are significantly improved, but less than the samples of example 3 and example 4.
Example 6
Prepared sea urchin-shaped NiCo with mesoporous structure2O4A stereo-structure graphene microsphere.
0.8724g of 0.003mol of nickel nitrate hexahydrate, 1.7462g of 0.006mol of cobalt nitrate hexahydrate, 2.1622g of 0.036mol of urea, 100mg of hydrophilic stereo-structure graphene and 2mL of polyethylene glycol-400 are ultrasonically dispersed in 60mL of deionized water. The resulting mixture was transferred to a 100mL polytetrafluoroethylene-lined hydrothermal reaction kettle and heated at 110 ℃ for 8 h. After cooling to room temperature, the precipitate was collected by suction filtration through a No. 6 sand core funnel and washed alternately with deionized water and anhydrous ethanol 3 times. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4A precursor of the stereostructured graphene. Mixing NiCo2O4The precursor of the stereo-structured graphene is in the air atmosphere for 2min-1The temperature rise rate of the catalyst is calcined for 1.5h at the temperature of 350 ℃ to obtain the sea urchin-shaped NiCo with the mesoporous structure2O4The aperture and the specific surface area of the composite material are respectively 3.80nm and 110.6m2g–1The pore diameter and specific surface area of the composite material are both smaller than those of the composite materials of examples 2 to 5. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is used as the cathode material of the lithium ion battery and is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 1350mA h g and g, respectively, at a current density-1And 990mA h g–1. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g-1The first discharge capacity and the 50 th cycle discharge capacity were 798mA h g, respectively, at a current density-1And 285mA h g–1. Indicating that NiCo is obtained under the technical conditions2O4The lithium/sodium storage performance of the stereo-structure graphene composite is lower than that of the embodiment 3 to the embodiment 5.
Example 7
Prepared sea urchin-shaped NiCo with mesoporous structure2O4A stereo-structure graphene microsphere.
0.8724g of 0.003mol of nickel nitrate hexahydrate, 1.7462g of 0.006mol of cobalt nitrate hexahydrate, 2.1622g of 0.036mol of urea, 100mg of hydrophilic stereo-structure graphene and 2mL of polyethylene glycol-400 are ultrasonically dispersed in 60mL of deionized water. The resulting mixture was transferred to a 100mL polytetrafluoroethylene-lined hydrothermal reaction kettle and heated at 105 ℃ for 6 h. After cooling to room temperature, the precipitate was collected by suction filtration through a No. 6 sand core funnel and washed alternately with deionized water and anhydrous ethanol 3 times. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4A precursor of the stereostructured graphene. Mixing NiCo2O4Precursor of stereo-structured graphene in air for 2min-1The temperature rise rate of the catalyst is calcined for 1 hour at the temperature of 330 ℃ to obtain the sea urchin-shaped NiCo with the mesoporous structure2O4A stereo-structure graphene microsphere. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is used as a lithium ion battery cathode material and is 0.5A g-1The first discharge capacity and the 10 th cycle discharge capacity were 1300mA h g at current density-1And 900mA h g–1. When the material is used as a negative electrode material of a sodium-ion battery, the material is at 0.5A g-1First discharge capacity and 10 th cycle discharge at current densityThe capacities were 645mAh g, respectively-1And 450mA h g–1。
Example 8
Prepared sea urchin-shaped NiCo with mesoporous structure2O4A stereo-structure graphene microsphere.
0.8724g of 0.003mol of nickel nitrate hexahydrate, 1.7462g of 0.006mol of cobalt nitrate hexahydrate, 2.1622g of 0.036mol of urea, 100mg of hydrophilic stereo-structure graphene and 2mL of polyethylene glycol-400 are ultrasonically dispersed in 60mL of deionized water. The resulting mixture was transferred to a 100mL polytetrafluoroethylene-lined hydrothermal reaction kettle and heated at 110 ℃ for 4 h. After cooling to room temperature, the precipitate was collected by suction filtration through a No. 6 sand core funnel and washed alternately with deionized water and anhydrous ethanol 3 times. Drying the precipitate in a vacuum drying oven at 60 ℃ for 4h to obtain NiCo2O4A precursor of hydrophilic three-dimensional structured graphene. Mixing NiCo2O4Precursor of hydrophilic three-dimensional constructed graphene in air for 2min-1The temperature rise rate of the catalyst is calcined for 1 hour at the temperature of 335 ℃, and the sea urchin-shaped NiCo with the mesoporous structure is obtained2O4A stereo-structure graphene microsphere. The prepared sea urchin-shaped NiCo with the mesoporous structure2O4The stereo-structure graphene microsphere is used as a lithium ion battery cathode material and is 1A g-1At a current density, the first discharge capacity and the 200 th-cycle discharge capacity were 1308mA h g-1And 500mA h g–1. When the material is used as a negative electrode material of a sodium ion battery, the material is at 1A g-1At a current density, the first discharge capacity and the 10 th-cycle discharge capacity were 638mA h g-1And 372mA h g–1。
TABLE 1 lithium/sodium storage Properties of the products prepared under different experimental control technical conditions
As can be seen from the lithium/sodium storage properties of the products prepared under different experimental control technical conditions in Table 1, the sea urchin-like NiCo prepared after the stereostructured graphene is added2O4VerticalCompared with sea urchin-shaped NiCo without added three-dimensional structure graphene, the structure-built graphene microsphere is formed by the sea urchin-shaped NiCo2O4The microspheres have higher discharge capacity and cycle stability. This is due to the coating of the sea urchin-like NiCo2O4The three-dimensional graphene on the surface of the microsphere has a three-dimensional conductive network capable of improving the electronic conductivity of the material, and meanwhile, the three-dimensional graphene can also relieve NiCo2O4Volume change during charge/discharge. Furthermore, in order to obtain NiCo with large specific surface area and high electrochemical performance2O4The calcining temperature of the stereo-structured graphene microspheres is controlled to be 300-335 ℃.
