CN114873582A - Nano onion carbon and preparation method thereof, and electrode material and preparation method thereof - Google Patents

Nano onion carbon and preparation method thereof, and electrode material and preparation method thereof Download PDF

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CN114873582A
CN114873582A CN202210723751.0A CN202210723751A CN114873582A CN 114873582 A CN114873582 A CN 114873582A CN 202210723751 A CN202210723751 A CN 202210723751A CN 114873582 A CN114873582 A CN 114873582A
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electrode material
nickel
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onion carbon
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唐水花
余虹霖
杨爽
余丽梅
谢雨航
徐铭杰
熊宏禧
汪霄汉
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Southwest Petroleum University
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Abstract

The invention discloses a nano onion carbon and a preparation method thereof, and an electrode material and a preparation method thereof, wherein the preparation method of the nano onion carbon comprises the following steps: s1: respectively preparing a nano silicon dioxide dispersion solution and a nickel-cobalt salt mixed solution; s2: adding the nano silicon dioxide dispersion solution into the nickel cobalt salt mixed solution, stirring uniformly, adding a pH regulator to regulate the pH value of the mixed solution to 7-10, stirring for reaction for 2-6 h, and then filtering and washingObtaining a precipitation reaction product; s3: calcining the precipitation reactant at 350-450 deg.C for 4-6 h to obtain NiCo/SiO 2 (ii) a S4: at Ar and H 2 Under the atmosphere condition, the NiCo/SiO is mixed with the mixture 2 Reducing at 500-600 deg.C for 0.5-1.5 h to obtain reduced product; s5: at Ar and C 3 H 8 Growing the reduced product at 550-650 deg.C for 0.5-1 h under atmosphere, and washing to obtain the nanometer onion carbon. The invention can further regulate and control and optimize the microstructure and the energy storage performance of the material in a nanoscale, and improves the specific capacitance and the stability of the electrode material.

Description

Nano onion carbon and preparation method thereof, and electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of supercapacitors, in particular to nano onion carbon and a preparation method thereof, and an electrode material and a preparation method thereof.
Background
The storage of intermittent renewable energy sources (such as wind, solar and tidal energy) is of great importance for sustainable energy utilization and consumption. Among many energy storage devices, supercapacitors have a wide range of applications in various fields due to their advantages of ultra-high power density, stable cycle life, fast and effective charging and discharging behavior, and very low resistance. However, the supercapacitor has a problem of too low energy density compared to the battery, and one of the methods to improve this deficiency is to develop an electrode material having high energy density.
The nickel-cobalt sulfide has the characteristics of high oxidation-reduction rate, large specific surface area and the like, is favorable for accelerating the electron transmission and diffusion rate, and can be used as a pseudocapacitance material. And compared with single cobalt sulfide and nickel sulfide, the nickel cobalt sulfide has many advantages: the nickel and cobalt have a metal synergistic effect, the element valence state is more, more electrons can participate in the electron gain and loss between the oxidation reduction, the performance of the electrode material can be effectively improved, and the specific capacitance is effectively improved. However, nickel cobalt sulfide is easy to expand in volume and collapse in structure during oxidation and reduction, so that the rate capability of nickel cobalt sulfide is poor, and the nickel cobalt sulfide cannot be widely applied.
Disclosure of Invention
In view of the above problems, the present invention is directed to nano onion Carbons (CNOs) and a method of preparing the same, and an electrode material and a method of preparing the same.
The technical scheme of the invention is as follows:
in one aspect, a preparation method of nano onion carbon is provided, which comprises the following steps:
s1: respectively preparing a nano silicon dioxide dispersion solution and a nickel-cobalt salt mixed solution;
s2: adding the nano silicon dioxide dispersion solution into the nickel cobalt salt mixed solution, stirring uniformly, adding a pH regulator to regulate the pH value of the mixed solution to 7-10, stirring and reacting for 2-6 h at room temperature, and then filtering and washing to obtain a precipitation reaction product;
s3: calcining the precipitation reactant at 350-450 ℃ for 4-6 h to obtain NiCo/SiO 2 ；
S4: at Ar and H 2 Under the atmosphere condition, the NiCo/SiO is mixed with the mixture 2 Reducing at 500-600 deg.C for 0.5-1.5 h to obtain reduced product;
s5: at Ar and C 3 H 8 Growing the reduced product at 550-650 deg.C for 0.5-1 h under atmosphere, and washing to obtain the nanometer onion carbon.
