CN110415986B - Ni-doped CoO/C composite material and preparation method thereof - Google Patents
Ni-doped CoO/C composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010902 straw Substances 0.000 claims abstract description 50
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 38
- 235000009566 rice Nutrition 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
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- 238000001354 calcination Methods 0.000 claims description 15
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 15
- 239000003990 capacitor Substances 0.000 abstract description 13
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 229910003266 NiCo Inorganic materials 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000003763 carbonization Methods 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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 belongs to the technical field of electrode material preparation, and particularly relates to a Ni-doped CoO/C composite material and a preparation method thereof. The composite material is characterized in that CoO doped with Ni is loaded on the surface of C, and the C is a rice straw biomass carbon material. The invention also provides a preparation method of the Ni-doped CoO/C composite material, and the Ni-doped CoO/C composite material prepared by the method is needle-shaped. Has the advantages that: the Ni-doped CoO/C composite material prepared by the method has the advantages of large specific surface area, good stability, good crystallization and no agglomeration, and has a wide application prospect when being used as an electrode material of a capacitor.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a Ni-doped CoO/C composite material and a preparation method thereof.
Background
With the rapid development of agriculture and industry, along with the rapid growth of population, the global energy consumption rate is very remarkable, and energy exhaustion and environmental pollution are two major problems facing human development at present, so that a novel energy storage and energy conversion device which is low in cost, easy to obtain, environment-friendly and sustainable must be vigorously developed to meet the development of modern society and increasingly outstanding environmental problems. The carbon material is easy to obtain, particularly the biomass carbon material, the biomass carbon has high stability and extremely strong adsorption performance, is widely distributed in the atmosphere and the earth surface environment, has good chemical stability and electrical conductivity, and is low in cost and easy to obtain.
With the rapid development of world economy and the continuous acceleration of the global process of economy, people have more and more requirements on energy, high-efficiency energy storage electric appliances are widely concerned, and an electrochemical super capacitor is one of the energy storage devices which are widely researched at present. The super capacitor has larger power density and can provide enough instantaneous power for braking of the vehicle. In addition, the super capacitor can also be applied to the aspects of military industry, material transportation, electronic storage devices and the like, and has wide application prospect.
NiCo of different forms and structures2O4The preparation is researched by a plurality of chemists, such as CN106938859A, CN104701036A and CN106882845A, tubular, graded flower-shaped and mesoporous echinoid NiCo is prepared respectively2O4。NiCo2O4The main problem of the cathode material is that the volume change is too obvious in the process of lithium intercalation and deintercalation, and the pulverization phenomenon is easy to occur, so that the electrochemical cyclicity of the material is not ideal.
Chinese patent application CN104624191A discloses a CoO/C catalyst and a preparation method thereof. The method adopts high-temperature reflux and temperature programming methods to obtain the CoO/C catalyst with the nano particle size, and ammonia water, cobalt salt and carbon powder are uniformly mixed and subjected to temperature programming to obtain the CoO/C catalyst. Weiwei Yuan, namely 'Porous CoO/C polyhydrodra as anode material for Li-ion batteries', adopts a hydrothermal impregnation method to prepare uniform, graded and Porous CoO/C polyhedrons, each CoO/C polyhedron consists of a plurality of ordered nano particles (about 100 nanometers), and the polyhedral CoO/C composite material has limited specific surface area and influences the electrochemical performance of the polyhedral CoO/C composite material as a capacitor electrode material.
Therefore, the prepared capacitor electrode material with large specific surface area and high conductivity has very important practical application value for improving the electrochemical performance of the capacitor.
Disclosure of Invention
In order to further improve the electrochemical performance of the capacitor electrode material, the invention provides a Ni-doped CoO/C composite material and a preparation method thereof. The combination of CoO and rice straw enables CoO to be uniformly dispersed on the surface of rice straw biochar, and NiCo is solved2O4The material is easy to pulverize, poor in stability and the like, and the conductivity of the composite material can be improved by doping Ni, so that a foundation is laid for the commercial application of the electrode material of the super capacitor.
