CN114388278A - Preparation method and application of corn straw-based pseudocapacitance electrode material - Google Patents
Preparation method and application of corn straw-based pseudocapacitance electrode material Download PDFInfo
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- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 66
- 235000005822 corn Nutrition 0.000 title claims abstract description 66
- 239000010902 straw Substances 0.000 title claims abstract description 45
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 14
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 12
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 12
- 239000011565 manganese chloride Substances 0.000 claims description 12
- 229940099607 manganese chloride Drugs 0.000 claims description 12
- 235000002867 manganese chloride Nutrition 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000011056 performance test Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
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- 239000003990 capacitor Substances 0.000 claims description 4
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- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
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- 238000002791 soaking Methods 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims 1
- 238000002847 impedance measurement Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
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- 239000011664 nicotinic acid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010907 stover Substances 0.000 description 2
- 238000010521 absorption reaction 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
- 238000007599 discharging Methods 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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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Abstract
The invention provides a preparation method and application of a corn straw-based pseudocapacitance electrode material2Under protection, continuously heating and roasting at a certain heating rate. The obtained sample is washed by HCl and deionized water respectively and dried for standby. Then weighing urea, an activating agent and deionized water, adding the urea, the activating agent and the deionized water into a hydrothermal reaction kettle, putting the corn straw skeleton into the mixed solution for reaction, washing and drying the mixture, and then adding the corn straw skeleton into the hydrothermal reaction kettleThe product obtained is in N2Under protection, the carbon-based composite material is obtained by calcination, and the electrochemical performance of the carbon-based composite material is measured under a three-electrode system. The invention is realized by adding N2And (3) carrying out temperature programming carbonization under protection, etching and forming pores to prepare a hollow porous corn straw carbon skeleton, growing a transition bimetallic oxide on the surface of the carbon skeleton in situ by adopting a hydrothermal method, and applying the transition bimetallic oxide to an electrochemical electrode material.
Description
The technical field is as follows:
the invention relates to the technical field of super capacitors, in particular to a preparation method and application of a corn straw-based transition bimetal oxide pseudocapacitance electrode material.
Background art:
with the continuous increase of energy consumption and the continuous improvement of environmental protection requirements, the development of energy storage materials faces huge challenges. In various energy storage equipment, ultracapacitor System (SCs) is the novel energy storage device between traditional condenser and battery, and this device has characteristics such as high-energy pulse, charge-discharge process are fast and stable safety. The performance of SCs depends to a large extent on the electrode material. Currently, various materials (e.g., carbon materials, transition metal oxides, conductive polymers) are widely studied as electrode materials. Wherein, transition metal oxide RuO2Exhibit very high electrochemical performance, but the commercial application thereof is limited by high cost (J.W.Long, K.E.Swider, C.I.Merzbacher, D.R.Rolison, Langmuir,15, 780-. Therefore, efforts have been made to find inexpensive transition metal oxides having good capacitive properties. However, when the single metal oxides are used as electrode materials, the structures change after several hundred cycles, and thus they show disadvantages of low conductivity and poor cycle performance.
Transition bimetal oxides are of widespread interest because they contain two metal ions to provide more abundant redox reactions (l.q.mai, f.yang, y.l.zhao, x.xu, l.xu, y.z.luo, nat.commun.,2,381(2011), l.y.lin, h.y.lin, w.l.hong, Thin solid films ms.667,69-75 (2018)), w.qiu, h.xiao, m.yu, chem.eng.j.352,996-1003 (2018)), d.khalafalah, o.y.alothtoman, h.fouad, j.electroum.soc.165, F1067-F1074(2018)), however, there are two short plates as electrode materials: on one hand, the conductivity of the oxide-doped carbon nano-particles is enhanced relative to that of oxides, but needs to be further improved so as to solve the defect of poor dynamic performance in redox reaction; on the other hand, the Faraday redox reaction only occurs on the surface of the electrode material, and the diffusion distance of the electrolyte entering the electrode is short, so that the interior of the electrode is difficult to participate in the storage process of electrochemical charges. Therefore, the search for new preparation methods to overcome these problems has been the main research direction.
