CN111816867B - Sea urchin-shaped NiCo with mesoporous structure 2 O 4 Preparation method and application of three-dimensional construction graphene microsphere composite material - Google Patents
Sea urchin-shaped NiCo with mesoporous structure 2 O 4 Preparation method and application of three-dimensional construction graphene microsphere composite material Download PDFInfo
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Abstract
Sea urchin-shaped NiCo with mesoporous structure 2 O 4 The 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) Carrying out hydrothermal reaction on the mixed solution to obtain a nickel cobaltate precursor; (4) Calcining the nickel cobaltate precursor in air atmosphere to obtain the mesoporous NiCo 2 O 4 A 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 the negative electrode material of a sodium ion battery, the first discharge specific capacity is as high as 818.4mA h g ‑1 。
Description
Technical Field
The invention relates to a mesoporous NiCo structure 2 O 4 A stereo-structure graphene microsphere, in particular to sea urchin-shaped NiCo with a mesoporous structure 2 O 4 Preparation 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. But 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, which 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 Compd.,2020, 153945, zhang J F, ji G J and the like, appl.Surf.Sci., 2020,513 145854. Nevertheless, the two-dimensional graphene is easy to agglomerate and agglomerate, and is not easy to store and use. 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. Currently, constructing graphene with a three-dimensional (3D) structure has proven to be a strategy that can effectively provide a self-supporting structure, prevent graphene nanoplatelets from aggregating, and improve the energy storage performance of graphene-based materials, with unique 3D structures providing channels that can satisfy sodium ion transport (Li Y, li Z S et al, adv.mater, 2013,25 (17): 2474-2480 luo r, ma Y T et al, ACS appl.mater.inter.2020, doi: 10.1021/acsami.0c04481; chen W, ning Y et al, mater.lett.2019, 236-621.
NiCo 2 O 4 Is 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 NiCo 2 O 4 In the electrochemical reaction of (2), ni is present 3 + /Ni 2+ And Co 3+ /Co 2+ Two redox couples provide two active centers for the pseudocapacitance. With a single component of the metal oxide Co 3 O 4 Binary metal oxide NiCo, as opposed to NiO 2 O 4 Has high conductivity, mechanical stability, theoretical capacity and low cost. To improve NiCo 2 O 4 Many efforts have been made to improve the electrochemical properties of NiCo 2 O 4 Surface modification, nanocrystallization, and mixing with various carbons to form a composite material (Wu Gongying, wang Huanwen, journal of physico-chemistry 2013,29 (7), 1501-1506). Nickel nitrate hexahydrate, cobalt nitrate hexahydrate and NH 4 F. 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 16194-16201) A one-dimensional porous NiCo was synthesized by a solvothermal method 2 O 4 Micro rod at 100mA g -1 When 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 431.1mA h g -1 . (Li Fangfang, wang Hongbin, wang Runwei, et al, proc. Of higher school chemistry, 2017,38 (11): 1913-1920) rod-like NiCo was synthesized by a one-step hydrothermal method 2 O 4 The @ C complex of100mA g -1 At a current density of (b), niCo 2 O 4 The discharge capacities of the @ C compound as the lithium ion battery anode material after the initial time and the 5-time circulation are 767.2mA h g -1 And 650.1mA h g -1 . (Zhang Mingmei, li Yuan, xie Jimin, etc., chinese patent CN 106169384A discloses a three-dimensional mesoporous NiCo 2 O 4 The 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 NiCo 2 O 4 The nitrogen-doped graphene composite electrode material. Chinese patent CN 104882298A discloses a microwave method for preparing NiCo 2 O 4 A 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 NiCo 2 O 4 A 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 prepared 2 O 4 Preparation method of three-dimensional structure graphene microsphere composite material, wherein the obtained material is 100mA g -1 The lithium ion battery cathode material and the sodium ion battery cathode material are respectively used under current density, and the first discharge specific capacity is 1403mA h g -1 And 818.4mA h g -1 The material has good rate capability and cycling stability.
