CN112409028B - CC-NiO-CuCoS composite material and preparation method and application thereof - Google Patents
CC-NiO-CuCoS composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112409028B CN112409028B CN202011171824.7A CN202011171824A CN112409028B CN 112409028 B CN112409028 B CN 112409028B CN 202011171824 A CN202011171824 A CN 202011171824A CN 112409028 B CN112409028 B CN 112409028B
- Authority
- CN
- China
- Prior art keywords
- nio
- composite material
- cuco
- drying
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a CC-NiO-CuCoS composite material, which is prepared from CC, niO and CuCo 2 S 4 Forming; the NiO nano-sheets are not stacked and the conductive substrate is beneficial to ultra-high speed transportation of electrons; the microstructure of NiO is a nano-sheet structure, is loaded on the surface of CC and is used for providing an additional pseudo capacitor; cuCo 2 S 4 The microstructure of (2) is a nanoparticle structure, is attached to the surfaces of the CC and the NiO nano-sheets and has the functions of stabilizing the flaky structure of NiO and coating the partially exposed CC. The catalyst is prepared by two-step hydrothermal preparation by using CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea as starting raw materials. The preparation method comprises the following steps: 1) Cleaning and activating CC; 2) Preparing a CC-NiO composite material; 3) CC-NiO-CuCo 2 S 4 And (4) preparing the composite material. The specific capacitance is 840 Fg ‑1 (ii) a The cycling stability after 3000 cycles was 100%.
Description
Technical Field
The invention relates to a preparation technology of carbon cloth as a matrix material and a metal oxide, in particular to a carbon-based Super Capacitor (SCs) composite material and a preparation method and application thereof.
Background
Supercapacitors (SCs) have attracted considerable attention for their superior power density, ultra-long cycle stability, and fast charge and discharge rates, and have become the power sources for portable electronic products and electric/hybrid vehicles. The electrode material is one of the key elements of the SCs, and plays an important role in improving the electrochemical performance of the SCs. In order to meet the increasing energy/power density requirements, great efforts are made to find advanced electrode materials.
The construction of self-supporting arrays on conductive substrates is an effective method to improve the electrochemical performance of transition metal oxides as electrode materials, not only to reduce the agglomeration of active species and provide more electroactive sites without the use of polymeric binders and conductive additives, but also to construct nanoscale arrays for electron transport and to buffer structural stresses during electrochemical reactions. Especially in recent years, with the rapid development of flexible/wearable electronic devices and the increasing demand for flexible energy storage devices, flexible conductive substrates for direct growth of electroactive materials are receiving increasing attention. Carbon Cloth (CC) with high conductivity, good flexibility and excellent mechanical properties has become an ideal conductive substrate for supporting active materials and has been widely used in the field of flexible energy storage.
In the prior art, S.D. Dhas et al successfully coated NiO on CC as electrode material of super capacitor by hydrothermal method (Synthesis of NiO nanoparticles for supercapacitor application as an electrode material [ J ] J]Vacuum, volume 181. 2020). However, the specific capacitance of the resulting material in a 1M KOH aqueous electrolyte was 132 Fg -1 (ii) a After 500 cycles, the final capacity was 75% of the initial capacity. It is clear that the cycle performance obtained by this prior art is very low. According to the experimental procedures described in the literature, the inventor finds that the reason that the cycle performance of the material obtained by the technical scheme is low is that the NiO nano-sheets are hydrothermally prepared into powder and coated on the carbon cloth through the polyvinylidene fluoride binder, the powder prepared by the method is easy to stack among nano-layers, the adhesion between the powder and the carbon cloth is not high, the problem of falling of a load is caused, and the electrochemical stability of the NiO nano-sheet layer is seriously lost. However, when CC is used as a base material, it is effective to increase the specific capacitance of the composite material by supporting another material.
The problems of specific capacitance and cycle performance can be solved by controllingThe microstructure of the composite material is improved, and a NiO nano-sheet composite electrode material with the diameter of about 200nm and the thickness of about 25nm and controllable size and thickness is prepared on CC by a chemical precipitation method in the prior art Liu, QX et al (Rsc Adv, 737 volume in 2017, page number: 23143-23148, ISSN. Is realized at 1 ag −1 At a discharge current density of 600.3 fg, the specific capacitance of -1 (ii) a At 2A g -1 After 3000 cycles at current density of (c), the final capacity was 98.1% of the initial capacity. Although this technique improves the specific capacitance performance of the composite, the cycling performance still does not meet the application requirements of supercapacitors.
The performance of the supercapacitor is improved by loading metal sulfides on the surface of the CC, such as the prior art Xie, T et al (EUR J INFO CHEM, no. 43 of 2018, page numbers: 4711-4719, ISSN: 1434-1948) growth of CuCo directly on the CC substrate by a hydrothermal synthesis route 2 S 4 And (3) microspheres. Is realized at 1 ag -1 Can provide 166.67 mAh g -1 At a capacitance of 5 ag -1 After 3000 cycles at current density of (c), the final capacity was 91.25% of the initial capacity. This technique also suffers from a rapid decay in cycle performance.