After millions of years of evolution and evolution, organisms form various and unique complex structures (H.ZHou, T.Fan, D.ZHang, ChemSusChem,4,1344 1387 (2011); Z.P.Qiu, Y.S.Wang, X.Bi, T.ZHou, J.ZHou, J.P.ZHao, Z.C.Miao, W.M.Yi, P.Fu, S.P.ZHuo, J.Power Sources,376, 82-90 (2018)) in order to facilitate the transportation and absorption of nutrient ions, and the materials prepared by the biomimetic induction method retain the microstructure and the morphology of biomass and have excellent performance and are widely concerned by people, wherein the biomass carbon material has a highly hollow and porous structure, can provide a larger specific surface area, shorten an ion transportation path, is beneficial to the rapid transmission of charges in an electrode, and effectively increases the conductivity of the materials.
The invention content is as follows:
the invention aims to provide a preparation method and application of a corn straw-based pseudocapacitance electrode material.
The technical scheme of the invention is as follows:
a preparation method of a corn straw-based pseudocapacitance electrode material comprises the following steps:
(1) pretreatment: weighing 2g of corn straws, putting the corn straws into a 100ml hydrothermal reaction kettle, adding 0.1mol/L citric acid to completely immerse the corn straws in the citric acid, heating the mixture to react for 6 hours at 200 ℃, then washing the mixture with deionized water and drying the mixture to obtain a corn straw hydrothermal carbon raw material;
(2) adding the corn straw hydrothermal carbon raw material obtained in the step (1) into an electrolyte, soaking for 12 hours, and drying for 12 hours at 60 ℃ to obtain a corn straw material before carbonization;
(3) carbonizing treatment: putting the corn straw material before carbonization obtained in the step (2) into a tubular heating furnace, and adding N2Roasting under protection, wherein the roasting process is divided into three stages: firstly, setting a heating rate, heating to 350 ℃ and maintaining for 0.5 hour; then raising the temperature to 550 ℃ and maintaining the temperature for 0.5 hour; finally, continuously heating to 700 ℃ and maintaining for 2 hours; naturally cooling to obtainTo corn stalk carbon;
(4) washing the corn stalk carbon obtained in the step (3) with 1mol/L HCl and deionized water respectively, etching and forming holes, and drying to obtain a hollow porous corn stalk carbon skeleton;
(5) activation treatment: weighing 0.54g of urea, an activating agent and 35ml of deionized water, adding the urea, the activating agent and the deionized water into a 40ml hydrothermal reaction kettle, then putting the corn stalk carbon skeleton obtained in the step (4) into the mixed solution for hydrothermal reaction, growing a transition bimetallic oxide on the surface of the corn stalk carbon skeleton in situ, washing the transition bimetallic oxide with the deionized water, drying, and adding the obtained product into an N reactor2And calcining for 2 hours under protection to obtain the carbon-based composite material.
Preferably, the electrolyte in step (2) is KOH, NaOH or Na2SO4(ii) a The concentration of the electrolyte is 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L or 7 mol/L.
Preferably, the temperature rise rate in step (3) is 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min.
Preferably, the temperature of the hydrothermal reaction in step (5) is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or 200 ℃; the hydrothermal reaction time is 12 hours, 16 hours, 24 hours, 36 hours, or 72 hours.
Preferably, the temperature of the calcination in the step (5) is 350 ℃, 400 ℃, 500 ℃ or 600 ℃.
Preferably, the activating agent in the step (5) is a mixture of cobalt chloride and nickel chloride, a mixture of manganese chloride and cobalt chloride or a mixture of manganese chloride and ferric chloride, wherein the molar ratio of cobalt chloride to nickel chloride is 1:2, the molar ratio of manganese chloride to cobalt chloride is 1:2, and the molar ratio of manganese chloride to ferric chloride is 1: 2.