The invention realizes the purpose through the following technical scheme: sea urchin-shaped NiCo with mesoporous structure 2 O 4 The preparation method of the three-dimensional construction graphene microsphere composite material comprises the following steps:
(1) Placing the three-dimensional structure graphene powder into a hydrothermal kettle lined with polytetrafluoroethylene, adding 68wt% 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 1g: 25-70 mL, the reaction temperature is 80-160 ℃, the reaction time is 10-36 h, and the temperature for drying the three-dimensional structure graphene powder is 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 0.1g: 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 to 4ml;
(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 NiCo 2 O 4 The dosage ratio of (A) to (B) is 0.1g: 0.3-1.2 g;
(5) Transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene for 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) Calcining the precursor D in a muffle furnace at the temperature of 280-360 ℃ for 1-4 h to obtain the mesoporous NiCo 2 O 4 A three-dimensional structure graphene microsphere compound.
Furthermore, the temperature/time of the hydrothermal reaction is 95-110 ℃/8-4 h.
Furthermore, the calcining temperature is controlled between 300 and 335 ℃.
The mesoporous NiCo 2 O 4 Graphene microsphere compound for three-dimensional constructionThe preparation method comprises the following steps:
(1) Placing the three-dimensional structure graphene powder into a hydrothermal kettle lined with polytetrafluoroethylene, adding 68wt% 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 1g: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 0.1g:30mL, and ultrasonic treatment time is 30min;
(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 0.003mol:0.006mol:0.036mol:2ml;
(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 NiCo 2 O 4 The dosage ratio of the components is 0.1g:0.72g;
(5) Transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene for 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 NiCo 2 O 4 A three-dimensional structure graphene microsphere compound.
The prepared mesoporous NiCo 2 O 4 Application of the three-dimensional structure graphene microsphere compound in a lithium ion battery cathode material.
The prepared mesoporous NiCo 2 O 4 Application 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 invention 2 O 4 The stereo-structured graphene microsphere composite electrode material has controllable microsphere size and controllable nanorod size 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 138.81m 2 g –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 -1 The first discharge specific capacity is respectively up to 1403mA h g -1 And 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 structure 2 O 4 An 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 a mesoporous structure 2 O 4 SEM image of stereo-structured graphene.
FIG. 4 shows a sea urchin-like NiCo with mesoporous structure 2 O 4 A nitrogen adsorption-desorption curve chart of the three-dimensional constructed graphene.
FIG. 5 shows sea urchin-like (a) NiCo 2 O 4 And (b) NiCo 2 O 4 The stereo-structured graphene microsphere is used as the cathode material of the lithium ion battery and is 0.1A g -1 Cycling performance at current density.
FIG. 6 shows sea urchin-like (a) NiCo 2 O 4 And (b) NiCo 2 O 4 The stereo-structured graphene microsphere is used as a sodium ion battery cathode material and is 0.1A g -1 Cycling performance at current density.
Detailed Description
The technical scheme of the invention is further explained by combining the implementation 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 68wt% 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 structure graphene powder. The product is proved to have a three-dimensional structure through SEM analysis; XPS analysis showed that sp was present in the product 2 C; 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 68wt% of nitric acid. The prepared product is the hydrophilic three-dimensional structure graphene. As shown in fig. 1 and 2.
Example 2
Preparation of sea urchin-shaped NiCo with mesoporous structure 2 O 4 . 0.8724g of 0.003mol nickel nitrate hexahydrate, 1.7462g of 0.006mol cobalt nitrate hexahydrate, 2.1622g of 0.036mol urea and 2mL polyethylene glycol-400 were dissolved in 60mL deionized water. The resulting solution was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8h. 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 NiCo 2 O 4 And (3) precursor. Mixing NiCo 2 O 4 The precursor is in air for 2min -1 Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure 2 O 4 Sea urchin shaped NiCo 2 O 4 Has a pore diameter and a specific surface area of 3.98nm and 125.71m respectively 2 g –1 . The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 Used as the negative electrode material of the lithium ion battery, is 0.1A g -1 Under the current density, the first discharge capacity and the 50 th cycle discharge capacity are 1409.6mA h g -1 And 610.7mA h g –1 As shown in fig. 5 a. The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 Used as the negative electrode material of sodium ion battery, is 0.1A g -1 At a current density, the first discharge capacity and the 50 th-cycle discharge capacity were 638mA h g -1 And 214.6mA hg –1 As shown in fig. 6 a.
