CN115215380A - Cobaltosic oxide/nitrogen-doped graphene oxide material, preparation method thereof and application thereof in sodium-ion battery - Google Patents

Cobaltosic oxide/nitrogen-doped graphene oxide material, preparation method thereof and application thereof in sodium-ion battery Download PDF

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CN115215380A
CN115215380A CN202210823826.2A CN202210823826A CN115215380A CN 115215380 A CN115215380 A CN 115215380A CN 202210823826 A CN202210823826 A CN 202210823826A CN 115215380 A CN115215380 A CN 115215380A
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nitrogen
graphene oxide
doped graphene
cobaltosic
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CN115215380B (en
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陈建
胡茂源
张文静
岳晨曦
唐丽平
伍言康
雷志强
唐湖林
李大舜
代祖洋
房新华
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Sichuan University of Science and Engineering
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Abstract

The invention relates to the technical field of sodium ion battery cathode materials, and provides a cobaltosic oxide/nitrogen-doped graphene oxide material, a preparation method thereof and application thereof in a sodium ion battery. Mixing graphene oxide, a nitrogen source, a cobalt source and water to obtain a suspension, carrying out hydrothermal reaction on the suspension to obtain a precursor, and directly freeze-drying the precursor to obtain a precursor; and sintering the precursor to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material. The method provided by the invention can improve the nitrogen doping amount in the composite material and improve the electrochemical performance of the composite material. The cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the method is used as a negative electrode material of a sodium ion battery, and the sodium ion battery has high specific capacity, rate capability and cycling stability.

Description

Cobaltosic oxide/nitrogen-doped graphene oxide material, preparation method thereof and application of material in sodium-ion battery
Technical Field
The invention relates to the technical field of sodium ion battery cathode materials, in particular to a cobaltosic oxide/nitrogen-doped graphene oxide material, a preparation method thereof and application thereof in a sodium ion battery.
Background
The lithium ion battery has excellent electrochemical properties such as high working voltage, long cycle life, high energy density and the like, and is widely developed and applied in the fields of new energy automobiles and energy storage equipment at present. But in the long run, the shortage and uneven distribution of global lithium resources will severely limit the development of lithium ion batteries. The chemical reaction mechanism of the sodium ion battery is similar to that of the lithium ion battery, the sodium ion battery can be compatible with the production equipment of the lithium ion battery, and meanwhile, the sodium ion battery is considered as a potential substitute of the lithium ion battery due to the abundant global sodium resource and the cost lower than that of the lithium ion battery.
However, since the diffusion rate of sodium ions in the negative electrode material is lower than that of lithium ions, reversible storage of sodium ions at room temperature is more difficult, resulting in poor cycle stability of the sodium ion battery. Transition metal oxides are commonly used as the negative electrode material for sodium storage in the prior art, wherein Co 3 O 4 Has the advantages of high theoretical specific capacity, reversible sodium storage and the like, and is used in large quantities. However, co 3 O 4 The volume change and expansion are large, the initial coulombic efficiency is low, the conductivity is poor in the charge-discharge process, and the electrochemical performance of the sodium ion battery cathode material is not favorably improved.
In order to solve the above problems, the prior art mostly uses Co 3 O 4 And the carbon nano fiber and the carbon nano tube are compounded with various carbon materials, such as carbon nano fiber, carbon nano tube and the like, so that the electrochemical performance of the material is improved. Meanwhile, nitrogen doping can improve the structural defects of the carbon material and reduce Na + The barrier entering the carbon material indirectly generates more pore structures and wrinkle structures, thereby forming larger specific surface area and further improving the electrochemical performance of the material. The cobalt oxide @ nitrogen-doped multi-walled carbon nanotube/polypyrrole composite material (DOI: 10.1016/j. Colsurffb.2021.111840) is prepared by Sivalignam Ramesh and the like, but the doping amount of nitrogen elements on the carbon material is 3.15%, the content is lower, and the improvement on the electrochemical performance of the material is limited.
Disclosure of Invention
In view of this, the invention provides a cobaltosic oxide/nitrogen-doped graphene oxide material, a preparation method thereof and application thereof in a sodium-ion battery. The preparation method provided by the invention can dope more nitrogen elements on the carbon material in the cobaltosic oxide/nitrogen-doped graphene oxide material, and the electrochemical performance of the composite material is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of cobaltosic oxide/nitrogen-doped graphene oxide material, which comprises the following steps:
mixing graphene oxide, a nitrogen source, a cobalt source and water to obtain a suspension;
carrying out hydrothermal reaction on the suspension to obtain a precursor solution;
directly freeze-drying the precursor liquid to obtain a precursor;
and sintering the precursor to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material.