The application of the pseudocapacitance electrode material prepared by the preparation method of the pseudocapacitance electrode material is that the prepared carbon-based composite material is used as an electrode material of a super capacitor or an ion battery to carry out electrochemical performance tests on different electrolytes.
Preferably, the electrochemical performance is testedThe sweep rate of the cyclic voltammetry curve is 3-10 mV.s-1The working window is 0-0.6V.
Preferably, the constant current charge and discharge current density of the electrochemical performance test is 5-20 mA-cm-2The voltage window is 0-0.6V.
Preferably, the impedance of the electrochemical performance test is measured at a frequency of 100kHz to 0.005 Hz.
The invention has the beneficial effects that:
the invention is technically characterized in that: using corn stalk carbon as skeleton, passing through N2The preparation method comprises the steps of carrying out temperature programming carbonization under protection, etching and pore forming to prepare a hollow porous corn straw carbon skeleton, then guiding transition metal ions to grow in situ on the surface of the hollow porous corn straw carbon skeleton by adopting a hydrothermal method, growing transition bimetallic oxide in situ on the surface of the hollow porous corn straw carbon skeleton, realizing the bionic design and preparation of carbon-based transition bimetallic oxide with a controllable structure by controlling various parameters such as temperature, time and additive types in the reaction process, and applying the bionic design and preparation to electrochemical electrode materials. The invention develops a high-performance supercapacitor electrode composite material which is cheap and easy to obtain, and the electrode material has a highly hollow and porous microstructure and morphology of biomass carbon, good conductivity and mechanical ductility and the characteristic of high specific capacity of transition bimetallic oxide through the complementary and synergistic effects of the two materials. The electrochemical performance of the capacitor is improved. Opens up a new direction for the research of preparing novel high-performance electrode materials and also provides a new idea for the design of the corn straw-based composite material.
The carbon-based composite material prepared by the invention has the performances of high conductivity and large energy density, and has become a leading-edge field and a key problem for improving the performance research of Supercapacitors (SCs) as a novel electrode material.
Description of the drawings:
FIG. 1 is an XPS plot of nickel cobaltate.
FIG. 2 is an SEM image, an SEM spectrum and an EDS spectrum of corn stover carbon of example 1, wherein (a) is the SEM spectrum of corn stover carbon; (b) - (d) is the SEM spectrogram of corn stalk based nickel cobaltate; and (e) an EDS spectrogram of the corn straw-based nickel cobaltate.
Fig. 3 is a graph of electrochemical performance of the electrode material of example 1.
The specific implementation mode is as follows:
the technical solution and effects of the present invention will be further described with reference to examples. The particular methods, formulations and descriptions used are not intended to be limiting.
Example 1: see figures 1-3 for the following: a preparation method of a corn straw-based pseudocapacitance electrode material comprises the following steps:
(1) pretreatment: weighing 2g of corn straws, putting the corn straws into a 100ml hydrothermal reaction kettle, adding 0.1mol/L citric acid to completely immerse the corn straws in the citric acid, heating the mixture to react for 6 hours at 200 ℃, then washing the mixture with deionized water and drying the mixture to obtain a corn straw hydrothermal carbon raw material;
(2) adding the corn straw hydrothermal carbon raw material obtained in the step (1) into 4 mol/L40 ml KO H solution, soaking for 12 hours, and drying for 12 hours at 60 ℃ to obtain a corn straw material before carbonization;
(3) carbonizing treatment: putting the corn straw material before carbonization obtained in the step (2) into a tubular heating furnace, and adding N2Roasting under protection, wherein the roasting process is divided into three stages: firstly, setting a heating rate of 5 ℃/min, heating to 350 ℃ and maintaining for 0.5 hour; then raising the temperature to 550 ℃ and maintaining the temperature for 0.5 hour; finally, continuously heating to 700 ℃ and maintaining for 2 hours; naturally cooling to obtain corn stalk carbon;
(4) washing the corn stalk carbon obtained in the step (3) with 1mol/L HCl and deionized water respectively, etching and forming holes, and drying to obtain a hollow porous corn stalk carbon skeleton;
(5) activation treatment: weighing 0.54g of urea, 1.19g of cobalt chloride, 0.59g of nickel chloride and 35ml of deionized water, adding the weighed materials into a 40ml hydrothermal reaction kettle, wherein the molar ratio of the cobalt chloride to the nickel chloride is 1:2, then putting the corn straw carbon skeleton obtained in the step (4) into the mixed solution for hydrothermal reaction, reacting for 6 hours at 120 ℃, growing a transition bimetallic oxide on the surface of the corn straw carbon skeleton in situ, then washing with the deionized water and drying, and placing the obtained product on the surface of the corn straw carbon skeletonN2And calcining the carbon-based composite material for 2 hours at 350 ℃ under the protection of the carbon-based composite material.