Example 3
Preparation of sea urchin-shaped NiCo with mesoporous structure 2 O 4 A 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 stereostructured graphene and 2mL 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 8h. 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 deg.C for 4 hr to obtain NiCo 2 O 4 A precursor of stereostructured graphene. Mixing NiCo with a solvent 2 O 4 The precursor of the stereo-structured graphene is in the air atmosphere for 2min -1 Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structure graphene microspheres are shown in figures 2 and 3, and the aperture and the specific surface area of the composite material are respectively 4.45nm and 138.81m 2 g –1 As shown in FIG. 4, the pore size and specific surface area of the composite material are both greater than those of a single NiCo 2 O 4 The sample is mentionedHigh. The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structured graphene microsphere is used as a lithium ion battery cathode material and is 0.1A g -1 At a current density, the first discharge capacity and the 50 th-cycle discharge capacity were 1403mA h g and g, respectively -1 And 1027mA h g –1 As shown in fig. 5 b. The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structured graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g -1 The first discharge capacity and the 50 th cycle discharge capacity were 819mA hr g at current density, respectively -1 And 314mA h g –1 As shown in fig. 6 b. Shows NiCo 2 O 4 NiCo obtained by coating surface of graphene through three-dimensional construction 2 O 4 Single NiCo prepared under the same technical condition of lithium/sodium storage performance ratio of three-dimensional structure graphene composite 2 O 4 Are all obviously improved.
Example 4
Preparation of sea urchin-shaped NiCo with mesoporous structure 2 O 4 A three-dimensional structure graphene microsphere.
1.7448g of 0.006mol nickel nitrate hexahydrate, 3.4924g of 0.012mol cobalt nitrate hexahydrate, 4.3244 g of 0.072mol urea, 200mg of hydrophilic stereostructured graphene, 3mL of polyethylene glycol-400 were ultrasonically dispersed in 60mL deionized water. The resulting mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8h. 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 NiCo 2 O 4 A precursor of stereostructured graphene. Mixing NiCo 2 O 4 The precursor of the stereo-structured graphene is in the air atmosphere for 2min -1 The temperature rise rate of the catalyst is calcined for 2 hours at the temperature of 300 ℃ to obtain the sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The aperture and the specific surface area of the composite material are respectively 4.40nm and 129.03m 2 g –1 The 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. To be preparedSea urchin-shaped NiCo with mesoporous structure 2 O 4 The stereo-structured graphene microsphere is used as a lithium ion battery cathode material and is 0.1A g -1 At a current density, the first discharge capacity and the 50 th-cycle discharge capacity were 1370 mA hr g -1 And 1001mA h g –1 . The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structure graphene is used as the cathode material of the sodium-ion battery and is 0.1A g -1 The first discharge capacity and the 50 th cycle discharge capacity were 810mA h g and g, respectively, at a current density -1 And 310mA h g –1 . Shows the resulting NiCo 2 O 4 The 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 structure 2 O 4 A stereo-structure graphene microsphere.