Therefore, the morphology of the material is controlled by a reasonable preparation method, the CC material and the transition metal oxide composite electrode material are obtained, and the method is an effective way for improving the material performance.
Disclosure of Invention
The invention aims to provide a stable carbon-based composite material, and a preparation method and application thereof.
In order to improve the electrochemical performance and the electrochemical cycling stability of the carbon-based composite material, niO nano sheets are loaded on a CC (carbon composite) substrate material, and CuCo is coated on the surfaces of the CC and the NiO nano sheets 2 S 4 The technical method of the nano-particles is used for preparing the CC-NiO-CuCoS composite material with stable structure.
Wherein, the load NiO has the following advantages: 1.NiO belongs to a pseudo-capacitance electrode material; 2. the metal oxide has high theoretical specific capacitance, high chemical and thermal stability and easy use; 3, the NiO material has low cost.
By loading NiO on the carbon-based material, the electrochemical reaction active sites of the composite material can be increased, the ion exchange rate of the composite material in the electrochemical reaction process is accelerated, and an additional pseudo-capacitance is provided for the composite material, so that the purpose of improving the electrochemical performance of the composite material is achieved.
Coated with CuCo 2 S 4 Has the advantages that: excellent electrochemical performance, low cost and non-toxicity, and it has better electronic conductivity than copper or cobalt oxide alone, at least two orders of magnitude higher.
By coating CuCo on CC material 2 S 4 The specific surface area of the composite material can be effectively increased, and the lamellar structure collapses in the charge and discharge process, so that the aim of improving the electrochemical cycle stability of the composite material is fulfilled.
In conclusion, the CC load can provide NiO with additional pseudo-capacitance and coated CuCo 2 S 4 The two materials of the nano-particles can generate good synergistic effect while exerting own unique advantages, and the purpose of greatly improving the electrochemical performance and the cycling stability of the CC composite material with stable structure can be achieved at the same time.
In addition, the CC is introduced as a substrate material, so that on one hand, the loading material has the effect of less sheet accumulation, on the other hand, the contact area of the carbon-based composite material and the electrolyte is enlarged, and the diffusion of ions can be accelerated, thereby achieving the purpose of improving the overall super-capacitor performance and the electrochemical stability of the composite material.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the CC-NiO-CuCoS composite material is formed from CC, niO and CuCo 2 S 4 Forming; the NiO nano-sheets are not stacked and the conductive substrate is beneficial to ultra-high speed transportation of electrons; the microstructure of NiO is a nano-sheet structure, is loaded on the surface of the CC and is used for providing an additional pseudo-capacitor; cuCo 2 S 4 The microstructure of (a) is a nanoparticle structure, is attached to the surfaces of the CC and NiO nano-sheets and has the function ofThe sheet structure of NiO and the exposed CC of the coating part are stabilized, so that the electrochemical performance of the material is prevented from being influenced by the structural collapse in the test process.
The substrate material is prepared by a two-step hydrothermal method by taking CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea as starting raw materials.
The preparation method of the CC-NiO-CuCoS composite material comprises the following steps:
step 1) activating CC, namely ultrasonically cleaning CC in an ether solution and absolute ethyl alcohol deionized water respectively, activating the CC in concentrated nitric acid with a certain mass fraction under a certain condition, and then cleaning the CC with deionized water and absolute ethyl alcohol and drying the CC to obtain activated CC;
the mass fraction of the concentrated nitric acid solution in the step 1 is 69%; the activation condition of the step 1 is that the activation temperature is 80-90 ℃ and the activation time is 3-4 h; the cleaning condition in the step 1 is ultrasonic for 15-20 min; the drying condition of the step 1 is that the drying temperature is 60-100 ℃, and the drying time is 12-24 h.
Step 2) preparing a CC-NiO composite material, namely putting the activated CC obtained in the step 1, nickel nitrate hexahydrate, ammonium fluoride and urea into water according to the certain substance quantity ratio, carrying out hydrothermal reaction under certain conditions, cleaning and drying after the reaction is finished, and annealing under certain conditions to obtain the CC-NiO composite material;
in the step 2, the mass ratio of the nickel nitrate hexahydrate, the ammonium fluoride and the urea is 1; the hydrothermal reaction condition of the step 2 is that the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 12 h; the cleaning conditions of the step 2 are the same as the cleaning conditions of the step 1; the drying condition of the step 2 is that the drying temperature is 60-100 ℃, and the drying time is 20-24 h; the annealing condition of the step 2 is that the annealing temperature is 350 ℃, and the annealing time is 2 h.
Step 3) preparing the CC-NiO-CuCoS composite material, namely, firstly, preparing the monohydrate copper acetate and the tetrahydrate cobalt acetate according to the ratio of the monohydrate copper acetate, the tetrahydrate cobalt acetate and the thiourea which meet a certain substance amountDissolving cobalt acetate hydrate in ethylene glycol to prepare a mixed solution, stirring for a certain time, adding thiourea, stirring for a certain time, adding the CC-NiO composite material obtained in the step (2) into the mixed solution after the mixing is finished, carrying out secondary hydrothermal treatment under a certain condition, washing with deionized water and absolute ethyl alcohol after the reaction is finished, and drying to obtain the CC-NiO-CuCo 2 S 4 A composite material.