Electrochemical performance study of the carbon-based composite material obtained in example 1: the platinum sheet and the saturated calomel electrode are respectively used as a counter electrode and a reference electrode, and the electrode material, the acetylene black and the polytetrafluoroethylene are uniformly coated on a 1cm multiplied by 1cm foamed nickel electrode after being mixed according to the mass ratio of 80:15: 5. And 2mol/L KOH solution is used as electrolyte, and electrochemical performance test is carried out on the electrolyte. The sweep rate of the cyclic voltammetry curve is 3-10mV · s-1, the working window is 0-0.6V, the current density of constant current charging and discharging is 5-20mA · cm-2, the voltage window is 0-0.6V, and the measurement frequency of the impedance is 100kHz-0.005 Hz.
For example 1, the specific capacitance was 3181.82F/g at a current density of 5mA/cm2 according to the CP characteristic curve of fig. 3 and the calculation formula C of specific capacitance ═ I Δ t/m Δ V. The special structure of the corn stalk carbon is shown to enable electrolyte ions in the solution to be rapidly inserted and removed, and the specific capacitance is higher. According to the CEIS characteristic curve of fig. 3, it can be further confirmed that the corn stalk nickel carbonyl cobaltate has smaller internal resistance.
Example 2: other experimental conditions were the same as in example 1, and NaOH or Na was used as the electrolyte in step (2)2SO4Different electrochemical performances can be obtained.
Example 3: the other experimental conditions are the same as those in example 1, and the concentration of the electrolyte in the step (2) is set to be 1mol/L, 2mol/L, 3mol/L, 5mol/L, 6mol/L or 7mol/L, so that the corn straw carbon-based nickel cobaltate material with different structures is prepared.
Example 4: the other experimental conditions are the same as the example 1, and the temperature rise rate in the step (3) is set to be 1 ℃/min, 2 ℃/min, 3 ℃/min and 4 ℃/min, so that different corn straw carbon-based nickel cobaltate materials can be prepared.
Example 5: the other experimental conditions are the same as those of the example 1, the activating agents adopt manganese chloride and cobalt chloride, and the molar ratio of the manganese chloride to the cobalt chloride is 1: 2; or the activating agent adopts manganese chloride and ferric chloride, and the molar ratio of the manganese chloride to the ferric chloride is 1:2, so as to prepare the corn straw carbon-based transition bimetallic oxide material with different structures.
Example 6: the other experimental conditions are the same as the example 1, and the temperature of the hydrothermal reaction in the step (5) is set to be 100 ℃, 110 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or 200 ℃, so that the carbon-based transition bimetallic oxide material of the corn straws with different structures is prepared.
Example 7: in other experimental conditions, the hydrothermal reaction time in the step (5) is set to be 12 hours, 16 hours, 24 hours, 36 hours or 72 hours as in example 1, so as to prepare the carbon-based transition bimetallic oxide material with different structures from the corn stalks.
Example 8: the other experimental conditions are the same as the example 1, and the calcining temperature in the step (5) is set to be 400 ℃, 500 ℃ or 600 ℃, so that the corn straw nickel carbonyl cobaltate material with different structures is prepared.