2.6172g of 0.009mol nickel nitrate hexahydrate, 5.2386g of 0.018mol cobalt nitrate hexahydrate, 6.4866 g of 0.108mol urea, 300mg of hydrophilic stereostructured graphene, 6mL of polyethylene glycol-400 were ultrasonically dispersed in 60mL deionized water. The resulting mixture was transferred to a 100mL teflon lined hydrothermal reaction kettle and heated at 95 ℃ for 8h. 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 deg.C for 4 hr to obtain NiCo 2 O 4 A precursor of the stereostructured graphene. Mixing NiCo 2 O 4 The precursor of the stereo-structured graphene is in the air atmosphere for 2min -1 Calcining the mixture at the temperature of 300 ℃ for 2 hours to obtain the sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The aperture and the specific surface area of the composite material are respectively 4.25nm and 126.7m 2 g –1 The pore diameter and the specific surface area of the composite material are both larger than those of single NiCo 2 O 4 The samples were improved but less than the samples of examples 3 and 4. The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structured graphene microsphere is used as a lithium ion battery cathode material and is 0.1A g -1 The first discharge capacity and the 50 th cycle discharge capacity were 1365mA h g and g, respectively, at current density -1 And 995mA h g –1 . The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structured graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g -1 The first discharge capacity and the 50 th cycle discharge capacity were respectively 800mA hr g at current density -1 And 300.4mA hr g –1 . Shows NiCo 2 O 4 NiCo obtained after surface coating of graphene through three-dimensional construction 2 O 4 Single NiCo with lithium/sodium storage performance ratio of stereostructure graphene composite 2 O 4 Both are significantly improved, but less than the samples of example 3 and example 4.
Example 6
Prepared sea urchin-shaped NiCo with mesoporous structure 2 O 4 A stereo-structure graphene microsphere.
0.8724g 0.003mol nickel nitrate hexahydrate, 1.7462g 0.006mol cobalt nitrate hexahydrate, 2.1622g 0.036mol urea, 100mg hydrophilic stereostructured graphene, 2mL polyethylene glycol-400 was ultrasonically dispersed in 60mL deionized water. The resulting mixture was transferred to a 100mL polytetrafluoroethylene-lined hydrothermal reaction kettle and heated at 110 ℃ for 8h. 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 NiCo 2 O 4 A precursor of the stereostructured graphene. Mixing NiCo with a solvent 2 O 4 The precursor of the stereo-structured graphene is in the air atmosphere for 2min -1 The 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 structure 2 O 4 The aperture and the specific surface area of the composite material are respectively 3.80nm and 110.6m 2 g –1 The 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 structure 2 O 4 The stereo-structured graphene microsphere is used as a lithium ion battery cathode material and is 0.1A g -1 First discharge capacity and 50 th cycle at current densityThe discharge capacities were 1350mA hr g, respectively -1 And 990mA h g –1 . The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structured graphene is used as a negative electrode material of a sodium ion battery and is 0.1A g -1 The first discharge capacity and the 50 th cycle discharge capacity were 798mA hr g, respectively, at a current density -1 And 285mA h g –1 . Indicating that NiCo is obtained under the conditions of this technique 2 O 4 The 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 structure 2 O 4 A stereo-structure graphene microsphere.