The technical scheme of the invention is carried out as follows:
a Ni-doped CoO/C composite material is characterized in that Ni-doped CoO is loaded on the surface of C, and the C is a rice straw biomass carbon material.
Furthermore, the composite material is needle-shaped, has a large specific surface area, and is favorable for improving the electrochemical performance of the composite material.
The invention also aims to provide a preparation method of the Ni-doped CoO/C composite material, which comprises the following steps:
(1) dissolving soluble cobalt salt in deionized water to obtain a cobalt salt water solution;
(2) placing soluble nickel salt and urea in the cobalt salt water solution obtained in the step (1), and performing ultrasonic treatment to obtain a mixed solution;
(3) placing the carbonized rice straws into the mixed solution obtained in the step (2), carrying out hydrothermal reaction, taking out the carbonized rice straws after the reaction is finished, and drying the carbonized rice straws for later use;
(4) and (4) calcining the carbonized rice straws dried in the step (3) in a nitrogen atmosphere to obtain the Ni-doped CoO/C composite material.
After the hydrothermal reaction is finished, replacing the solvent in the hydrothermal reaction kettle with methanol or ethanol, replacing once every 3-24 hours for 2-8 times, and drying at normal temperature to obtain a sample NiCo2O4。
Preferably, the soluble cobalt salt in the step (1) is one or more of cobalt acetate tetrahydrate, cobalt chloride and cobalt nitrate hexahydrate; in the step (2), the soluble nickel salt is nickel sulfate hexahydrate or/and nickel nitrate hexahydrate; the mol ratio of the soluble cobalt salt to the soluble nickel salt to the urea is 1: (0.2-20): (1-50).
Preferably, the hydrothermal reaction in the step (3) is carried out at a temperature of 100-200 ℃ for 3-48 h.
Preferably, the carbonized rice straws obtained in the step (3) are obtained by calcining the rice straws at the temperature of 500-900 ℃ for 4-8h under the nitrogen condition.
Preferably, the ultrasonic treatment in the step (2) is carried out for 30-60 min at the frequency of 50-100 kHz.
Preferably, the calcining condition in the step (4) is calcining for 1-6 hours at the temperature of 350-1000 ℃.
The invention has the beneficial effects that:
(1) compared with the polyhedral shape of the CoO/C composite material in the prior art, the prepared Ni-doped CoO/C composite material has the advantages of larger specific surface area, good stability, good crystallization and no agglomeration, has larger application prospect when being used as an electrode material of a capacitor, can greatly relieve the volume expansion effect of the material in the charge-discharge process, and further improves the chemical electricity storage performance and the electrochemical performance.
(2) The Ni-doped CoO/C composite material obtained by adopting a one-step hydrothermal method has the characteristic of simple operation; compared with the common carbon material in the prior art, the rice straw biomass carbon material has the advantages that the Ni-doped CoO is easier to load due to the surface texture structure, and the dispersion is uniform and regular, so that the CoO agglomeration cannot be caused; meanwhile, the rice straw is used as a raw material, so that the preparation cost is reduced, and the method has the characteristics of low price, easiness in obtaining, environmental friendliness and sustainability, is beneficial to the construction of an environment-friendly society, and meets the requirement of green chemistry.
(3) The invention takes hydrothermal synthesis method as assistance to synthesize NiCo2O4Loaded on the surface of a biomass carbon material of rice straws, carbonized to prepare Ni-dopedThe CoO/C composite material optimizes the process reaction conditions, greatly simplifies the synthesis process and reduces the experiment cost.