In the step 3, the mass ratio of the copper acetate monohydrate, the cobalt acetate tetrahydrate and the thiourea is 1; in the step 3, when the copper acetate monohydrate and the cobalt acetate tetrahydrate are dissolved in the ethylene glycol, the stirring time is 30-60min, and then the thiourea is added and stirred for 30-60min; the condition of the secondary hydrothermal in the step 3 is that the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 hours; the cleaning conditions of the step 3 are the same as the cleaning conditions of the step 1; the drying condition of the step 3 is that the drying temperature is 80 ℃ and the drying time is 12 h.
The application of the CC-NiO-CuCoS composite material as the electrode material of the super capacitor can charge and discharge in the range of 0-0.4V and the discharge current density is 1 Ag -1 The specific capacitance is 600-900F g -1 。
Discharging in the range of 0-0.4V at a discharge current density of 2 Ag -1 The cycling stability after 3000 cycles was 100%.
The obtained CC-NiO-CuCoS composite material with stable structure is subjected to experimental detection, and the result is as follows:
the CC-NiO-CuCoS composite material with stable structure is tested by X-ray diffraction (XRD) and can be obtained from diffraction crystal faces corresponding to different diffraction peaks, and the composite material is prepared from C, niO and CuCo 2 S 4 The three substances are formed;
the CC-NiO-CuCoS composite material with stable structure is tested by a scanning electron microscope, and the flaky NiO can be seen to be distributed on the CC fiber strip-shaped surface structure; cuCo 2 S 4 The nano particles are distributed on the NiO nano sheet and the CC, which shows that the CC-NiO-CuCoS composite material with stable structure is successfully prepared;
and (3) carrying out electrochemical test and electrochemical cycling stability test on the structurally stable CC-NiO-CuCoS composite material:
discharging in the range of 0-0.4V at a discharge current density of 1 Ag -1 The specific capacitance of the structurally stable CC-NiO-CuCoS composite material is 840 Fg -1 ；
At a discharge current density of 2 ag -1 In the process, the CC-NiO-CuCoS composite material supercapacitor electrode with stable structure is charged for 3000 circles within the range of 0-0.4V, and the cycle stability is 100%.
Therefore, compared with the prior art, the CC-NiO-CuCoS composite material has the following advantages:
1. the invention adopts CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper nitrate monohydrate, cobalt acetate tetrahydrate and thiourea as initial raw materials, and the CC-NiO-CuCo with stable structure is prepared by two-step hydrothermal preparation 2 S 4 The composite material realizes the effect of improving the stability of the super capacitor, and the specific capacitance is 840 Fg -1 ；
The specific surface area of the CC-NiO-CuCoS composite material is increased by modifying the CC through the NiO nano sheets, and meanwhile, an additional pseudo capacitor is provided for the base material, so that the integral specific capacitance of the composite material is improved;
3. coated CuCo 2 S 4 The nano particles increase the specific surface area of the NiO nano sheet, reduce the interlayer spacing, accelerate the ion migration rate, and prevent the collapse of the lamellar structure of the material in the long-time charge-discharge process, thereby improving the cycling stability of the material;
4. supported NiO and coated CuCo 2 S 4 Not only play a corresponding role respectively, but also NiO and CuCo 2 S 4 The synergistic effect exists between the two components, so that the CC-NiO-CuCoS composite material obtains high specific capacitance performance and cycle stability;
5. fibrous CC is introduced as a substrate material, so that on one hand, the overall appearance of the material is effectively controlled, on the other hand, the contact area of the CC-NiO-CuCoS composite material and an electrolyte is enlarged, and the diffusion of ions is accelerated, thereby improving the overall super-capacitor performance of the composite material.
Therefore, the invention has wide application prospect in the field of super capacitor materials.
Description of the drawings:
FIG. 1 is an XRD of the CC-NiO composite prepared in step 2 of example 1;
FIG. 2 is a scanning electron micrograph of the CC-NiO composite material prepared in step 2 of example 1 with a ruler length of 2 μm;
FIG. 3 is a graph showing the charge and discharge curves of the structurally stable CC-NiO-CuCoS composite prepared in example 1 and the CC-NiO composite prepared in step 2 of example 1;
FIG. 4 is an XRD of the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 5 is a scanning electron microscope image of the CC-NiO-CuCoS composite material with stable structure prepared in example 1 under the condition that the length of a ruler is 500 nm;
FIG. 6 is a graph showing the charge and discharge curves of the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 7 is a cycle life curve for the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 8 is a SEM of the post-cycle of the structurally stable CC-NiO-CuCoS composite prepared in example 1;
FIG. 9 is a CC-CuCo prepared in comparative example 1 2 S 4 XRD of the composite material;
FIG. 10 is a view showing CC-CuCo prepared in comparative example 1 2 S 4 Scanning electron microscope images of the composite material under the length of the ruler of 3 mu m;
FIG. 11 shows the structurally stable CC-NiO-CuCoS composite prepared in example 1 and CuCo prepared in comparative example 1 2 S 4 A charge-discharge curve graph of the composite material;
FIG. 12 is a NiO-CuCo prepared in comparative example 2 2 S 4 XRD of the composite material;
FIG. 13 is a NiO-CuCo prepared in comparative example 2 2 S 4 Scanning electron microscope images of the composite material under the length of the ruler of 1 micron;
FIG. 14 shows the structurally stable CC-NiO-CuCoS composite prepared in example 1 and the NiO-CuCo composite prepared in comparative example 2 2 S 4 And (3) a charge-discharge curve diagram of the composite material.