Preferably, the mass ratio of graphene oxide to water in the suspension is 0.06-0.15, and the mass ratio of graphene oxide, nitrogen source and cobalt source is 0.06-0.15.
Preferably, the cobalt source comprises Co (NO) 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O、CoF 2 、CoCl 2 、 CoBr 2 Or CoI 2 (ii) a The nitrogen source comprises melamine or urea.
Preferably, the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 8-12 h.
Preferably, the temperature of the freeze drying is-60 to-40 ℃, and the time is 24 to 48 hours.
Preferably, the sintering temperature is 400-500 ℃, the time is 1-2 h, and the heating rate of heating to the sintering temperature is 2-10 ℃/min.
The invention also provides the cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the preparation method in the technical scheme, which comprises nitrogen-doped graphene oxide and cobaltosic oxide particles distributed on the nitrogen-doped graphene oxide, wherein the cobaltosic oxide particles are spherical or quasi-spherical, the particle size of the cobaltosic oxide particles is 10-20 nm, and the nitrogen doping amount of the cobaltosic oxide/nitrogen-doped graphene oxide material is not less than 4.2wt%.
Preferably, the loading amount of the cobaltosic oxide in the cobaltosic oxide/nitrogen-doped graphene oxide material is 46-50 wt%.
The invention also provides application of the cobaltosic oxide/nitrogen-doped graphene oxide material in the technical scheme as a sodium ion battery cathode material.
The invention provides a preparation method of cobaltosic oxide/nitrogen-doped graphene oxide material, which comprises the following steps: mixing graphene oxide, a nitrogen source, a cobalt source and water to obtain a suspension; carrying out hydrothermal reaction on the suspension to obtain a precursor solution; directly freeze-drying the precursor liquid to obtain a precursor; and sintering the precursor to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material. According to the invention, graphene oxide, a nitrogen source and a cobalt source are subjected to hydrothermal reaction to prepare a precursor solution, the precursor solution is freeze-dried, more nitrogen elements capable of being fixed on graphene are reserved, then the nitrogen elements are fixed on the graphene in a sintering manner, the nitrogen doping amount in the composite material is increased, the nitrogen doping can reduce the positive charge density around carbon atoms and increase the structural defects of active sites or carbon materials, so that the diffusion of electrolyte to electrodes and the adsorption of sodium are better promoted, and the Na is increased + The migration rate in the electrode reduces the internal impedance of the electrode and improves the electrochemical performance of the composite material.
The invention also provides the cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the preparation method in the scheme. In the cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the invention, the cobaltosic oxide is spherical particles, the particle size is 10-20 nm, the problem of volume expansion of the cobaltosic oxide in the charging and discharging processes can be relieved by smaller particle size, the nitrogen doping amount in the cobaltosic oxide/nitrogen-doped graphene oxide material is not less than 4.2wt%, the nitrogen doping can improve the structural defects of the carbon material, and reduce Na + The carbon material enters a potential barrier of the carbon material, more pore structures and wrinkle structures are indirectly generated, so that a larger specific surface area is formed, and the electrochemical performance of the material is further improved.
The invention also provides application of the cobaltosic oxide/nitrogen-doped graphene oxide material in the technical scheme as a negative electrode material of a sodium-ion battery. Data of the embodiment of the invention show that the cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the invention has higher reversible capacity, longer cycle performance and better rate performance, and can be used as a negative electrode material of a sodium-ion battery.
Drawings
Fig. 1 is a flow chart of the cobaltosic oxide/nitrogen-doped graphene oxide material prepared in example 1;
fig. 2 is a scanning electron micrograph of graphene oxide prepared in example 1;
FIG. 3 shows Co prepared in example 1 3 O 4 Scanning electron micrographs of/N-GNS;
FIG. 4 shows Co prepared in example 1 3 O 4 a/N-GNS transmission electron microscope image and an element distribution diagram;
FIG. 5 shows Co 3 O 4 N-GNS and Co 3 O 4 XPS spectra of (1);
FIG. 6 shows Co 3 O 4 TG analysis result chart of/N-GNS;
fig. 7 is a schematic structural view of a CR2032 button cell in example 1;
FIG. 8 shows Co 3 O 4 /N-GNS、Co 3 O 4 The result graphs of multiplying power performance and cycle stability performance of the graphene oxide (GNS) and the nitrogen-doped graphene oxide (N-GNS);
FIG. 9 shows Co 3 O 4 And Co 3 O 4 Electrochemical impedance spectrum of/N-GNS.