Claims (10)
1. A preparation method of a corn straw-based pseudocapacitance electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment: weighing 2g of corn straws, putting the corn straws into a 100ml hydrothermal reaction kettle, adding 0.1mol/L citric acid to completely immerse the corn straws in the citric acid, heating the mixture to react for 6 hours at 200 ℃, then washing the mixture with deionized water and drying the mixture to obtain a corn straw hydrothermal carbon raw material;
(2) adding the corn straw hydrothermal carbon raw material obtained in the step (1) into an electrolyte, soaking for 12 hours, and drying for 12 hours at 60 ℃ to obtain a corn straw material before carbonization;
(3) carbonizing treatment: putting the corn straw material before carbonization obtained in the step (2) into a tubular heating furnace, and adding N2Roasting under protection, wherein the roasting process is divided into three stages: firstly, setting a heating rate, heating to 350 ℃ and maintaining for 0.5 hour; then raising the temperature to 550 ℃ and maintaining the temperature for 0.5 hour; finally, continuously heating to 700 ℃ and maintaining for 2 hours; naturally cooling to obtain corn stalk carbon;
(4) washing the corn stalk carbon obtained in the step (3) with 1mol/L HCl and deionized water respectively, etching and forming holes, and drying to obtain a hollow porous corn stalk carbon skeleton;
(5) activation treatment: 0.54g of urea, activator and 35ml of deionized water were weighed inPutting the corn stalk carbon skeleton obtained in the step (4) into a 40ml hydrothermal reaction kettle, then putting the corn stalk carbon skeleton into the mixed solution for hydrothermal reaction, growing transition bimetallic oxide on the surface of the corn stalk carbon skeleton in situ, then washing with deionized water and drying, and putting the obtained product in N2And calcining for 2 hours under protection to obtain the carbon-based composite material.
2. The preparation method of the pseudocapacitance electrode material according to claim 1, characterized by comprising the following steps: the electrolyte in the step (2) is KOH, NaOH or Na2SO4(ii) a The concentration of the electrolyte is 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L or 7 mol/L.
3. The preparation method of the pseudocapacitance electrode material according to claim 1, characterized by comprising the following steps: the heating rate in the step (3) is 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min.
4. The preparation method of the pseudocapacitance electrode material according to claim 1, characterized by comprising the following steps: the temperature of the hydrothermal reaction in the step (5) is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or 200 ℃; the hydrothermal reaction time is 12 hours, 16 hours, 24 hours, 36 hours, or 72 hours.
5. The preparation method of the pseudocapacitance electrode material according to claim 1, characterized by comprising the following steps: the calcination temperature in the step (5) is 350 ℃, 400 ℃, 500 ℃ or 600 ℃.
6. The preparation method of the pseudocapacitance electrode material according to claim 1, characterized by comprising the following steps: the activating agent in the step (5) is a mixture of cobalt chloride and nickel chloride, a mixture of manganese chloride and cobalt chloride or a mixture of manganese chloride and ferric chloride, wherein the molar ratio of cobalt chloride to nickel chloride is 1:2, the molar ratio of manganese chloride to cobalt chloride is 1:2, and the molar ratio of manganese chloride to ferric chloride is 1: 2.
7. The application of the pseudocapacitance electrode material prepared by the preparation method of the pseudocapacitance electrode material as claimed in any one of claims 1 to 6 is characterized in that: the prepared carbon-based composite material is used as an electrode material of a super capacitor or an ion battery to carry out electrochemical performance tests on different electrolytes.
8. The use of a pseudocapacitive electrode material according to claim 7, wherein: the sweep rate of the cyclic voltammetry curve of the electrochemical performance test is 3-10 mV.s-1The working window is 0-0.6V.
9. The use of a pseudocapacitive electrode material according to claim 7, wherein: the current density of constant current charge and discharge in the electrochemical performance test is 5-20 mA-cm-2The voltage window is 0-0.6V.
10. The use of a pseudocapacitive electrode material according to claim 7, wherein: the impedance measurement frequency of the electrochemical performance test is 100kHz-0.005 Hz.
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