Detailed Description
The CC-NiO-CuCoS composite material is described in detail by the embodiment and the attached drawings in the specification, and the CC-NiO composite material and the CC-CuCo composite material are respectively provided by the step 2 of the embodiment 1 and the comparative examples 1 and 2 2 S 4 Composite material, niO-CuCo 2 S 4 The preparation method and the performance characterization of the composite material prove that the invention has CC, niO and CuCo 2 S 4 The three components have synergistic effect. The examples are not intended to limit the invention.
Example 1
A preparation method of a CC-NiO-CuCoS composite material comprises the following steps:
step 1) activating CC, namely ultrasonically cleaning the CC of 2cm X2cm in size in 40mL of diethyl ether solution with the mass fraction of 99%, 40mL of absolute ethyl alcohol and 40mL of deionized water for 15min, boiling in 40mL of concentrated nitric acid with the mass fraction of 69% in water bath at 80-90 ℃ for 4 hours for activation, cleaning in the deionized water and the absolute ethyl alcohol for three times after the water bath is finished, and drying at 60 ℃ for 12 hours to obtain the activated CC;
and 2) preparing the CC-NiO composite material, namely putting the activated CC obtained in the step 1, nickel nitrate hexahydrate, ammonium fluoride and urea into 60mL of water according to the mass ratio of the nickel nitrate hexahydrate, the ammonium fluoride and the urea being 1.
The method for calculating the load on the carbon cloth comprises the following steps: 1. testing the mass and the area of the carbon cloth before loading; 2. testing the mass of the loaded carbon cloth, and calculating to obtain the mass difference; 3. dividing the mass difference by the area of the carbon cloth to obtain the loading capacity of unit area; 4. under the same conditions, the average unit area load capacity is obtained by a plurality of sample tests.
The average load capacity of the NiO nano-sheets on the carbon cloth is 0.5mg cm through experiments and calculation -2 。
In order to compare with the CC-NiO-CuCoS composite material and prove the influence of NiO on the performance of the composite material, XRD, SEM and electrochemical tests are carried out on the CC-NiO composite material obtained in the step 2.
In order to prove that the CC-NiO composite material obtained in the step 2 successfully prepares NiO, an XRD test is carried out. The test results are shown in fig. 1, in which the corresponding (002) crystal plane at 2 θ =26.110 ° belongs to the diffraction crystal plane of CC; the corresponding (200) crystal plane at 2 θ =43.472 ° belongs to the diffractive crystal plane of NiO, so it can be demonstrated that the composition of the CC-NiO composite contains CC and NiO, i.e., niO was successfully prepared on CC through step 2.
In order to prove the micro morphology of NiO in the CC-NiO composite material obtained in the step 2, SEM test is carried out. The test result is shown in fig. 2, niO is a nano-sheet structure and is uniformly distributed on the surface of the CC, so that it can be proved that NiO nano-sheets are successfully loaded on the CC.
In order to prove the electrochemical performance of the CC-NiO composite material obtained in the step 2, an electrochemical test is carried out. The electrochemical tests carried out on all the materials of the invention adopt the following methods: the prepared composite material is used as a working electrode, and a calomel electrode and a platinum electrode are respectively used as a reference electrode and a counter electrode, and are immersed in 3M KOH solution to test the specific capacitance of the composite material under a three-electrode system. The test results are shown in FIG. 3, where the discharge current density is 1 Ag and the discharge current is in the range of 0-0.4V -1 The specific capacitance of the CC-NiO composite material is 13.625F g -1 In the comparative literature, the specific capacitance when NiO nano-sheets are loaded on a CC by a chemical precipitation method is 600.3F g -1 In the present study, the specific capacitance of CC-NiO was small, and it was analyzed that the specific capacitance was small due to the difference in the preparation method and experimental conditions.