Drawings
FIG. 1 is a NiCo sample obtained in example 12O4XRD spectrum of (1);
FIG. 2 shows NiCo obtained in example 12O4SEM topography of;
FIG. 3 is an XRD spectrum of the Ni-doped CoO/C composite material prepared in example 1;
FIG. 4 is an SEM topography (A) multiplied by 2.50k times of the Ni-doped CoO/C composite material prepared in example 1; (B) x 30.0k times;
FIG. 5 shows the straw after carbonization and NiCo obtained in example 12O4And the specific capacitance plot of the resulting CoO/C composite of example 1;
FIG. 6 shows the straw after carbonization and NiCo obtained in example 12O4And specific capacitance cycle performance plot of the CoO/C composite obtained in example 1;
FIG. 7 shows the straw after carbonization and NiCo obtained in example 12O4And the cyclic voltammogram of the Ni-doped CoO/C composite material obtained in example 1, wherein A-the carbonized straw; B-NiCo from example 12O4(ii) a C-Ni-doped CoO/C composite obtained in example 1;
FIG. 8 shows the straw after carbonization and NiCo obtained in example 12O4And a constant current charge-discharge diagram of the Ni-doped CoO/C composite material obtained in example 1, wherein A-the carbonized straw; B-NiCo from example 12O4(ii) a C-Ni doped CoO/C composite obtained in example 1.
Detailed Description
The invention will be further explained below, and the invention is not limited to the contents of the following embodiments, wherein one or a combination of several specific embodiments can also achieve the object of the invention.
Example 1
(1) Weighing 0.73g of cobalt nitrate hexahydrate and 50mL of deionized water, and mixing to obtain a cobalt nitrate solution;
(2) respectively weighing 0.44g of nickel nitrate hexahydrate and 0.45g of urea, putting the nickel nitrate hexahydrate and the urea into the cobalt nitrate solution obtained in the step (1), and carrying out ultrasonic treatment for 30 minutes under the condition that the ultrasonic frequency is 60kHz to obtain a mixed solution; wherein the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea is 1:0.6: 3;
(3) taking a small piece of carbonized rice straw (the carbonization condition is that the rice straw is calcined for 3 hours at 650 ℃ under the condition of introducing nitrogen) and the mixed solution obtained in the step (2) to be transferred into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining together, then carrying out constant-temperature hydrothermal reaction, carrying out hydrothermal reaction for 24 hours at the temperature of 100 ℃, taking out the carbonized rice straw after the reaction kettle is cooled to room temperature, and drying at normal temperature for standby application;
(4) replacing the solvent in the reaction kettle with methanol once every 10 hours for 3 times, and drying at normal temperature; the obtained sample is in N2At 650 ℃ for 3 hours, to obtain a sample NiCo2O4；
(5) Putting the carbonized rice straws obtained in the step (3) into a porcelain boat, and introducing N2Under the condition of (1), calcining at 650 ℃ for 3 hours to prepare the Ni-doped CoO/C composite material.
NiCo prepared in this example2O4The XRD spectrum of (A) is shown in figure 1, NiCo2O4The positions of the standard diffraction peaks of (A) are consistent, indicating that the NiCo obtained2O4The sample was pure phase NiCo2O4A crystal; the SEM topography is shown in FIG. 2, and it can be seen that NiCo prepared by the preparation method of the invention2O4Is in the shape of cluster needle.
An XRD spectrogram of the Ni-doped CoO/C composite material prepared by the embodiment is shown in figure 3, CoO is prominent, and the capacitance performance is improved; the SEM topography is shown in figure 4, and it can be seen that the Ni-doped CoO/C composite material prepared by the method has the advantages that the Ni-doped CoO is highly dispersed on the surface of the rice straw biomass carbon material, is acicular and has a larger specific surface area, and the high dispersion of the Ni-doped CoO avoids the agglomeration of the material, so that the Ni-doped CoO/C composite material has a huge application prospect in the aspect of being used for capacitors.