Preferably, in step S1, when preparing the nano-silica dispersion solution, nano-silica with a diameter of 20-200 nm is used for preparation, and the solvent of the nano-silica dispersion solution is deionized water.
Preferably, in step S1, the molar ratio of the nickel salt to the cobalt salt is 1: 2-2: 1 when preparing the nickel-cobalt salt mixed solution.
Preferably, in the step S5, when washing is performed, the product is sequentially subjected to alkali washing and acid washing to remove SiO in the product 2 、Ni、Co。
Preferably, the alkali washing and the acid washing are carried out by washing with sodium hydroxide and hydrochloric acid, respectively, at 100 ℃ for 6 hours.
Correspondingly, the nano onion carbon is prepared by adopting the preparation method.
Correspondingly, the electrode material is a nickel-cobalt-sulfur electrode material, and the nano onion carbon prepared by the preparation method is loaded on the nickel-cobalt-sulfur electrode material.
Accordingly, the method for preparing the electrode material comprises the following steps:
s1': respectively preparing a nano onion carbon dispersion solution, a nickel chloride solution and a cobalt chloride solution;
s2': adding the nickel chloride solution and the cobalt chloride solution into the nano onion carbon dispersion solution, uniformly stirring, adding a sodium sulfide solution to obtain a precipitate, and continuously and uniformly stirring to obtain a reacted slurry;
s3': and (3) preserving the temperature of the reacted slurry for 6-10 h at the temperature of 100-140 ℃, and filtering, washing and vacuum-drying the preserved reactant to obtain the nano onion carbon supported nickel-cobalt-sulfur electrode material.
Preferably, in step S1', the solvent for preparing the nano onion carbon dispersion solution is ethylene glycol, and the solvents for preparing the nickel chloride solution and the cobalt chloride solution are deionized water.
Preferably, in step S3', the slurry after the reaction is heated and maintained by a microwave method, a solvothermal method, or a microwave solvothermal assist method.
The invention has the beneficial effects that:
on one hand, when the nano onion carbon is prepared by chemical vapor deposition, the method comprises the following steps: (1) using nano-SiO 2 As a substrate material, the nano carbon material can grow more orderly, the morphology of the nano carbon material is more controllable, and SiO is washed off subsequently 2 The nano onion carbon with a hollow structure is obtained, so that the specific surface area of the nano onion carbon can be effectively increased; (2) adopts nickel cobalt salt mixed solution asThe catalytic transition metal with the reactivity can effectively avoid the influence of other metals in the process of loading the nickel-cobalt-sulfur compound when the nickel-cobalt-sulfur compound is loaded; (3) propane is used as a carbon source gas, so that the temperature for growing the nano carbon material can be reduced, the reaction condition is mild, and higher yield can be obtained.
On the other hand, the novel electrode material is obtained by loading nano onion carbon on nickel-cobalt-sulfur, and the good conductivity of CNOs can promote the Faraday reaction of the electrode material to be more active, so that the electrode material has higher specific capacitance and better stability than the nickel-cobalt sulfide before loading. Therefore, the invention can improve the conductivity and stability of the nickel-cobalt-sulfur electrode material, is beneficial to the rapid transmission of electrons, and simultaneously refines the particle size of the nickel-cobalt-sulfur electrode material, so that more active substances are fully utilized, thereby improving the specific capacitance and stability of the electrode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic electron microscope image of the products of the steps of example 1 and the product of comparative example 2;
FIG. 2 shows CNOs and Ni in example 1 2 CoS 4 XRD result schematic diagram of/CNOs;
FIG. 3 is a graph showing the results of electrochemical tests of example 1 and comparative example 1;
FIG. 4 is a graph showing the results of electrochemical tests of example 1 and comparative example 2;
FIG. 5 is a graph showing the results of the cycle stability tests of example 1 and comparative example 2;
FIG. 6 is a graph showing the results of electrochemical tests of example 1 and examples 8 and 9;
FIG. 7 is a graph showing the results of electrochemical tests performed on an asymmetric supercapacitor assembled according to example 1.