Step 3) CC-NiO-CuCo 2 S 4 Preparing a composite material, dissolving copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea in ethylene glycol according to the mass ratio of 1And absolute ethyl alcohol are respectively washed for three times, and then vacuum drying is carried out for 12 hours at the temperature of 80 ℃, thus obtaining the CC-NiO-CuCo 2 S 4 Composite material, CC-NiO-CuCo for short 2 S 4 。
NiO-CuCo on the carbon cloth is obtained through experiments and calculation 2 S 4 Average loading of 1.25mg cm -2 。
In order to prove that the CC-NiO-CuCoS composite material obtained in the step 3 successfully prepares CuCo 2 S 4 XRD test was performed. The test results are shown in fig. 4, in which the corresponding (002) crystal plane at 2 θ =26.110 ° belongs to the diffraction crystal plane of CC; the corresponding (200) crystal plane at 2 θ =43.472 ° belongs to the diffractive crystal plane of NiO; the (111), (311), (400), (511) and (440) crystal planes respectively corresponding to 2 theta =16.190 °, 31.249 °, 37.933 °, 49.931 °, and 54.793 ° belong to CuCo 2 S 4 Thus, it can be confirmed that CC-NiO-CuCo 2 S 4 The composite material comprises CC, niO and CuCo 2 S 4 Namely, the CuCo is successfully prepared on the CC-NiO composite material through the step 3 2 S 4 。
In order to prove that CuCo in the CC-NiO-CuCoS composite material obtained in the step 3 2 S 4 The microscopic properties of (a) were subjected to SEM test. The test results are shown in FIG. 5, cuCo 2 S 4 Is in a nano-particle structure and is distributed on the surfaces of the CC and the NiO nano-sheets, so that the CC-NiO composite material is successfully coated with CuCo on the surface 2 S 4 And (3) nanoparticles.
In order to prove the electrochemical performance of the CC-NiO-CuCoS composite material obtained in the step 3, an electrochemical test is carried out. The test results are shown in FIG. 6, where the discharge current density is 1 ag at the time of charging in the range of 0-0.4V -1 The specific capacitance of the CC-NiO-CuCoS composite material is 840 Fg -1 。
In order to prove the structural stability and the cycling stability of the CC-NiO-CuCoS composite material obtained in the step 3, an electrochemical cycling stability test is carried out on the CC-NiO-CuCoS composite material, and an SEM test is carried out on the electrode material after cycling.
The results of the electrochemical cycling stability test are shown in FIG. 7It shows that the CC-NiO-CuCoS composite material has the discharge current density of 2A g in the voltage range of 0-0.4V -1 When the material is charged and discharged for 3000 circles, the cycling stability is 100 percent;
the SEM test of the electrode material after cycling showed no significant change in the structure of the material after cycling and before cycling, as shown in fig. 8.
The experiment proves that the CC-NiO-CuCoS composite material has good structural stability and cycle stability.
To demonstrate NiO and CuCo 2 S 4 The respective roles played in the composite materials were to provide comparative example 1, cuCo alone loaded on CC 2 S 4 Nanoparticles, i.e. CC-CuCo 2 S 4 The preparation method and test results of the composite material of (1).
Comparative example 1
Preparation method of CC-CuCoS composite material, steps not specifically described and example 1 CC-NiO-CuCo 2 S 4 The preparation method of the composite material is the same, except that: only the step 1 and the step 3 are carried out, the step 2 CC-NiO composite material is omitted, namely the process of loading NiO nano-sheets is not carried out, and the obtained material is named as CC-CuCo 2 S 4 Composite materials, CC-CuCo for short 2 S 4 。
CuCo on carbon cloth is obtained by experiment and calculation 2 S 4 Average loading of 0.55mg cm -2 。
To demonstrate the CC-CuCo obtained in comparative example 1 2 S 4 The composite material successfully prepares CuCo 2 S 4 XRD test was performed. The test results are shown in fig. 9, in which the corresponding (002) crystal plane at 2 θ =26.110 ° belongs to the diffraction crystal plane of CC; the (311), (400), (551) and (440) crystal planes respectively corresponding to 2 theta =31.249 °,2 theta =37.933 °,2 theta =49.931 ° and 2 theta =54.793 ° belong to CuCo 2 S 4 Thus, it can be confirmed that CC-CuCo 2 S 4 The composite material comprises CC and CuCo 2 S 4 I.e. the successful preparation of CuCo on CC by comparative example 1 2 S 4 。
To demonstrate the CC-CuCo obtained in comparative example 1 2 S 4 CuCo in composite material 2 S 4 The microscopic morphology of (a) was subjected to SEM test. The test results are shown in FIG. 10, cuCo 2 S 4 Is of a nano-particle structure and is uniformly distributed on the surface of the CC, so that the CC can be proved to be successfully coated with CuCo 2 S 4 And (3) nanoparticles.
To demonstrate the CC-CuCo obtained in comparative example 1 2 S 4 The electrochemical performance of the composite material is tested electrochemically. The test results are shown in FIG. 11, where the discharge current density is 1 Ag when the discharge is charged in the range of 0-0.4V -1 When it is CC-CuCo 2 S 4 The specific capacitance of the composite material is 315.25F g -1 。
To demonstrate the role of the CC substrate in the composite, comparative example 2 was provided, in which CuCo was supported on NiO nanoplates 2 S 4 Nanoparticles, i.e. NiO-CuCo 2 S 4 Preparation method and test result of composite material.