Detailed Description
The invention provides a preparation method of cobaltosic oxide/nitrogen-doped graphene oxide material, which comprises the following steps:
mixing graphene oxide, a nitrogen source, a cobalt source and water to obtain a suspension;
carrying out hydrothermal reaction on the suspension to obtain a precursor solution; directly freeze-drying the precursor liquid to obtain a precursor;
and sintering the precursor to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material.
Unless otherwise specified, the starting materials for the preparation used in the present invention are commercially available.
The method comprises the step of mixing graphene oxide, a nitrogen source, a cobalt source and water to obtain a suspension. In the invention, the graphene oxide is preferably prepared by a Hummers method. In the invention, the graphene oxide prepared by the Hummers method has fewer layers, can improve the surface area of the material, and is more favorable for improving the electrochemical performance of the material loaded with cobaltosic oxide. In a specific embodiment of the present invention, the method for preparing graphene oxide by using Hummers method preferably includes the following steps: adding 2.5g of crystalline flake graphite and 3g of sodium nitrate into a three-neck flask, and placing the three-neck flask in an ice-water bath for 10min; adding 150mL of 98wt% concentrated sulfuric acid into a three-neck flask, and stirring for 30min; adding 20g of potassium permanganate into a three-neck flask, stirring for 1h, and then continuing stirring for 24h at room temperature; adding 240mL of deionized water into the three-neck flask, and continuously stirring for 30min; finally, 700mL of deionized water and 80mL of 30wt% hydrogen peroxide are added to obtain a primary sample; and sequentially carrying out first acid washing, hydrogen peroxide washing, second acid washing and water washing on the primary sample, and drying the washed sample to obtain the graphene oxide. In the invention, the washing liquid used for the first acid washing is preferably 50-70 wt% of dilute sulfuric acid, the washing liquid used for the hydrogen peroxide washing is preferably 20-30 wt% of hydrogen peroxide, the washing liquid used for the second acid washing is preferably 36-38 wt% of hydrochloric acid solution, and the washing liquid used for the water washing is preferably deionized water. In the present invention, the molar mass ratio of the primary sample, sulfuric acid, hydrogen peroxide and hydrochloric acid is preferably 1. In the present invention, the first acid washing, hydrogen peroxide washing, second acid washing, and water washing are preferably performed in the following manner: the washing solution and the primary sample are stirred and then filtered. In the present invention, it is preferable that the deionized water after washing be neutral as a washing end point. In the present invention, the drying is preferably performed in a vacuum drying oven, and the temperature of the drying is preferably 80 ℃. The present invention does not particularly require the drying time, and the sample after washing may be dried to a constant weight.
In the present invention, the specific manner of mixing preferably includes the steps of: adding the graphene oxide into the water for ultrasonic dispersion to obtain a graphene oxide dispersion liquid; and sequentially adding a nitrogen source and a cobalt source into the graphene oxide dispersion liquid to obtain the suspension. In the present invention, the power of the ultrasonic dispersion is preferably 300 to 450W, more preferably 350 to 400W, and the time of the ultrasonic dispersion is preferably 1 to 2 hours, more preferably 1 to 1.5 hours. According to the invention, preferably, after the nitrogen source is completely dissolved, a cobalt source is added; the invention has no special requirement on the mode of dissolving the nitrogen source and the cobalt source in the graphene oxide dispersion liquid, so as to form uniform and stable suspension. According to the invention, the graphene oxide dispersion liquid is preferably prepared firstly, which is beneficial to improving the contact area of the graphene oxide with the nitrogen source and the cobalt source, so that more nitrogen source and cobalt ions are loaded into the graphene oxide sheet layer.