Example 2
(1) Weighing 0.73g of cobalt nitrate hexahydrate and 50mL of deionized water, and mixing to obtain a cobalt nitrate solution;
(2) respectively weighing 0.723g of nickel nitrate hexahydrate and 0.45g of urea, putting the nickel nitrate hexahydrate and the urea into the cobalt nitrate solution obtained in the step (1), and carrying out ultrasonic treatment for 30 minutes under the condition that the ultrasonic frequency is 60kHz to obtain a mixed solution; wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:1: 4;
(3) taking a small piece of carbonized rice straw (the carbonization condition is that the rice straw is calcined for 8 hours at 500 ℃ under the condition of introducing nitrogen) and the mixed solution obtained in the step (2) to be transferred into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining together, then carrying out constant-temperature hydrothermal reaction, carrying out hydrothermal reaction for 24 hours at the temperature of 110 ℃, taking out the carbonized rice straw after the reaction kettle is cooled to room temperature, and drying at normal temperature for standby application;
(4) replacing the solvent in the reaction kettle with ethanol, replacing once every 12 hours for 3 times, and drying at normal temperature; the obtained sample is in N2Calcining at 800 ℃ for 4 hours under the conditions of (1) to obtain a sample NiCo2O4；
(5) Putting the carbonized rice straws obtained in the step (3) into a porcelain boat, and introducing N2Calcining for 4 hours at 800 ℃ under the condition of (1) to obtain the Ni-doped CoO/C composite material.
Example 3
(1) Weighing 0.73g of cobalt nitrate hexahydrate and 50mL of deionized water, and mixing to obtain a cobalt nitrate solution;
(2) respectively weighing 0.87g of nickel nitrate hexahydrate and 0.48g of urea, putting the nickel nitrate hexahydrate and the urea into the cobalt nitrate solution obtained in the step (1), and carrying out ultrasonic treatment for 40 minutes under the condition that the ultrasonic frequency is 100kHz to obtain a mixed solution; the molar ratio of the medium cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:1.2: 3.2;
(3) taking a small piece of carbonized rice straw (the carbonization condition is that the rice straw is calcined for 5 hours at 900 ℃ under the condition of introducing nitrogen) and the mixed solution obtained in the step (2) to be transferred into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining together, then carrying out constant-temperature hydrothermal reaction, carrying out hydrothermal reaction for 12 hours at the temperature of 130 ℃, taking out the carbonized rice straw after the reaction kettle is cooled to the room temperature, and drying at the normal temperature for standby application;
(4) replacing the solvent in the reaction kettle with methanol once every 12 hours for 5 times; the obtained sample is in N2Calcining at 700 ℃ for 3 hours under the condition of (1) to obtain a sample NiCo2O4；
(5) Putting the carbonized rice straws obtained in the step (3) into a porcelain boat, and introducing N2And calcining at 700 ℃ for 3 hours to obtain the Ni-doped CoO/C composite material.
Example 4
(1) Weighing 0.73g of cobalt nitrate hexahydrate and 50mL of deionized water, and mixing to obtain a cobalt nitrate solution;
(2) respectively weighing 1.4530g of nickel nitrate hexahydrate and 0.4505g of urea, putting the nickel nitrate hexahydrate and the urea into the cobalt nitrate solution obtained in the step (1), and carrying out ultrasonic treatment for 20 minutes under the condition that the ultrasonic frequency is 100kHz to obtain a mixed solution; wherein the molar ratio of the cobalt nitrate hexahydrate to the nickel nitrate hexahydrate to the urea is 1:2: 3;
(3) taking a small piece of carbonized rice straw (the carbonization condition is that the rice straw is calcined for 7 hours at 700 ℃ under the condition of introducing nitrogen) and the mixed solution obtained in the step (2) to be transferred into a stainless steel hydrothermal kettle with a polytetrafluoroethylene lining, then carrying out constant-temperature hydrothermal reaction, carrying out hydrothermal reaction for 12 hours at the temperature of 150 ℃, taking out the carbonized rice straw after the reaction kettle is cooled to the room temperature, and drying at the normal temperature for standby application;
(4) replacing the solvent in the reaction kettle with methanol once every 12 hours for 5 times, and drying at normal temperature; the obtained sample is in N2Calcining at 800 ℃ for 2 hours under the condition of (1) to obtain a sample NiCo2O4；
(5) Putting the carbonized rice straws obtained in the step (3) into a porcelain boat, and introducing N2Calcining at 800 ℃ for 2 hours under the condition of (1) to obtain the Ni-doped CoO/C composite material.