Detailed Description
The invention is further illustrated with reference to the following figures and examples. It should be noted that, in the present application, the embodiments and the technical features of the embodiments may be combined with each other without conflict. It is noted that, unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The use of the terms "comprising" or "including" and the like in the present disclosure is intended to mean that the elements or items listed before the term cover the elements or items listed after the term and their equivalents, but not to exclude other elements or items.
The invention provides an electrode material, which is prepared by the following steps:
s1: preparing nano onion carbon.
In a specific embodiment, the nano onion carbon is prepared by the following sub-steps:
s11: respectively preparing a nano silicon dioxide dispersion solution and a nickel cobalt salt mixed solution.
In a specific embodiment, when the nano-silica dispersion solution is prepared, nano-silica with the diameter of 20-200 nm is adopted for preparation, and the solvent of the nano-silica dispersion solution is deionized water; when the nickel-cobalt salt mixed solution is prepared, the molar ratio of the nickel salt to the cobalt salt is 1: 2-2: 1.
S12: adding the nano silicon dioxide dispersion solution into the nickel cobalt salt mixed solution, stirring uniformly, adding a pH regulator to regulate the pH value of the mixed solution to 7-10, stirring and reacting for 2-6 h at room temperature, and then filtering and washing to obtain a precipitation reaction product;
s13: calcining the precipitation reactant at 350-450 ℃ for 4-6 h to obtain NiCo/SiO 2 。
S14: at Ar and H 2 Under the atmosphere condition, the NiCo/SiO is mixed with the mixture 2 Reducing at 500-600 deg.C for 0.5-1.5 h,obtaining a reduced product.
S15: at Ar and C 3 H 8 Growing the reduced product at 550-650 deg.C for 0.5-1 h under atmosphere, and washing to obtain the nanometer onion carbon.
In a specific embodiment, when washing is performed in step S15, the product is sequentially subjected to alkali washing and acid washing to remove SiO in the product 2 Ni, Co. Alternatively, when alkali washing and acid washing are carried out, washing is carried out for 6 hours at 100 ℃ by using sodium hydroxide and hydrochloric acid, respectively.
S2: and loading the nano onion carbon on a nickel-cobalt-sulfur electrode material to obtain the electrode material.
In a specific embodiment, step S2 specifically includes the following sub-steps:
s21: respectively preparing a nano onion carbon dispersion solution, a nickel chloride solution and a cobalt chloride solution;
in a specific embodiment, the solvent for preparing the nano onion carbon dispersion solution is ethylene glycol, and the solvents for preparing the nickel chloride solution and the cobalt chloride solution are deionized water.
S22: adding the nickel chloride solution and the cobalt chloride solution into the nano onion carbon dispersion solution, uniformly stirring, adding a sodium sulfide solution to obtain a precipitate, and continuously and uniformly stirring to obtain a reacted slurry;
in a specific embodiment, the weight percentage of the nano onion carbon is 5% -15% of the total weight of the four solutions after mixing. When the added CNOs is too small, the obtained nickel-cobalt sulfide has larger grain diameter and smaller electrochemical active area, so that the specific capacitance and the rate capability of the electrode material are reduced; when too much CNOs is added, the particle size of the electrode material can be made smaller, but the nickel cobalt sulfide active material is caused to be less, so that the specific capacitance of the electrode material is poor.
S23: and (3) preserving the temperature of the reacted slurry for 6-10 h at the temperature of 100-140 ℃, and filtering, washing and vacuum-drying the preserved reactant to obtain the nano onion carbon supported nickel-cobalt-sulfur electrode material.
In a specific embodiment, in step S23, the slurry after the reaction is heated and maintained by microwave, solvothermal or microwave-assisted solvothermal method.