In the present invention, the mass ratio of graphene oxide to water in the suspension is preferably 0.06 to 0.15:70, more preferably 0.08 to 0.14, and even more preferably 0.10 to 0.12, and in the present invention, the mass ratio of graphene oxide to water is preferably controlled within the above range, so that graphene oxide can be uniformly dispersed in water, and the effect of hydrothermal reaction can be improved. In the invention, the mass ratio of the graphene oxide, the nitrogen source and the cobalt source in the suspension is preferably 0.06-0.15; more preferably 0.08 to 0.14, 1.0 to 1.6, and still more preferably 0.10 to 0.12. In the present invention, the cobalt source preferably comprises Co (NO) 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O、CoF 2 、CoCl 2 、CoBr 2 Or CoI 2 More preferably C o (NO) 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O or CoCl 2 More preferably Co (NO) 3 ) 2 ·6H 2 O or Co SO 4 ·7H 2 O, most preferably Co (NO) 3 ) 2 ·6H 2 And (O). In the present invention, the nitrogen source preferably comprises urea or melamine, more preferably urea.
After the suspension is obtained, the invention carries out hydrothermal reaction on the suspension to obtain the precursor solution. In the present invention, the temperature of the hydrothermal reaction is preferably 150 to 200 ℃, more preferably 160 to 180 ℃, and further preferably 180 ℃; the hydrothermal reaction time is preferably 8 to 12 hours, more preferably 9 to 11 hours, and still more preferably 10 hours. In the present invention, the rate of temperature increase to the temperature required for the hydrothermal reaction is preferably 2 to 10 ℃/min, more preferably 5 to 7 ℃/min, and still more preferably 5 ℃/min. The temperature and the time of the hydrothermal reaction are preferably controlled within the range, so that the consistency and the perfection of the crystal morphology of the cobaltosic oxide can be improved and the defects of the crystal morphology can be reduced by avoiding the over-low reaction temperature and the incomplete hydrothermal reaction, and the cobaltosic oxide can be prevented from being seriously agglomerated or generating the morphology with larger sizes such as diamond or sheet due to the over-high reaction temperature, the specific surface area of the cobaltosic oxide can be reduced, the contact area of the material in the electrochemical reaction can be reduced, and the adverse effect on the electrochemical performance can be caused.
After the precursor liquid is obtained, the precursor liquid is directly freeze-dried to obtain the precursor. In the present invention, the temperature of the freeze-drying is preferably-60 to-40 ℃, more preferably-50 to-40 ℃, and still more preferably-50 ℃, and the time of the freeze-drying is preferably 24 to 48 hours, more preferably 28 to 40 hours, and still more preferably 30 to 36 hours. The method preferentially and directly carries out freeze drying on the precursor solution without suction filtration and centrifugation, provides more nitrogen sources for subsequent sintering, provides a foundation for improving the nitrogen doping amount, and simultaneously adopts freeze drying to further reduce the agglomeration condition of cobaltosic oxide particles and ensure that the graphene oxide keeps the original skeleton structure.
After obtaining the precursor, sintering the precursor to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material. In the present invention, the sintering temperature is preferably 400 to 500 ℃, more preferably 450 to 500 ℃, the sintering time is preferably 1 to 2 hours, more preferably 1.5 to 2 hours, and the temperature increase rate for increasing the temperature to the temperature required for sintering is preferably 2 to 10 ℃/min, more preferably 5 to 7 ℃/min, and further preferably 5 ℃/min. In the present invention, the sintering is preferably performed in an inert atmosphere, which is preferably a nitrogen, argon or helium atmosphere, more preferably an argon atmosphere. In the present invention, the sintering is preferably followed by natural cooling. According to the invention, the sintering conditions are preferably selected to ensure that nitrogen elements are fixed on the graphene oxide through three nitrogen-carbon chemical bonds of pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, and the crystal form of cobaltosic oxide is more perfect.
The invention provides a cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the preparation method in the technical scheme, which comprises nitrogen-doped graphene oxide and cobaltosic oxide particles distributed on the nitrogen-doped graphene oxide, wherein the cobaltosic oxide particles are spherical, the particle size of the cobaltosic oxide particles is 10-20 nm, and the nitrogen doping amount of the cobaltosic oxide/nitrogen-doped graphene oxide material is not less than 4.2wt%, and more preferably 4.2-4.5 wt%. The amount of the cobaltosic oxide supported on the cobaltosic oxide/nitrogen-doped graphene oxide material is preferably 46 to 50wt%, and more preferably 47 to 48.5wt%.