Comparative example 1
The carbonized rice straw of example 1 was omitted and step (5) was replaced as follows:
mixing NiCo in the step (4)2O4In general N2Calcining at 650 ℃ for 3 hours under the condition of (1), introducing acetylene gas with the gas flow of 5sccm and the gas introduction time of 4min,obtaining the Ni-doped CoO/C composite material.
Specific surface area and conductivity tests were performed on the Ni-doped CoO/C composite materials obtained in examples 1-4 and comparative example 1, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the Ni-doped CoO/C composite material prepared by the method has higher specific surface area and conductivity, and has larger application prospect in the aspect of capacitors; the Ni-doped CoO/C composite material prepared in the comparative example 1 has agglomeration, so that the specific surface area is not good.
And (3) electrochemical performance testing:
the electrochemical performance tests are all completed on the Shanghai Chenghua CHI660 electrochemical workstation. A three-electrode system is adopted: the platinum sheet electrode is a counter electrode, and the Saturated Calomel Electrode (SCE) is a reference electrode; a working electrode is also included.
Preparation of a working electrode: respectively mixing the carbonized straws and NiCo obtained in example 12O4And the Ni-doped CoO/C composite material obtained in the example 1 are respectively mixed with PVDF and acetylene black according to the mass ratio of 8:1:1, 2mL of isopropanol is added as a dispersing agent, and the mixture is fully stirred uniformly and uniformly subjected to ultrasonic oscillation. Uniformly coating the sample on a pretreated nickel screen with a coating area of 1cm to 1cm, drying in a vacuum drying oven at 60 ℃ for 12h, and controlling the electrode material (i.e. carbonized straws, NiCo obtained in example 1)2O4And the Ni-doped CoO/C composite obtained in example 1) at 0.01 mg.
Cyclic voltammetry curve tests are carried out by using the prepared three-electrode system, and cyclic voltammetry tests are carried out at scanning speeds of 0.005, 0.01, 0.02, 0.04 and 0.08V/s respectively. And (3) calculating the specific capacitance of the electrode by using a formula according to the cyclic voltammetry curve: cS＝∫IdV/2mv△V；
Wherein Cs is specific capacitance (F/g), I is current (A), m is electrode material mass (g), V is scanning speed (V/s), and DeltaV is potential window (V).
The specific capacitance was measured as shown in FIG. 5, and it can be seen that NiCo2O4The specific capacitance of the electrode material is the minimum, and is 425F/g at 5 mV/s; the specific capacitance of the carbonized straw electrode material is 481F/g under 5 mV/s; the specific capacitance of the Ni-doped CoO/C composite material obtained in the electrode material example 1 is 752F/g at 5 mV/s; the specific capacitance of the Ni-doped CoO/C composite material obtained in example 1 is the largest, and the specific capacitance value decreases with the increase of the scanning rate.
The specific capacitance of the Ni-doped CoO/C composite material prepared in examples 2-4 as an electrode material is 730-770F/g at 5 mV/s.
Cycle durability is one of the most important electrochemical properties of supercapacitors. The experimental results show that the cycle performance of each electrode material is shown in FIG. 6, and the cycle performance of the Ni-doped CoO/C composite material obtained in example 1 is obviously superior to that of carbonized straws and NiCo obtained in example 1 under the condition that the capacitance of the electrode changes under the condition that the current density is 1.0A/g in a constant-current charge-discharge test carried out for 2000 cycles2O4The material can run for a long period under the condition of high current density, the capacity retention of the capacitor is still good, the capacity retention rate of the Ni-doped CoO/C composite material electrode obtained in the embodiment 1 is 96.7% after 2000 cycles, and the service life is long.