Example 1
A nano onion carbon supported nickel-cobalt-sulfur motor material is prepared by the following steps:
(1) synthesis of CNOs
First, 700mgSiO 2 Ultrasonically dispersed in 60mL deionized water, and then 2mmolNi (NO) was added 3 ) 2 ·6H 2 O and 1mmolCo (NO) 3 ) 2 ·6H 2 O is stirred for 0.5h, and then 4g of NH dissolved in 30ml of DI is slowly added dropwise thereto 4 HCO 3 After which stirring was continued for 3 h. The precipitate obtained after filtration and washing is calcined for 5 hours at 400 ℃ to obtain 20 wt% NiCo/SiO 2 . Then 20 wt% NiCo/SiO 2 Placed in a tube furnace under Ar and H 2 At the flow rate of 100sccm, reducing at 550 ℃ for 1h, and then continuing to Ar and C 3 H 8 The growth was carried out at 600 ℃ for 0.5h at flow rates of 100sccm and 75sccm, respectively, to give untreated CNOs. Finally washing with 3M NaOH and 3M HCl respectively at 100 deg.C for 6h to remove SiO 2 And Ni, Co to obtain pure CNOs.
(2) Synthesis of Ni 2 CoS 4 /CNOs
Ultrasonically dispersing 30mg of pure CNOs prepared in the step (1) in 60mL of glycol to obtain a dispersion liquid of the CNOs; to the dispersion of CNOs was added 2mmol NiCl dissolved in 15mL deionized water 2 ·6H 2 O、1mmol CoCl 2 ·6H 2 O, stirring for 30min, and slowly adding 6mmol Na dissolved in 15mL deionized water 2 Precipitating the solution S, and continuously stirring for 30 min; carrying out microwave heating on the reacted slurry, respectively heating for 5min under the conditions that the power is 350W and 500W, and stirring for 10min after heating is finished; carrying out solvothermal reaction on the heated slurry for 8h at the temperature of 120 ℃; and after the reaction is finished, filtering, washing and vacuum drying the reactant to obtain the nano onion carbon supported nickel-cobalt-sulfur electrode material.
Example 2
Unlike example 1, the present example employed 350 ℃ and 6h as the calcination temperature in the synthesis of CNOs in step (1).
Example 3
Unlike example 1, in this example, the calcination temperature in the synthesis of CNOs in step (1) was 450 ℃ and the calcination time was 4 hours.
Example 4
Unlike example 1, the reduction time in the synthesis of CNOs in step (1) of this example was 0.5 h.
Example 5
Unlike example 1, this example employed 1.5h for the reduction time in the synthesis of CNOs in step (1).
Example 6
Unlike example 1, this example takes 0.8h for growth in step (1) of synthesizing CNOs.
Example 7
Unlike example 1, this example employed 1h for growth in step (1) of synthesizing CNOs
Example 8
Unlike example 1, this example synthesizes Ni in step (2) 2 CoS 4 The addition amount of nano onion carbon in CNOs is 20 mg.
Example 9
Unlike example 1, this example synthesizes Ni in step (2) 2 CoS 4 The addition amount of nano onion carbon in CNOs is 40mg
Example 10
Unlike example 1, this example synthesizes Ni in step (2) 2 CoS 4 The solvothermal temperature in the CNOs was 100 ℃.
Example 11
Unlike example 1, this example synthesizes Ni in step (2) 2 CoS 4 The solvothermal temperature in the/CNOs was 140 ℃.
Example 12
Unlike example 1, this example synthesizes Ni in step (2) 2 CoS 4 The temperature of solvothermal reaction in CNOs is 100 ℃, and the holding time is 6 h.
Example 13
Unlike example 1, this example synthesizes Ni in step (2) 2 CoS 4 The temperature of solvothermal reaction in CNOs is 100 ℃, and the holding time is 10 h.
Comparative example 1
Unlike example 1, this comparative example did not add SiO in step (1) 2 As the substrate material, CNOs are prepared directly under the condition without the substrate material.
Comparative example 2
Unlike example 1, this comparative example directly synthesizes Ni without loading nano onion carbon in step (2) without adding CNOs synthesized in step (1) 2 CoS 4 An electrode material.
The CNO synthesized in the step (1) of example 1 was subjected to a high-resolution transmission electron microscope and the Ni synthesized in the step (2) was subjected to 2 CoS 4 Ni synthesized by CNOs in scanning electron microscope and comparative example 2 2 CoS 4 Scanning electron microscopy characterization was performed and the results are shown in FIG. 1, where FIG. 1(a) is a high resolution transmission electron microscopy image of CNOs and FIG. 1(b) is Ni of example 1 2 CoS 4 FIG. 1(c) is a scanning electron microscope photograph of Ni of comparative example 2 2 CoS 4 Scanning electron microscopy images. As can be seen from fig. 1(a), CNOs exhibit an onion-like structure formed by wrapping a plurality of graphite layers, and the calculated graphite interlayer spacing is 0.34nm, which is consistent with the standard graphite interlayer spacing of 0.34nm, and thus it can be considered that highly graphitized CNOs are synthesized. As can be seen from fig. 1(b), the nickel-cobalt-sulfur is in a two-dimensional sheet structure and is uniformly distributed on the surface of the nano onion carbon; the nano onion carbon has good filling density, does not expand in the test process, and can effectively avoid structural collapse of the nickel-cobalt-sulfur electrode material in the redox process after the nano onion carbon is loaded with nickel-cobalt-sulfur, so that the structure is not obviously changed before and after the test, and the cycle stability of the nano onion carbon is greatly improved. It is clear from FIG. 1(c) that the nickel cobalt sulfide is laminated and will be in the process of oxidation-reductionThe structure collapse occurs in the process, and the rate capability is poor.
The product of the two steps of example 1 was subjected to X-ray diffraction testing and the results are shown in figure 2. As can be seen from fig. 2(a), the highly graphitized CNOs prepared by the present invention successfully has a strong peak at (002), and the nano carbon material prepared by the present invention has a high graphitization degree, and has good conductivity and chemical stability. FIG. 2(b) shows a diffraction peak at about 26 ℃ corresponding to graphitized carbon (002), demonstrating that CNOs are present in the prepared electrode material, and the other diffraction peaks are Ni, respectively 2 CoS 4 The (111), (220), (400), (511), (440), (533) and (444) planes of the crystal structure (PDF #24-0334) demonstrate successful Ni synthesis 2 CoS 4 the/CNOs electrode material.
Electrochemical tests were performed on the CNOs carbon material obtained in example 1 and the CNOs carbon material obtained in comparative example 1. Electrochemical tests were performed in a 6m koh electrolyte using the conventional three-electrode system with the CNOs prepared in example 1 and the CNOs carbon material prepared in comparative example 1 as working electrodes and platinum electrodes and Hg/HgO electrodes as counter and reference electrodes. CV test conditions: in the potential range of-1-0V, the sweep rate is 200mVs -1 (ii) a GCD test conditions: a potential range of-1-0V. The test results are shown in FIG. 3, in which FIG. 3(a) shows whether SiO is contained or not 2 The CV curve of the CNOs carbon material prepared by the substrate material can obviously show that the two prepared carbon materials have obvious internal rectangle and are obvious electric double layer capacitance. And contains SiO 2 The CV curve area of the CNOs carbon material prepared by the substrate material is obviously higher than that of the carbon material without SiO 2 CNOs carbon material obtained by using the carbon material as a substrate material. The corresponding GCD contrast curve (FIG. 3(b)) also demonstrates CV results, containing SiO 2 The specific capacitance value calculated by the CNOs carbon material prepared as the substrate material is far higher than that calculated by SiO-free carbon materials 2 CNOs carbon material obtained by using the carbon material as a substrate material. Besides, the multiplying power performance is greatly improved, and is 10Ag -1 At a current density of (2), contains SiO 2 The rate capability of the CNOs carbon material prepared by the method as a substrate material can reach 96%. Illustrating the addition of SiO 2 As a substrateThe material not only can enable CNOs to grow orderly, but also can increase the specific surface area of the carbon material and effectively improve the capacitance performance of the carbon material
For Ni prepared in example 1 2 CoS 4 CNOs electrode material and Ni produced in comparative example 2 2 CoS 4 The electrode material was subjected to electrochemical testing. Ni prepared as in example 1 using a conventional three-electrode system 2 CoS 4 CNOs and Ni from comparative example 2 2 CoS 4 As working electrodes, platinum electrodes and Hg/HgO electrodes were used as counter and reference electrodes, and electrochemical tests were carried out in 6MKOH electrolyte. CV test conditions: with a potential range of 0-0.5V and a sweep rate of 30mVs -1 (ii) a GCD test conditions: a potential range of 0.1-0.5V. Test conditions of EIS: frequency of 10 5 ─10 -2 Hz, amplitude of 5 mV. The test results are shown in FIG. 4, in which Ni is shown in FIG. 4(a) 2 CoS 4 And Ni 2 CoS 4 The CV curve of the/CNOs shows that the two prepared electrode materials have a pair of obvious redox peaks, which indicates that the electrode has the Faraday behavior of the battery type, and the peak current and CV integral area corresponding to the electrode material loaded with nano onion carbon are obviously higher than those of Ni 2 CoS 4 . The corresponding GCD contrast curve (FIG. 4(b)) also confirms the CV results, Ni 2 CoS 4 The specific capacitance value calculated by the/CNOs electrode material is far higher than that of Ni 2 CoS 4 An electrode material. By FIG. 4(c) Ni 2 CoS 4 And Ni 2 CoS 4 The electrode material of/CNOs is 5Ag -1 ─30Ag -1 The contrast of current density multiplying power can be seen as Ni 2 CoS 4 The initial specific capacitance of the/CNOs electrode material is 2450Fg -1 The rate capability is 90 percent and is far higher than that of Ni 2 CoS 4 Electrode material (1917 Fg) -1 79%). From FIG. 4(d), Ni can be seen 2 CoS 4 The Rs of the/CNOs electrode material is minimum, the smaller the resistance value of the electrode material is, the faster the charge transfer rate is, and the better the electrochemical performance is. By structural analysis of FIG. 4, it is confirmed that Ni 2 CoS 4 The electrochemical performance of the/CNOs electrode material is superior to that of Ni 2 CoS 4 . Analysis of causes: the nano onion carbon prepared by the method has better conductivity and stability, and can improve Ni 2 CoS 4 The nano onion carbon is used as a substrate material, so that volume expansion and structure collapse caused by a nickel-cobalt-sulfur compound in a synthesis process can be avoided, more active sites can be exposed, and the electrochemical performance of the nano onion carbon can be fully exerted.
For Ni prepared in example 1 2 CoS 4 CNOs electrode material and Ni produced in comparative example 2 2 CoS 4 The electrode material was subjected to a cycling stability test. The test conditions were the same as described above, and the results are shown in FIG. 5. As can be seen from FIG. 5, Ni 2 CoS 4 CNOs electrode material and Ni 2 CoS 4 The electrode material is 30Ag -1 The capacity retention rates after circulating for 2000 circles under the current density are respectively 96.4% and 86.5%, which proves that the nano onion carbon loaded nickel-cobalt-sulfur electrode material can improve the stability of the nickel-cobalt-sulfur electrode material.
For Ni prepared in example 1 2 CoS 4 Electrode materials of/CNOs (30mg) and Ni from example 8 2 CoS 4 /CNOs (20mg) and Ni from example 9 2 CoS 4 the/CNOs (40mg) electrode materials were subjected to electrochemical testing. The test conditions were the same as those described above, and the results are shown in FIG. 6. FIG. 6(a) shows Ni prepared by adding nano onion carbon in different amounts 2 CoS 4 /CNOs(20mg)、Ni 2 CoS 4 CNOs (30mg) and Ni 2 CoS 4 CV curve of/CNOs (40mg), it can be seen that the peak current and CV integrated area corresponding to 30mg of nano onion carbon added electrode material are obviously higher than those of the other two. The corresponding GCD contrast curve (FIG. 6(b)) also confirms the CV results, Ni 2 CoS 4 The specific capacitance value calculated by the/CNOs (30mg) electrode material is much higher than that of Ni 2 CoS 4 /CNOs (20mg) and Ni 2 CoS 4 Electrode materials of/CNOs (40 mg). When the amount of the nano onion carbon added is 20mg, 30mg, or 40mg in FIG. 6(c), the electrode material 5Ag is obtained -1 Has a specific capacitance value of 2044Fg at a current density of -1 、2450Fg -1 、1852Fg -1 Of which from 5Ag -1 ─30Ag -1 The multiplying power performance of (A) is respectively 85%, 90% and 88%. While Ni can be obtained from FIG. 6(d) 2 CoS 4 The Rs of the/CNOs (30mg) electrode material was the smallest. According to the above results, it is confirmed that the electrochemical performance of the electrode material prepared when the amount of the nano onion carbon added is 30mg is optimal.
For Ni prepared in example 1 2 CoS 4 the/CNOs electrode material and commercial Activated Carbon (AC) are assembled into an asymmetric supercapacitor for electrochemical test, and the electrochemical test is carried out under a two-electrode system. Wherein the anode material is Ni 2 CoS 4 The negative electrode material of the/CNOs is AC, the electrolyte is 6MKOH solution, and the diaphragm is non-woven fabric. The voltage window of CV test is 0-1.6V, and the scan rate is in the range of 20-200 mVs -1 (ii) a GCD test has charge-discharge voltage window of 0-1.6V; test conditions of EIS: frequency of 10 5 ─10 -2 Hz, amplitude of 5 mV; the test results are shown in FIG. 7. FIG. 7(a) shows a scan rate of 30mVs -1 Positive electrode material Ni 2 CoS 4 CV curve of/CNOs and negative electrode material AC. FIG. 7(b) explores at 50mVs -1 At scanning rate of Ni 2 CoS 4 The CV curves of the/CNOs AC asymmetric supercapacitors vary over different voltage windows (0-1.4V to 0-1.7V). It can be seen from FIG. 7(b) that when the voltage window is higher than 1.6V, the CV curve will show significant polarization, and therefore Ni 2 CoS 4 The optimal working voltage of the/CNOs AC asymmetric super capacitor is 0-1.6V. FIG. 7(c) shows Ni 2 CoS 4 CV curves of the/CNOs AC asymmetric super capacitor under different scanning speeds. From 20mVs -1 To 200mVs -1 At the sweep rate of (D), the CV curve shapes are somewhat similar, indicating that Ni is 2 CoS 4 the/CNOs AC asymmetric super capacitor has good reversibility and rapid dynamic charge and discharge behaviors. Ni calculated from the GCD curve of FIG. 7(d) 2 CoS 4 1Ag of/CNOs AC asymmetric super capacitor -1 Has an initial specific capacitance of 125Fg at a current density of -1 And the electrochemical performance is obviously improved compared with the conventional super capacitor.
In summary, the present invention uses nano-scale SiO 2 As a base material for preparing onion carbonThe obtained nano carbon material grows more orderly, the appearance is more controllable, and SiO is washed off subsequently 2 Then the nano onion carbon with a hollow structure can be obtained, and the specific surface area of the nano onion carbon can be effectively improved; the nickel-cobalt salt mixed solution is used as a catalytic transition metal with reaction activity, so that the influence of other metals in the process of loading the nickel-cobalt-sulfur compound is effectively avoided; and secondly, propane is used as a carbon source gas, so that the temperature for growing the nano carbon material can be reduced, the reaction condition is mild, and high yield can be obtained. And the closed spherical structure of the nano onion carbon has good filling density, so that charges can be quickly transferred on the surface of the nano onion carbon without entering the interior of the nano onion carbon, the expansion of the structure can not occur during testing, and the loaded nickel-cobalt-sulfur electrode material can not cause the collapse of the structure in the redox process, which is a characteristic that other nano carbon material composite nickel-cobalt-sulfur compounds do not have. Nickel cobalt sulfur is loaded on the nano onion carbon, so that the nickel cobalt sulfur can be deposited and grown on the surface of the nano onion carbon, and meanwhile, CNOs with good conductivity construct a perfect conductive network among nickel cobalt sulfur sheets, so that protons in the electrolyte can more quickly reach the lattice surface of the nickel cobalt sulfur on the inner layer to generate an oxidation-reduction reaction, and the electrochemical performance of the electrode material is effectively improved. Compared with the prior art, the invention has remarkable progress.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The preparation method of the nano onion carbon is characterized by comprising the following steps:
s1: respectively preparing a nano silicon dioxide dispersion solution and a nickel-cobalt salt mixed solution;
s2: adding the nano silicon dioxide dispersion solution into the nickel cobalt salt mixed solution, stirring uniformly, adding a pH regulator to regulate the pH value of the mixed solution to 7-10, stirring and reacting for 2-6 h at room temperature, and then filtering and washing to obtain a precipitation reaction product;
s3: calcining the precipitation reactant at 350-450 ℃ for 4-6 h to obtain NiCo/SiO 2 ；
S4: at Ar and H 2 Under the atmosphere condition, the NiCo/SiO is mixed with the mixture 2 Reducing at 500-600 deg.C for 0.5-1.5 h to obtain reduced product;
s5: at Ar and C 3 H 8 Growing the reduced product at 550-650 deg.C for 0.5-1 h under atmosphere, and washing to obtain the nanometer onion carbon.
2. The method for preparing nano onion carbon according to claim 1, wherein in step S1, nano silica with a diameter of 20-200 nm is used for preparing the nano silica dispersion solution, and the solvent of the nano silica dispersion solution is deionized water.
3. The method for preparing nano onion carbon according to claim 1, wherein in step S1, when preparing the nickel cobalt salt mixed solution, the molar ratio of nickel salt to cobalt salt is 1: 2-2: 1.
4. The method for preparing nano onion carbon according to claim 1, wherein in the step of washing in S5, the product is sequentially subjected to alkali washing and acid washing to remove SiO in the product 2 、Ni、Co。
5. The method for preparing nano onion carbon according to claim 4, wherein the alkali washing and the acid washing are performed by washing with sodium hydroxide and hydrochloric acid at 100 ℃ for 6 hours, respectively.
6. A nano onion carbon, characterized in that, it is prepared by the method of any one of claims 1 to 5.
7. An electrode material, wherein the electrode material is a nickel-cobalt-sulfur electrode material, and the nano onion carbon prepared by the preparation method of any one of claims 1 to 5 is loaded on the nickel-cobalt-sulfur electrode material.
8. The method for preparing an electrode material according to claim 7, comprising the steps of:
s1': respectively preparing a nano onion carbon dispersion solution, a nickel chloride solution and a cobalt chloride solution;
s2': adding the nickel chloride solution and the cobalt chloride solution into the nano onion carbon dispersion solution, uniformly stirring, adding a sodium sulfide solution to obtain a precipitate, and continuously and uniformly stirring to obtain a reacted slurry;
s3': and (3) preserving the temperature of the reacted slurry for 6-10 h at the temperature of 100-140 ℃, and filtering, washing and vacuum-drying the preserved reactant to obtain the nano onion carbon supported nickel-cobalt-sulfur electrode material.
9. The method for preparing an electrode material according to claim 8, wherein in step S1', the solvent for preparing the nano onion carbon dispersion solution is ethylene glycol, and the solvents for preparing the nickel chloride solution and the cobalt chloride solution are deionized water.
10. The method for preparing an electrode material according to claim 8, wherein in step S3', the slurry after the reaction is heated and maintained by a microwave method, a solvothermal method or a microwave solvothermal assisted method.
CN202210723751.0A 2022-06-23 2022-06-23 Nano onion carbon and preparation method thereof, and electrode material and preparation method thereof Pending CN114873582A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114105226A (en) * 2020-08-28 2022-03-01 南京理工大学 Nickel-cobalt-manganese sulfide @ hollow mesoporous carbon sphere nano composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN114105226A (en) * 2020-08-28 2022-03-01 南京理工大学 Nickel-cobalt-manganese sulfide @ hollow mesoporous carbon sphere nano composite material and preparation method thereof

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