The invention also provides application of the cobaltosic oxide/nitrogen-doped graphene oxide material in the technical scheme as a sodium-ion battery cathode material. The embodiment of the invention shows that the cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the method has good electrochemical performance and is suitable for being used as a negative electrode material of a sodium-ion battery.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
1. Preparation of graphene oxide
The graphene oxide adopted in the embodiment is prepared by a Hummers method, and the method comprises the following steps:
a. accurately weighing 2.5g of crystalline flake graphite and 3g of sodium nitrate, adding the crystalline flake graphite and the sodium nitrate into a 1000mL three-neck flask, and placing the three-neck flask in an ice-water bath for 10min;
b. accurately weighing 150mL of 98wt% concentrated sulfuric acid, adding into a three-neck flask, adding a stirrer, and stirring for 30min;
c. accurately weighing 20g of potassium permanganate, slowly adding the potassium permanganate into a three-neck flask, reacting for 1h, and finally stirring at room temperature for 24h, wherein the solution in the three-neck flask is changed from the initial dark green solution into a dark brown viscous solution;
d. adding 240mL of deionized water, continuing to react for 30min, and finally adding 700mL of deionized water and 80mL of 30wt% hydrogen peroxide, wherein the color of the solution in the three-neck flask is changed into yellow, so as to obtain a primary sample.
2. Purification of graphene oxide
Stirring and filtering the primary sample obtained in the step by adopting 70wt% dilute sulfuric acid, adding the solid obtained after filtering into 30wt% hydrogen peroxide for stirring and filtering, adding 31wt% hydrochloric acid into the solid obtained after filtering for stirring and filtering, and adding deionized water into the solid obtained after filtering for cleaning until the cleaning liquid obtained by filtering is neutral. Wherein, the molar mass ratio of the primary sample to the sulfuric acid to the hydrogen peroxide to the hydrochloric acid is 1. And (3) putting the solid sample obtained after the suction filtration into a vacuum drying oven, and drying at 80 ℃ to constant weight to obtain the graphene oxide.
3. The preparation method of the cobaltosic oxide/nitrogen-doped graphene oxide material comprises the following steps:
a. dispersing 0.12g of graphene oxide prepared by the method in 70mL (70 g) of deionized water, and carrying out ultrasonic treatment for 1h at 350W to obtain a graphene oxide dispersion liquid;
b. adding 0.8g of urea into the graphene oxide dispersion liquid obtained in the step a, dissolving the urea in an ultrasonic mode, and then adding 1g of Co (NO) 3 ) 2 ·6H 2 Dissolving the mixture in an ultrasonic mode to obtain suspension;
c. transferring the suspension obtained in the step b to a high-pressure hydrothermal reaction kettle with the volume of 150mL, heating to 180 ℃ at the heating rate of 5 ℃/min, and carrying out hydrothermal reaction for 10 hours to obtain a precursor solution;
d. d, freeze-drying the precursor solution obtained in the step c for 48 hours at the temperature of 50 ℃ below zero to obtain a precursor;
e. and d, sintering the precursor obtained in the step d, wherein the sintering atmosphere is argon atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min during sintering, preserving heat for 2h, and then naturally cooling to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material. For the convenience of subsequent description, the prepared cobaltosic oxide/nitrogen-doped graphene oxide material is referred to as Co for short 3 O 4 /N-GNS。
FIG. 1 shows the present embodimentExample preparation of Co 3 O 4 The flow chart of the/N-GNS specifically comprises the following steps: carrying out ice bath on the flake graphite and sodium nitrate, then adding concentrated sulfuric acid and potassium permanganate to react to obtain graphite oxide, and mixing the graphite oxide with urea and Co (NO) 3 ) 2 ·6H 2 Performing hydrothermal synthesis, freeze drying and high-temperature sintering on O in sequence to obtain Co 3 O 4 /N-GNS。
Graphene oxide and Co prepared in preparation example 1 were subjected to Scanning Electron Microscopy (SEM) 3 O 4 the/N-GNS was characterized and the results are shown in FIGS. 2 and 3. Wherein, FIG. 2 is a scanning electron microscope image of the graphene oxide prepared in example 1, and FIG. 3 is a scanning electron microscope image of the Co prepared in example 1 3 O 4 Scanning electron micrograph of/N-GNS. As can be seen from fig. 2, the flake graphite is peeled off by Hummers method to obtain graphene oxide, and the obtained graphene oxide has a layered structure and a smooth surface. As can be seen from FIG. 3, co 3 O 4 In the/N-GNS material, the surface of the nitrogen-doped graphene oxide sheet layer is not smooth any more, which is caused by Co 3 O 4 The nanoparticles are attached to the surface thereof.