The results show that the cycle performance of the Ni-doped CoO/C composite material of examples 2-4 is between 94% and 98% after 2000 cycles under the condition of high current density.
FIG. 7 shows the straw (A) after carbonization and NiCo obtained in example 1 at different scanning rates2O4(B) And cyclic voltammogram of the Ni-doped CoO/C composite (C) obtained in example 1. It can be seen that the cyclic voltammogram forms a graph similar to a rectangle, and the closer the curve is to a rectangle, the more desirable the capacitive performance. The specific surface area of the Ni-doped CoO/C composite material CoO/C obtained in example 1 is larger, the contact area with the electrolyte is increased, and therefore the resistivity of the electrode in the electrolyte is reduced, and better conductivity is presented.
FIG. 8 shows the carbonized straw (A) obtained in example 1NiCo2O4(B) And the constant current charging and discharging curves of 6M KOH of the Ni-doped CoO/C composite material (C) obtained in example 1 at different current densities of 1A/g, 2A/g, 3A/g and 4A/g. As can be seen from FIG. 8, the current density is increased from 1A/g to 4A/g, the voltage and the time are in a nonlinear relationship, and the charge-discharge time of the Ni-doped CoO/C composite material obtained in example 1 is longest as an electrode material, which indicates that the internal resistance of the Ni-doped CoO/C composite material prepared by the invention is the smallest of the three materials, and the side shows that the conductivity of the material is better, and the material shows more excellent capacitance characteristics.
Claims (6)
1. A preparation method of a Ni-doped CoO/C composite material is characterized by comprising the following steps:
(1) dissolving soluble cobalt salt in deionized water to obtain a cobalt salt water solution;
(2) placing soluble nickel salt and urea in the cobalt salt water solution obtained in the step (1), and performing ultrasonic treatment to obtain a mixed solution;
(3) placing the carbonized rice straws into the mixed solution obtained in the step (2), carrying out hydrothermal reaction, taking out the carbonized rice straws after the reaction is finished, and drying the carbonized rice straws for later use;
(4) calcining the carbonized rice straws dried in the step (3) in a nitrogen atmosphere to obtain a Ni-doped CoO/C composite material;
the composite material is characterized in that CoO doped with Ni is loaded on the surface of C, and the C is a rice straw biomass carbon material;
the calcination in the step (4) is carried out for 1-6 h at the temperature of 650-1000 ℃.
2. The preparation method according to claim 1, wherein the soluble cobalt salt in step (1) is one or more of cobalt acetate tetrahydrate, cobalt chloride and cobalt nitrate hexahydrate; in the step (2), the soluble nickel salt is nickel sulfate hexahydrate or/and nickel nitrate hexahydrate; the mol ratio of the soluble cobalt salt to the soluble nickel salt to the urea is 1: (0.2-20): (1-50).
3. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (3) is carried out at a temperature of 100 to 200 ℃ for 3 to 48 hours.
4. The preparation method as claimed in claim 1, wherein the carbonized rice straw in step (3) is obtained by calcining rice straw at 500-900 ℃ for 4-8h under nitrogen.
5. The method according to claim 1, wherein the ultrasonic treatment in the step (2) is ultrasonic treatment at a frequency of 50 to 100kHz for 30 to 60 min.
6. The method of claim 1, wherein the composite material is needle-shaped.
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Application publication date: 20191105 Assignee: Jiangsu Ningda environmental protection Co.,Ltd. Assignor: JIANGSU University OF TECHNOLOGY Contract record no.: X2023980054656 Denomination of invention: A Ni doped CoO/C composite material and its preparation method Granted publication date: 20210518 License type: Common License Record date: 20240103 |