0.8724g 0.003mol nickel nitrate hexahydrate, 1.7462g 0.006mol cobalt nitrate hexahydrate, 2.1622g 0.036mol urea, 100mg hydrophilic stereo-structured graphene, 2mL polyethylene glycol-400 were ultrasonically dispersed in 60mL deionized water. The resulting mixture was transferred to a 100mL polytetrafluoroethylene-lined hydrothermal reaction kettle and heated at 105 ℃ for 6h. 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 NiCo 2 O 4 A precursor of the stereostructured graphene. Mixing NiCo 2 O 4 Precursor of stereo-structured graphene in air for 2min -1 The 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 structure 2 O 4 A three-dimensional structure graphene microsphere. The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structure graphene microsphere is used as the cathode material of the lithium ion battery and is 0.5A g -1 The first discharge capacity and the 10 th cycle discharge capacity were 1300mA h g at current density -1 And 900mA h g –1 . When the material is used as a sodium ion battery anode material, the material is 0.5A g -1 At a current density, the first discharge capacity and the 10 th-cycle discharge capacity were 645mA h g and g, respectively -1 And 450mA h g –1 。
Example 8
Prepared sea urchin-shaped NiCo with mesoporous structure 2 O 4 A 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 stereostructured graphene, 2mL of polyethylene glycol-400 were ultrasonically dispersed in 60mL deionized water. The resulting mixture was transferred to a 100mL polytetrafluoroethylene lined hydrothermal reaction kettle and heated at 110 ℃ for 4h. After cooling to room temperature, the precipitate was collected by suction filtration with a 6 # sand core funnel and washed alternately 3 times with deionized water and absolute ethanol. Drying the precipitate in a vacuum drying oven at 60 deg.C for 4 hr to obtain NiCo 2 O 4 A precursor of hydrophilic three-dimensional structured graphene. Mixing NiCo 2 O 4 Precursor of hydrophilic three-dimensional constructed graphene in air for 2min -1 The 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 obtained 2 O 4 A three-dimensional structure graphene microsphere. The prepared sea urchin-shaped NiCo with the mesoporous structure 2 O 4 The stereo-structured graphene microsphere is used as a lithium ion battery cathode material and is 1A g -1 At a current density, the first discharge capacity and the 200 th-cycle discharge capacity were 1308mA h g -1 And 500mA h g –1 . When the material is used as a sodium ion battery anode material, the surface roughness is 1A g -1 At a current density, the first discharge capacity and the 10 th-cycle discharge capacity were 638mA h g -1 And 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 added 2 O 4 Compared with sea urchin-shaped NiCo without added stereostructural graphene, the stereostructural graphene microsphere 2 O 4 The microspheres have higher discharge capacityAmount and cycling stability. This is due to the coating of the sea urchin-like NiCo 2 O 4 The 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 NiCo 2 O 4 Volume change during charge/discharge. Furthermore, in order to obtain NiCo with large specific surface area and high electrochemical performance 2 O 4 The calcining temperature of the stereo-structured graphene microspheres is controlled to be 300-335 ℃.
Claims (6)
1. Sea urchin-shaped NiCo with mesoporous structure 2 O 4 The 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 68wt% 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 1g: 25-70 mL of graphene powder, the reaction temperature is 80-160 ℃, the reaction time is 10-36 h, and the temperature for drying the three-dimensional structure graphene powder is 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 0.1g: 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 to 4ml;
(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 NiCo 2 O 4 The dosage ratio of the components is 0.1g: 0.3E1.2g；
(5) Transferring the solution C into a hydrothermal kettle lined with polytetrafluoroethylene for 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 NiCo 2 O 4 A three-dimensional structure graphene microsphere compound.
2. The mesoporous NiCo of claim 1 2 O 4 The preparation method of the three-dimensional structure graphene microsphere compound is characterized in that the hydrothermal reaction temperature/time is 95-110 ℃/8-4 h.
3. The mesoporous NiCo of claim 1 2 O 4 The 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 1 2 O 4 The 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 68wt% 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 1g:40mL, the reaction temperature is 120 ℃, the reaction time is 24 hours, and the temperature for drying and stereostructuring the 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 use amount ratio of the hydrophilic three-dimensional structure graphene powder to the deionized water is 0.1g:30mL, and the ultrasonic time is 30min;
(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 0.003mol:0.006mol:0.036mol:2ml;
(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 NiCo 2 O 4 The dosage ratio of the components is 0.1g:0.72g;
(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) Calcining the precursor D in a muffle furnace at the calcining temperature of 300 ℃ for 2 hours to obtain the mesoporous NiCo 2 O 4 A three-dimensional structure graphene microsphere compound.
5. The mesoporous NiCo prepared in claim 1 2 O 4 Application of the three-dimensional structure graphene microsphere compound in a lithium ion battery cathode material.
6. The mesoporous NiCo prepared in claim 1 2 O 4 Application of the three-dimensional structure graphene microsphere compound in a sodium ion battery cathode material.
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