To characterize Co 3 O 4 The distribution condition of the nano particles on the nitrogen-doped graphene oxide adopts a transmission electron microscope to carry out Co 3 O 4 The morphology and element distribution of the/N-GNS are further characterized, and the characterization result is shown in FIG. 4. FIG. 4 shows Co prepared in example 1 3 O 4 A transmission electron micrograph and an element distribution map of the/N-GNS. In FIG. 4, a to b are Co 3 O 4 High magnification images of/N-GNS with a 50nm scale in a and 10nm scale in b, as can be seen from a and b, co prepared in example 1 3 O 4 Co on/N-GNS 3 O 4 The size of the nano particles is between 10 and 20nm, and the nano particles are spherical. c is Co 3 O 4 HR-TEM image of the nanoparticles, with a scale of 5nm, measured a interplanar spacing of lattice fringes of 0.467nm, corresponding to cubic Co 3 O 4 Corresponds to the (111) plane of (B), indicating that cubic Co is obtained 3 O 4 . d and e are Co 3 O 4 Maping plot of/N-GNS, with scale 200 in dThe scale in nm, e is 500nm, f is the distribution diagram of the elements, and the scale in f is 500nm. As can be seen by combining the graphs of d, e and f, the atoms of Co, C, O and N are in Co 3 O 4 Homogeneous distribution on/N-GNS, indicating Co 3 O 4 The particles are uniformly distributed on the nitrogen-doped graphene oxide.
Analysis of Co by X-ray photoelectron Spectroscopy (XPS) 3 O 4 Surface elemental composition and valence of/N-GNS, with Co 3 O 4 For comparison. The results are shown in FIG. 5. FIG. 5 shows Co 3 O 4 N-GNS and Co 3 O 4 XPS spectra of (1). As can be seen from FIG. 5, co, C, O and N are present in Co 3 O 4 In the/N-GNS sample. Co 3 O 4 Only Co and O were found among the constituent elements of (A), indicating that the sample was not contaminated during the synthesis and that the prepared cobalt-containing oxide was indeed Co 3 O 4 . By calculation, a nitrogen content of 4.2wt% was obtained.
Measurement of Co by thermogravimetric analysis (TG) 3 O 4 Co in/N-GNS 3 O 4 The loading amount of TG analysis was: in an air environment, co is added at a rate of 5 ℃/min 3 O 4 The temperature of the/N-GNS was increased from room temperature to 800 ℃. The test results are shown in FIG. 6, where FIG. 6 shows Co 3 O 4 TG analysis of/N-GNS as shown in FIG. 6, co 3 O 4 The mass loss of the/N-GNS below 200 ℃ is mainly physically absorbed water on the surface of the material, and when the temperature is increased to 600 ℃, co 3 O 4 The quality of the/N-GNS is stable in the air environment, and the Co is remained in the material 3 O 4 From which can be calculated, co 3 O 4 The loading was 48.5wt%.
4. Electrochemical performance test
1. The preparation of the electrode slice comprises the following steps:
a. according to the active substance: conductive agent: binder =8:1:1, weighing an active substance, conductive carbon black SuperP and carboxymethyl cellulose (CMC) (the mass percentage of the CMC is 1%) solution for later use;
b. grinding and mixing the weighed CMC solution and Super P in a mortar uniformly, adding an active substance, continuously grinding and mixing uniformly to obtain pasty slurry;
c. spreading the cut Cu foil on a coating machine, cleaning with absolute ethyl alcohol to remove dirt and dust, and then adjusting the height of a scraper to ensure that the scraping thickness of the slurry is 100 mu m;
d. transferring the obtained ground slurry to a Cu foil for blade coating and drying, and then performing roll-in treatment on the dried Cu foil by using a roll squeezer;
e. transferring the rolled Cu foil to a vacuum drying oven at 80 ℃ for drying for 12h to obtain a copper foil coated with an active substance;
2. button cell assembly
The test cell adopted in this embodiment is a CR2032 button cell, which mainly comprises an anode, a cathode, a diaphragm, an electrolyte, a cell case, and the like, and a metal sodium sheet is used as a counter electrode, a glass fiber commercial microporous membrane is used as the diaphragm, the structural schematic diagram of the button cell is shown in fig. 7, fig. 7 is the structural schematic diagram of the CR2032 button cell in embodiment 1, and the positive electrode case, the cathode electrode sheet, the diaphragm, the metal sodium sheet, the gasket, the spring piece, and the cathode case are sequentially arranged from bottom to top in the diagram.