Comparative example 2
Preparation method of NiO-CuCoS composite material, steps not specifically described and example 1 CC-NiO-CuCo 2 S 4 The preparation method of the composite material is the same, except that: only the step 2 and the step 3 are carried out, the step 1 CC is omitted for activation, namely the NiO nano-sheet is directly prepared and CuCo is loaded without adopting CC as a substrate 2 S 4 Nano particles, and the obtained material is named as NiO-CuCo 2 S 4 Composite materials, niO-CuCo for short 2 S 4 。
To demonstrate that the NiO-CuCo obtained in comparative example 2 2 S 4 The composite material successfully prepares NiO and CuCo 2 S 4 XRD test was performed. The test result is shown in fig. 12, in which the corresponding (200) crystal plane at 2 θ =43.253 ° belongs to the diffractive crystal plane of NiO; the (111), (311), (400), (551) and (440) crystal planes respectively corresponding to 2 theta =16.19 °,2 theta =31.249 °,2 theta =37.933 °,2 theta =49.931 ° and 2 theta =54.793 ° belong to CuCo 2 S 4 So that NiO-CuCo can be confirmed 2 S 4 The composite material comprises NiO and CuCo 2 S 4 Namely, cuCo was successfully prepared on NiO by comparative example 1 2 S 4 。
To demonstrate that the NiO-CuCo obtained in comparative example 2 2 S 4 NiO and CuCo in composite material 2 S 4 The microscopic morphology of (a) was subjected to SEM test. The test result is shown in FIG. 13, the NiO nano-sheet has obvious stacking structure, cuCo 2 S 4 The nanoparticle structure is not evident.
To demonstrate that the NiO-CuCo obtained in comparative example 2 2 S 4 The electrochemical performance of the composite material is tested electrochemically. The test results are shown in FIG. 14, where the discharge current density is 1 Ag when the discharge is charged in the range of 0-0.4V -1 When the specific capacitance is 164 Fg -1 。
According to the results obtained from the foregoing experimental tests,
1. the specific capacitance of the CC-NiO composite obtained in step 2 and the CC-NiO-CuCoS composite obtained in step 3 in example 1 can be seen as follows: is coated with CuCo 2 S 4 Then, the specific capacitance is 13.625F g -1 Is lifted to 840 Fg -1 The cycle performance is improved from 75% in the literature to 100% in the study; it can be further demonstrated that CuCo is added 2 S 4 Post NiO and CuCo 2 S 4 The method has a synergistic effect, and finally, ultrahigh specific capacitance performance and cycle stability are obtained.
2. Comparative example 1 CC-CuCo 2 S 4 As can be seen from the specific capacitance of the CC-NiO-CuCoS composite material obtained in example 1, the NiO nano-sheets are constructed to support CuCo 2 S 4 After the internal frame of the nanoparticles, the specific capacitance is from 315.25F g -1 Is lifted to 840 Fg -1 It turns out that these nanoplatelets are interconnected to each other and form a network with spaced voids, which results in a large surface area and an efficient buffering of volume changes.
3. Comparative example 2 NiO-CuCo 2 S 4 The specific capacitance of the CC-NiO-CuCoS composite material obtained in the example 1 is from 164 Fg -1 Is lifted to 840 Fg -1 . The test result shows that: CC as substrate material to CC-NiO-CuCo 2 S 4 The overall appearance of the composite material can play a decisive role, and the CC is taken as a conductive substrate, thereby being beneficial to the ultra-high speed transportation of electrons and ensuring that the CC-NiO-CuCo 2 S 4 The contact area of the composite material and the electrolyte is increased, so that the diffusion of ions is accelerated.
Claims (6)
1. A preparation method of a CC-NiO-CuCoS composite material is characterized by comprising the following steps:
step 1) activating CC, namely ultrasonically cleaning CC in an ether solution and absolute ethyl alcohol deionized water respectively, activating the CC in concentrated nitric acid with a certain mass fraction under a certain condition, and then cleaning the CC with deionized water and absolute ethyl alcohol and drying the CC to obtain activated CC;
step 2) preparing a CC-NiO composite material, namely putting the activated CC obtained in the step 1), nickel nitrate hexahydrate, ammonium fluoride and urea into water together with the nickel nitrate hexahydrate, the ammonium fluoride and the urea according to a certain substance quantity ratio, carrying out hydrothermal reaction under certain conditions, cleaning and drying after the reaction is finished, and annealing under certain conditions to obtain the CC-NiO composite material;
the mass ratio of nickel nitrate hexahydrate, ammonium fluoride and urea in the step 2) is 1;
step 3) CC-NiO-CuCo 2 S 4 Preparing a composite material, namely dissolving copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea in glycol to obtain a mixed solution, stirring the mixed solution for a certain time, adding thiourea into the mixed solution, stirring the mixed solution for a certain time, adding the thiourea into the mixed solution, adding the CC-NiO composite material obtained in the step 2) into the mixed solution after the mixing is finished, carrying out second hydrothermal treatment under a certain condition, washing the mixed solution by deionized water and absolute ethyl alcohol after the reaction is finished, and drying the washed solution to obtain the CC-NiO-CuCo composite material 2 S 4 A composite material;
the obtained CC-NiO-CuCo 2 S 4 The composite material consists of CC, niO and CuCo 2 S 4 Forming; wherein CC is a matrix material and the microscopic morphology is a fibrous structureThe NiO nano-sheets are not stacked by providing a substrate, and the conductive substrate is favorable for ultra-high-speed transportation of electrons; the microstructure of NiO is a nano-sheet structure, is loaded on the surface of the CC and is used for providing an additional pseudo-capacitor; cuCo 2 S 4 The microstructure of the NiO nano-film is a nano-particle structure and is attached to the surfaces of the CC and the NiO nano-film, and the function of stabilizing the flaky structure of the NiO and coating part of the exposed CC is realized; the catalyst is prepared by a two-step hydrothermal method by taking CC, nickel nitrate hexahydrate, ammonium fluoride, urea, copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea as starting materials;
the mass ratio of copper acetate monohydrate, cobalt acetate tetrahydrate and thiourea in the step 3) is 1.