Claims (6)
1. Sea urchin-shaped NiCo with mesoporous structure2O4The preparation method of the three-dimensional construction graphene microsphere composite material is characterized by comprising the following steps:
(1) placing the three-dimensional structure graphene powder into a hydrothermal kettle lined with polytetrafluoroethylene, adding 68 wt% of nitric acid, heating the hydrothermal kettle at a constant temperature, naturally cooling the hydrothermal kettle to room temperature after the reaction is finished, filtering, collecting and precipitating to obtain hydrophilic three-dimensional structure graphene powder, wherein when the hydrophilic three-dimensional structure graphene powder is prepared, the dosage ratio of the three-dimensional structure graphene to the nitric acid is 1 g: 25-70 mL of the graphene powder, the reaction temperature of 80-160 ℃, the reaction time of 10-36 h, and the temperature for drying the three-dimensional structure graphene powder of 50-90 ℃;
(2) ultrasonically dispersing the hydrophilic three-dimensional structure graphene powder obtained in the step (1) into deionized water to obtain a uniformly dispersed hydrophilic three-dimensional structure graphene solution A, wherein the dosage ratio of the hydrophilic three-dimensional structure graphene powder to the deionized water is 0.1 g: 20-50 mL, and 5-40 min of ultrasonic time;
(3) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea and polyethylene glycol-400 by using deionized water to obtain a solution B, wherein the dosage ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate, the urea and the polyethylene glycol-400 is 0.003-0.009 mol: 0.006-0.018 mol: 0.036-0.108 mol: 2-4 ml;
(4) mixing solution A and solution B to obtainSolution C, when preparing mixed solution C, hydrophilic three-dimensional structure graphene and NiCo2O4The dosage ratio of the components is 0.1 g: 0.3-1.2 g;
(5) transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene, carrying out constant-temperature thermal reaction, filtering and washing to obtain a three-dimensional constructed graphene-coated nickel cobaltate precursor D, wherein the constant-temperature reaction temperature is 85-160 ℃ and the reaction time is 4-20 h when the three-dimensional constructed graphene-coated nickel cobaltate precursor D is prepared;
(6) placing the precursor D in a muffle furnace for calcining at the temperature of 280-360 ℃ for 1-4 h to obtain the mesoporous NiCo2O4A three-dimensional structure graphene microsphere compound.
2. The mesoporous NiCo of claim 12O4The preparation method of the three-dimensional construction graphene microsphere compound is characterized in that the hydrothermal reaction temperature/time is 95-110 ℃/8-4 h.
3. The mesoporous NiCo of claim 12O4The preparation method of the three-dimensional structure graphene microsphere compound is characterized in that the calcining temperature is controlled to be 300-335 ℃.
4. The mesoporous NiCo of claim 12O4The preparation method of the three-dimensional structure graphene microsphere compound is characterized by comprising the following steps:
(1) placing the three-dimensional structure graphene powder into a hydrothermal kettle lined with polytetrafluoroethylene, adding 68 wt% of nitric acid, heating the hydrothermal kettle at a constant temperature, naturally cooling the hydrothermal kettle to room temperature after the reaction is finished, filtering, collecting and precipitating to obtain hydrophilic three-dimensional structure graphene powder, wherein when the hydrophilic three-dimensional structure graphene powder is prepared, the dosage ratio of the three-dimensional structure graphene to the nitric acid is 1 g: 40mL, the reaction temperature is 120 ℃, the reaction time is 24 hours, and the temperature for drying the three-dimensional graphene powder is 60 ℃;
(2) ultrasonically dispersing the hydrophilic three-dimensional structure graphene powder obtained in the step (1) into deionized water to obtain a uniformly dispersed hydrophilic three-dimensional structure graphene solution A, wherein the dosage ratio of the hydrophilic three-dimensional structure graphene powder to the deionized water is 0.1 g: 30mL, and the ultrasonic time is 30 min;
(3) dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate, urea and polyethylene glycol-400 by using deionized water to obtain a solution B, wherein when a mixed solution B is prepared, the dosage ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate, the urea and the polyethylene glycol-400 is 0.003 mol: 0.006 mol: 0.036 mol: 2 ml;
(4) mixing the solution A and the solution B to obtain a solution C, and preparing the mixed solution C by using the hydrophilic three-dimensional structure graphene and NiCo2O4The dosage ratio of the components is 0.1 g: 0.72 g;
(5) transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene, carrying out constant-temperature thermal reaction, filtering and washing to obtain a three-dimensional constructed graphene-coated nickel cobaltate precursor D, wherein the constant-temperature reaction temperature is 95 ℃ and the reaction time is 8 hours when the three-dimensional constructed graphene-coated nickel cobaltate precursor D is prepared;
(6) placing the precursor D in a muffle furnace for calcining at the calcining temperature of 300 ℃ for 2h to obtain the mesoporous NiCo2O4A three-dimensional structure graphene microsphere compound.
5. The mesoporous NiCo prepared in claim 12O4Application of the three-dimensional structure graphene microsphere compound in a lithium ion battery cathode material.
6. The mesoporous NiCo prepared in claim 12O4Application of the three-dimensional structure graphene microsphere compound in a sodium ion battery cathode material.
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