In this example, the active materials used were each Co 3 O 4 /N-GNS、Co 3 O 4 Graphene oxide (GNS) and nitrogen-doped graphene oxide (N-GNS), wherein GNS is the graphene oxide prepared in example 1, and the preparation method of N-GNS is the same as that of Co prepared in example 1 except that a cobalt source is not added 3 O 4 The conditions for the/N-GNS are the same. And (3) preparing the active substance according to the preparation methods of the electrode plate and the button cell to obtain the CR2032 button cell, and testing the rate capability and the cycle stability performance. The results are shown in FIG. 8, where FIG. 8 shows Co 3 O 4 /N-GNS、Co 3 O 4 Graph showing the results of multiplying power performance and cycling stability of graphene oxide (GNS) and nitrogen-doped graphene oxide (N-GNS), wherein a in FIG. 8 is Co 3 O 4 /N-GNS、Co 3 O 4 GNS and N-GNS electrodes at 0.05, 0.1, 0.2, 0.5, 1 A.g -1 The current density and the voltage window of the battery are 0.005-3V. The results show that Co 3 O 4 the/N-GNS electrode has better rapid charge and discharge performance. Co 3 O 4 the/N-GNS electrode is at 0.05, 0.1, 0.2, 0.5, 1 A.g -1 Has a stable capacity of current density of 389, 336, 293, 236 and 183mAh g -1 . When the current density is recovered to 0.05 A.g -1 The capacity of the electrode was then restored to about 363mAh g -1 At a high current density (1A. G) -1 ) Lower, co 3 O 4 Specific capacity of/N-GNS (183 mAh. G) -1 ) Higher than N-GNS (78 mAh g) -1 ) And Co 3 O 4 (3mAh·g -1 ). This indicates that Co is present 3 O 4 the/N-GNS electrode can be charged and discharged at a relatively high rate. b is Co 3 O 4 /N-GNS、Co 3 O 4 Comparison of cycling performance of the GNS and N-GNS electrodes. As can be seen from b, co 3 O 4 the/N-GNS electrode exhibited a higher capacity. Co 3 O 4 the/N-GNS electrode showed a high initial discharge/charge capacity of 630/616 mAh.g -1 The Coulombic Efficiency (CE) was 97%, and the capacity after 100 cycles was 323mAh · g -1 At this time, the Coulombic Efficiency (CE) was 100%. Co 3 O 4 the/N-GNS electrode has a higher capacity than the initial discharge/charge capacity of the N-GNS electrode of 415/140 mAh g -1 Much higher than pure Co 3 O 4 Initial discharge/charge capacity of 398mAh g -1 /386mAh·g -1 Pure Co 3 O 4 Has a 100 th discharge/charge capacity of only 16/16mAh g -1 It can be seen that pure Co 3 O 4 The capacity of the electrode decays more rapidly. This is due to pure Co 3 O 4 The particles expand greatly in volume during charging and discharging, resulting in failure of the electrode.
Measuring Co using Electrochemical Impedance Spectroscopy (EIS) 3 O 4 And Co 3 O 4 The electrochemical performance of the/N-GNS is shown in FIG. 9, and the result is shown in FIG. 9, in which Co is shown in FIG. 9 3 O 4 And Co 3 O 4 Electrochemical impedance spectroscopy of/N-GNS. As can be seen from FIG. 9, the size of the semi-circle diameter in the high frequency region is related to the charge transfer resistance of the electrode interface, the diameterThe smaller the charge transfer resistance at the electrode interface, the smaller the Co 3 O 4 Half-circle diameter ratio Co of/N-GNS in high-frequency region 3 O 4 To be small, indicating that Co 3 O 4 Impedance ratio Co of/N-GNS 3 O 4 Much lower. The nitrogen-doped graphene oxide framework has large specific surface area and high conductivity, is favorable for electron transfer and conduction, can promote charge transfer in the composite material, and is Co in a curve obtained by fitting in a low-frequency region 3 O 4 The slope of the fitted curve of the/N-GNS is less than Co 3 O 4 Indicating sodium ion in Co 3 O 4 Higher diffusion coefficient in/N-GNS than Co 3 O 4 . The results in FIG. 9 show that sodium ions are present in Co 3 O 4 De-intercalation of/N-GNS electrodes, compare Co 3 O 4 With smoother diffusion behavior.