2. The method of claim 1, wherein: the mass fraction of the concentrated nitric acid solution in the step 1) is 69%; the activation condition of the step 1) is that the activation temperature is 80-90 ℃, and the activation time is 3-4 h; the cleaning condition in the step 1) is ultrasonic for 15-20 min; the drying condition of the step 1) is that the drying temperature is 60-100 ℃, and the drying time is 12-24 h.
3. The method of claim 1, wherein: the hydrothermal reaction condition of the step 2) is that the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 12 h; the cleaning conditions of the step 2) are the same as the cleaning conditions of the step 1); the drying condition of the step 2) is that the drying temperature is 60-100 ℃, and the drying time is 20-24 h; the annealing condition of the step 2) is that the annealing temperature is 350 ℃, and the annealing time is 2 h.
4. The method of claim 1, wherein: in the step 3), the stirring time is 30-60min when the copper acetate monohydrate and the cobalt acetate tetrahydrate are dissolved in the ethylene glycol, and the stirring time after thiourea is added is 30-60min; the second hydrothermal condition in the step 3) is that the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 hours; the cleaning conditions of the step 3 are the same as the cleaning conditions of the step 1); the drying condition of the step 3 is that the drying temperature is 80 ℃ and the drying time is 12 h.
5. The application of the CC-NiO-CuCoS composite material obtained by the preparation method according to claim 1 as a supercapacitor electrode material is characterized in that: discharging in the range of 0-0.4V at a discharge current density of 1 Ag -1 The specific capacitance is 600-900 Fg -1 。
6. The application of the CC-NiO-CuCoS composite material prepared by the preparation method according to claim 1 as a supercapacitor electrode material is characterized in that: discharging in the range of 0-0.4V at a discharge current density of 2 Ag -1 The cycling stability after 3000 cycles was 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011171824.7A CN112409028B (en) | 2020-10-28 | 2020-10-28 | CC-NiO-CuCoS composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011171824.7A CN112409028B (en) | 2020-10-28 | 2020-10-28 | CC-NiO-CuCoS composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112409028A CN112409028A (en) | 2021-02-26 |
| CN112409028B true CN112409028B (en) | 2022-10-11 |
Family
ID=74841744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011171824.7A Active CN112409028B (en) | 2020-10-28 | 2020-10-28 | CC-NiO-CuCoS composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112409028B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115440503B (en) * | 2022-08-22 | 2023-05-12 | 桂林电子科技大学 | Cobalt copper sulfide nanosheets and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107154486A (en) * | 2017-05-17 | 2017-09-12 | 厦门大学 | A kind of cupric multi-element metal sulfide is the sodium-ion battery of negative material |
| WO2019019412A1 (en) * | 2017-07-26 | 2019-01-31 | 中能中科（天津）新能源科技有限公司 | Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof |
| CN109678133A (en) * | 2019-01-14 | 2019-04-26 | 桂林电子科技大学 | A kind of C-base composte material and its preparation method and application of nickel oxide doping |
| CN111825127A (en) * | 2020-07-07 | 2020-10-27 | 江苏大学 | Preparation method and application of metal nickel-based nano material |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2297383A1 (en) * | 2008-06-18 | 2011-03-23 | Board of Trustees of the University of Arkansas | Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives |
| KR20150004640A (en) * | 2013-07-03 | 2015-01-13 | 주식회사 포스코 | Wire rod having excellent cold forging characteristics and method for manufacturing the same |
| CN106315695B (en) * | 2016-08-24 | 2018-10-30 | 福州大学 | A kind of strawberry-like cobalt acid nickel nano material and preparation method thereof |
| CN108530109B (en) * | 2018-03-23 | 2021-03-23 | 西北工业大学 | Anti-oxidation coating with 1500-1700 ℃ on surface of carbon/carbon composite material and preparation method thereof |
| CN108365210A (en) * | 2018-04-12 | 2018-08-03 | 桂林电子科技大学 | A kind of activated carbon carbon-sulfur materials and its preparation method and application |
| CN108455592B (en) * | 2018-04-28 | 2021-09-24 | 福州大学 | Preparation method of nitrogen-doped porous carbon/carbon nanotube composite with interpenetrating network structure |
| CN109216707A (en) * | 2018-09-12 | 2019-01-15 | 成都理工大学 | CuCo2S4@Ni composite material and preparation method and application |
| CN110407605B (en) * | 2019-08-07 | 2021-11-16 | 哈尔滨师范大学 | Preparation process of porous supercapacitor material |