In conclusion, the Co prepared by the invention 3 O 4 the/N-GNS electrode has high reversible capacity, long cycle performance and good rate performance. The nitrogen-rich graphene oxide nanosheets can induce more topological defects on the graphene oxide layer to form a disordered carbon structure, so that the diffusion of the electrolyte to the electrode and the adsorption of sodium are better promoted. Furthermore, nanocrystallized Co 3 O 4 The spherical particles are uniformly dispersed on the nitrogen-doped graphene oxide nanosheets, and the nano spherical or quasi-spherical shape and uniform distribution state of the spherical particles effectively slow down Co 3 O 4 The electrode failure caused by volume expansion in the charging and discharging process improves the electrochemical performance of the material.
Example 2
The graphene oxide prepared in example 1 was used in an amount of 0.1g, the mass of urea was 1.0g, and the type of cobalt source was CoSO 4 ·7H 2 O in an amount of 1.5g, hydrothermal reaction time of 8 hours, freeze-drying time of 36 hours, and sintering temperature of 400 ℃ were carried out under the same conditions as in example 1.
Example 3
With the graphene oxide prepared in example 1,the amount of the catalyst was adjusted to 0.15g, the mass of urea was adjusted to 1.5g, and the kind of cobalt source was adjusted to CoCl 2 The amount of the catalyst used was 3.0g, the rate of heating to the temperature required for hydrothermal reaction was 10 ℃/min, the temperature of freeze-drying was-40 ℃, the time of freeze-drying was 24 hours, the holding time of sintering was 1 hour, and the remaining conditions were the same as in example 1.
Example 4
The graphene oxide prepared in example 1 was used in an amount of 0.06g, the mass of urea was 0.8g, and the type of cobalt source was CoCl 2 The amount of the catalyst used was 1.0g, the rate of heating to the temperature required for the hydrothermal reaction was 2 ℃/min, the hydrothermal reaction time was 12 hours, the freeze-drying temperature was-40 ℃, the freeze-drying time was 30 hours, the sintering holding time was 1.5 hours, and the other conditions were the same as in example 1.
Cobaltosic oxide/nitrogen-doped graphene oxide materials prepared in examples 2 to 4 and Co prepared in example 1 3 O 4 The electrochemical performance of the/N-GNS is similar.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of cobaltosic oxide/nitrogen-doped graphene oxide material is characterized by comprising the following steps:
mixing graphene oxide, a nitrogen source, a cobalt source and water to obtain a suspension;
carrying out hydrothermal reaction on the suspension to obtain a precursor solution;
directly freeze-drying the precursor liquid to obtain a precursor;
and sintering the precursor to obtain the cobaltosic oxide/nitrogen-doped graphene oxide material.
2. The preparation method according to claim 1, wherein the mass ratio of graphene oxide to water in the suspension is 0.06-0.15, and the mass ratio of graphene oxide, the nitrogen source and the cobalt source is 0.06-0.15.
3. The method of claim 1 or 2, wherein the cobalt source comprises Co (NO) 3 ) 2 ·6H 2 O、CoSO 4 ·7H 2 O、CoF 2 、CoCl 2 、CoBr 2 Or CoI 2 (ii) a The nitrogen source comprises melamine or urea.
4. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 8-12 h.
5. The method according to claim 1, wherein the temperature of the freeze-drying is-60 to-40 ℃ and the time is 24 to 48 hours.
6. The method according to claim 1, wherein the sintering temperature is 400-500 ℃, the time is 1-2 h, and the heating rate for heating to the sintering temperature is 2-10 ℃/min.
7. The cobaltosic oxide/nitrogen-doped graphene oxide material prepared by the preparation method according to any one of claims 1 to 6, which comprises nitrogen-doped graphene oxide and cobaltosic oxide particles distributed on the nitrogen-doped graphene oxide, wherein the cobaltosic oxide particles are spherical or quasi-spherical, the particle size of the cobaltosic oxide particles is 10 to 20nm, and the nitrogen-doped amount of the cobaltosic oxide/nitrogen-doped graphene oxide material is not less than 4.2wt%.
8. The cobaltosic oxide/nitrogen-doped graphene oxide material according to claim 7, wherein the loading amount of the cobaltosic oxide in the cobaltosic oxide/nitrogen-doped graphene oxide material is 46-50 wt%.
9. Use of the cobaltosic oxide/nitrogen-doped graphene oxide material of claim 7 or 8 as a negative electrode material for a sodium-ion battery.
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