| CN111785526B (en) * | 2020-06-10 | 2022-04-26 | 桂林电子科技大学 | Polypyrrole-coated Ni-Co-S nanoneedle array composite material and preparation method and application thereof |
| CN111777069B (en) * | 2020-07-20 | 2022-12-23 | 桂林电子科技大学 | MXene composite material with stable structure and preparation method and application thereof |
-
2020
- 2020-10-28 CN CN202011171824.7A patent/CN112409028B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107154486A (en) * | 2017-05-17 | 2017-09-12 | 厦门大学 | A kind of cupric multi-element metal sulfide is the sodium-ion battery of negative material |
| WO2019019412A1 (en) * | 2017-07-26 | 2019-01-31 | 中能中科（天津）新能源科技有限公司 | Carbon nanoparticle-porous framework composite material, lithium metal complex of carbon nanoparticle-porous framework composite material, preparation methods therefor, and applications thereof |
| CN109678133A (en) * | 2019-01-14 | 2019-04-26 | 桂林电子科技大学 | A kind of C-base composte material and its preparation method and application of nickel oxide doping |
| CN111825127A (en) * | 2020-07-07 | 2020-10-27 | 江苏大学 | Preparation method and application of metal nickel-based nano material |
Non-Patent Citations (1)
| Title |
|---|
| 水热共沉积C/C复合材料的Ni催化石墨化及性能研究;潘利敏等;《陕西科技大学学报》;20181022(第05期);第129-134页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112409028A (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dai et al. | MOF-derived Co3O4 nanosheets rich in oxygen vacancies for efficient all-solid-state symmetric supercapacitors | |
| Azam et al. | Recent advances of silicon, carbon composites and tin oxide as new anode materials for lithium-ion battery: A comprehensive review | |
| Young et al. | High energy density supercapacitors composed of nickel cobalt oxide nanosheets on nanoporous carbon nanoarchitectures | |
| Abouali et al. | Electrospun carbon nanofibers with in situ encapsulated Co3O4 nanoparticles as electrodes for high-performance supercapacitors | |
| Pan et al. | Interlayer spacing regulation of NiCo-LDH nanosheets with ultrahigh specific capacity for battery-type supercapacitors | |
| Mondal et al. | Highly porous NiCo2O4 nanoflakes and nanobelts as anode materials for lithium-ion batteries with excellent rate capability | |
| Xu et al. | Facilely hierarchical growth of N-doped carbon-coated NiCo2O4 nanowire arrays on Ni foam for advanced supercapacitor electrodes | |
| Kumar et al. | Faster ion switching NiCo2O4 nanoparticle electrode-based supercapacitor device with high performances and long cycling stability | |
| Wang et al. | Approaching the downsizing limit of silicon for surface‐controlled lithium storage | |
| Cai et al. | Three-dimensional Co3O4@ NiMoO4 core/shell nanowire arrays on Ni foam for electrochemical energy storage | |
| CN108258334B (en) | Composite flexible electrode, preparation method and application thereof | |
| Chen et al. | Controlled Synthesis of Carbon Nanofibers Anchored with Zn x Co3–x O4 Nanocubes as Binder-Free Anode Materials for Lithium-Ion Batteries | |
| Zhang et al. | NiMn-layered double hydroxides chemically anchored on Ti3C2 MXene for superior lithium ion storage | |
| Wang et al. | Simple solvothermal synthesis of magnesium cobaltite microflowers as a battery grade material with high electrochemical performances | |
| Sun et al. | Novel bake-in-salt method for the synthesis of mesoporous Mn3O4@ C networks with superior cycling stability and rate performance | |
| CN111777069B (en) | MXene composite material with stable structure and preparation method and application thereof | |
| Shi et al. | 3D mesoporous hemp-activated carbon/Ni3S2 in preparation of a binder-free Ni foam for a high performance all-solid-state asymmetric supercapacitor | |
| Lv et al. | One-pot synthesis of NiCo2O4/rGO/NF hybrid electrode materials realizing ultrahigh capacitance and rapid charge/discharge at large current density | |
| Yue et al. | Hierarchical structured Cu/Ni/TiO2 nanocomposites as electrodes for lithium-ion batteries | |
| CN113690429A (en) | Carbon-coated graphene/metal oxide composite material and preparation method thereof | |
| Li et al. | NiCo2S4 combined 3D hierarchical porous carbon derived from lignin for high-performance supercapacitors | |
| Han et al. | Temperature-induced hierarchical Tremella-like and Pinecone-like NiO microspheres for high-performance supercapacitor electrode materials | |
| Zhu et al. | CoO quantum dots anchored on reduced graphene oxide aerogels for lithium-ion storage | |
| He et al. | NiGa2O4 nanosheets in a microflower architecture as anode materials for Li-Ion capacitors | |
| CN113539699A (en) | ACNFs @ Ni-Mn-P nanosheet array composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |