CN111584245B - Three-dimensional network structure composite material and preparation method and application thereof - Google Patents
Three-dimensional network structure composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 74
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002077 nanosphere Substances 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 5
- 238000010899 nucleation Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 31
- 229910021389 graphene Inorganic materials 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910021382 natural graphite Inorganic materials 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910019131 CoBr2 Inorganic materials 0.000 claims description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 claims description 2
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000002070 nanowire Substances 0.000 abstract description 9
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 239000002060 nanoflake Substances 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 229910021281 Co3O4In Inorganic materials 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000008240 homogeneous mixture Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000004729 solvothermal method Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910000943 NiAl Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 sulfonic Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- H01G11/24—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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- 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
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- 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 discloses a three-dimensional network structure composite material, a preparation method and application thereof, belonging to the field of nano composite material preparation3O4@Fe2O3The composite material is prepared by Co3O4Nanowire-interconnected rGO thin plate connection to form network-shaped rGO/Co3O4Post-embedded Fe2O3Nanosphere pair rGO/Co3O4Modification to produce rGO/Co3O4@Fe2O3Composite material of said rGO/Co3O4In situ synthesis of Fe at the network2O3Nucleation sites for nanospheres. Conductive one-dimensional Co of the invention3O4The nanowires provide high-speed channels for electron transport between two separate rGO nanoflakes, connect the entire network, enhance the conductivity of the material, rGO/Co3O4As Fe2O3Support material for nucleation and growth of nanospheres and promoting Fe2O3The electric conductivity of the nanospheres improves the electrochemical performance of the composite material.
Description
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to a three-dimensional network structure rGO/Co3O4@Fe2O3Composite materialA material and a preparation method and application thereof.
Background
Environmental and resource issues have been a focus of worldwide concern for the twenty-first century. Because of the gradual shortage of petroleum resources, a new generation energy storage device with no pollution, high safety performance, low production cost, high energy density and high power is urgently needed to replace a power battery used by a traditional energy automobile.
Among various intelligent devices, supercapacitors are widely regarded as an important class of energy storage devices, with their unique advantages of high power density, fast charging capability, good rate retention capability, and long cycle life. Supercapacitors can be divided into Electric Double Layer Supercapacitors (EDLCs) and pseudo-capacitive supercapacitors by charge storage mechanisms, which have been combined later to form hybrid supercapacitors. For electric double layer supercapacitors, the adsorption/desorption of ions by the interface between the electrode and the electrolyte contributes to the formation of capacitance (non-faradaic effect). High surface area carbon materials are often used as electrode materials for electric double layer supercapacitors. For a pseudocapacitive supercapacitor, the capacitance (faraday capacitance) is due to a redox reaction at or near the active material interface. Compared with EDLCs, the pseudocapacitive super capacitor has higher energy density due to the highly reversible redox reaction. Transition metal oxides, particularly oxides having a particular morphology or nanostructure, are attractive pseudocapacitive electrode materials. Among these metal oxides, Fe2O3、Co3O4The transition metal oxide compound is researched as a candidate material of a pseudo-capacitance electrode due to excellent physical and electrochemical properties, such as higher theoretical specific capacitance and good electrochemical properties.
Recently, researchers at home and abroad optimize the electrochemical performance from the aspects of comprehensive strategies, structural diversity, material compositions and the like. For example Qu et al [ Commun.2018,54,10355]A bubble-like auxiliary structure (CoMoO) of a hollow cobalt-based sphere was reported4). The obtained hollow ball is favorable for the diffusion of electrolyte, and greatly reduces the expansionThe specific capacitance of the dispersion path at 1A/g was 1381F/g, and the specific capacitance at 10A/g was 742F/g, and the dispersion path was excellent in cycle stability in a supercapacitor. Zheng et al [ Chemical Engineering Journal 240(2014) 264-]Adopts a simple hydrothermal method to prepare needle-shaped Co anchored on Graphene Oxide (GO) with different mass ratios3O4A composite material. Co3O4GO nanocomposite material due to Co3O4And GO has strong synergistic effect, so that the specific capacitance of 157.7F/g is obtained when the current density is 1A/g, and the capacity retention rate reaches 70% after 4000 cycles under the current density of 0.2A/g. A morphology modification process can be used to obtain three-dimensional interconnected Fe with an average diameter of 10-20nm2O3Nanospheres. As an electrode, this iron oxide structure has good cycling performance and high rate capability, which can be attributed to the facile transport of ions and electrons and the abundance of active sites. However, since the volume change is large during the charge and discharge processes, the conductivity is poor, and the observed specific capacitance value is often lower than the theoretical value. Fe2O3、Co3O4Or other transition metal oxide-based compounds, have limited practical applications in energy storage devices, despite their easily controllable morphology. A stable conductive scaffold is needed to make up for the disadvantages of poor conductivity, small surface area, and poor mechanical stability.
Graphene is a compound represented by sp2The two-dimensional carbon allotrope composed of hybridized carbon atoms can be used as a proper supporting material due to the excellent electrochemical performance and larger surface area. With the incentive of graphene discovery, scientists invest in a great deal of effort to combine nanomaterials with graphene to obtain graphene-supported composites. Strategies have been developed to synthesize graphene structures from low-dimensional transition metal active components. Pseudo-capacitive transition metal active elements integrated with graphene are referred to as hybrid capacitors. To our knowledge, the integration of nanowires and nanospheres with graphene layers as mixed networks is a new graphene-based mixed structure strategy, but there are few reports.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a three-dimensional network structure rGO/Co3O4@Fe2O3The composite material and the preparation method thereof are used for preparing the super capacitor with good electrochemical performance by taking the composite material as the cathode of the super capacitor.
The technical scheme adopted by the invention is as follows:
three-dimensional network structure rGO/Co3O4@Fe2O3Composite material, said three-dimensional network structure rGO/Co3O4@Fe2O3The composite material is prepared by Co3O4The nanowires are connected with the interconnected rGO thin plate to form a network-shaped rGO/Co3O4Post-embedded Fe2O3Nanosphere pair rGO/Co3O4Modification to produce rGO/Co3O4@Fe2O3A composite material.
The invention takes rGO thin slice as a support and then passes through one-dimensional Co3O4Nanowire (Co)3O4NWs) interconnected, finally embedded with Fe2O3Nanosphere (Fe)2O3NSs), conductive one-dimensional Co3O4The nanowires provide high-speed channels for electron transport between two separate rGO nanoflakes, the connections form an overall network, enhancing the conductivity of the material, rGO/Co3O4As Fe2O3Support material for nucleation and growth of nanospheres and promoting Fe2O3The electric conductivity of the nanospheres improves the electrochemical performance of the composite material.
Preferably, said rGO/Co3O4At the network of (A) is Fe2O3Nucleation sites of nanospheres, the Fe2O3Nanospheres are synthesized in situ.
Three-dimensional network structure rGO/Co3O4@Fe2O3The preparation method of the composite material comprises the following steps:
s1, modifying graphene oxide GO: pouring the stripped graphene oxide GO into a reaction kettle, and reacting for 8-48h at the temperature of 100-400 ℃ by using a thermal reduction method to obtainThe concentration of the rGO is 0.5-3 mg/mL/H2O solution; the objective is and incorporates surfactants (e.g. PSS) including hydroxyl, sulfonic, carbonyl and carboxyl functional groups into the surface of rGO layers;
s2 preparation of rGO/Co by hydrothermal method3O4: dispersing a cobalt salt aqueous solution and a mixed solution of urea and ammonium fluoride dissolved in ethanol in rGO/H2In O solution, the mixed solution of cobalt salt, urea dissolved in ethanol and ammonium fluoride and rGO/H2The ratio of the amounts of O substances is (0.5-2): 180: (40-800), uniformly mixing, transferring the mixture into an autoclave for reaction at the temperature of 180 ℃ and 220 ℃ for 10-14h, and then centrifugally separating out rGO/Co3O4Precipitating and washing the precursor to prepare rGO/Co3O4A suspension; wherein urea is used as a precipitator, and precipitates are formed by uniform reaction of hydrolysis in a cobalt salt solution, ammonium fluoride can improve the reaction rate on one hand and adjust the stability of the reaction on the other hand, thereby being beneficial to forming the Co with a needle-like structure3O4A nanowire;
S3:rGO/Co3O4@Fe2O3preparing a composite material: mixing iron or ferrous salt, urea and NH4F addition of rGO/Co3O4Stirring and dissolving the suspension vigorously, and then dripping ethanol, wherein the adding amount of the ferric salt or ferrous salt is equivalent to that of rGO/Co3O41-4 times of the total amount of the components, transferring the mixture into an autoclave for reaction at the temperature of 180-220 ℃ for 22-26h, performing precipitation centrifugal separation, washing for a plurality of times, and drying to obtain the rGO/Co3O4@Fe2O3A composite material.
Preferably, the graphene oxide GO prepared in step S1 includes the specific steps of:
s1-1, adding 60-98% concentrated H in 15-90ml at the temperature below 5 DEG C2SO4Adding 1-5g of natural graphite powder, stirring vigorously to obtain KMnO powder 0.5-15 times of natural graphite powder4Slowly adding the mixture into a water bath at the temperature of between 10 and 80 ℃, dropwise adding deionized water which is 10 to 300 times of the natural graphite powder, violently stirring the mixture, and continuously adding H2O2To obtain a yellow colorRepeatedly washing the color dispersion liquid with water and dilute hydrochloric acid solution; the acid solution can be a dilute hydrochloric acid solution with the mass fraction of 1-5%.
S1-2, repeatedly washing and dispersing the graphene oxide GO in deionized water to obtain a graphene oxide suspension liquid with the concentration of 0.5-2.0mg/ml, and ultrasonically stripping for 0.5-3h to obtain stripped graphene oxide GO.
Preferably, said H2O2The mass fraction is 20-30%.
Preferably, the cobalt salt aqueous solution in step S2 is CoF2，CoCl2，CoBr2，CoI2，CoOCo(OH)2Or Co (NO)3)2The concentration of the formed solution is 0.1-4 mol/L.
Preferably, the mass ratio of the ethanol, the urea and the ammonium fluoride added in the steps S2 and S2 is (10-328): 1: (0.5-17).
Preferably, rGO/Co in step S23O4The suspension is rGO/Co3O4The suspension formed in the PSS solution has a concentration of 0.5-2.0 g/L.
Preferably, the ferric salt or ferrous salt is FeCl3·6H2O、Fe2(SO4)3、FeCl2Or FeSO4。
The three-dimensional network structure rGO/Co3O4@Fe2O3The composite material is applied to the cathode material of the super capacitor.
Compared with the prior art, the invention has the beneficial effects that:
(1) rGO/Co prepared by the invention3O4@Fe2O3Three-dimensional networks integrate three important characteristics as negative electrodes: 1) co3O4The nanowires provide an interconnected bridge to allow the electrolyte to penetrate into the entire electrode, facilitating rapid transfer and diffusion of the electrolyte; 2) co on rGO nanosheets3O4The nanowires serve as a high conductive path for charge transport, and can connect two rGO nanosheets to establish an electron transport bridge, so that the interconnected hybrid network has high conductivity; 3) with other hybridizations obtained by mechanical mixing methodsCompared with rGO/Co3O4In-situ hydrothermal process of hybrid network close contact to make Fe2O3Highly dispersed, uniformly distributed Fe nanospheres2O3The nanosphere not only has higher capacitance, but also has higher conductivity, and is beneficial to the mass transfer process in electrochemical reaction; thus the rGO/Co of the invention3O4@Fe2O3The three-dimensional network integrates the mechanical stability, the conductivity and the particle dispersibility as a negative electrode, so that the electrochemical performance is obviously improved;
(2) with pure 1D Co3O4Compared with nano-wires, the rGO/Co prepared by the invention3O4@Fe2O3The specific capacitance of the hybrid network used as a pseudocapacitance material is 784F/g under the condition that the current density is 1A/g, and the hybrid network has good circulation stability;
(3) rGO/Co prepared by the invention3O4@Fe2O3The mixed network is taken as a negative electrode, the NiAl LDH is taken as a positive electrode, and the asymmetric super capacitor NiAl LDH// rGO/Co is assembled3O4@Fe2O3The excellent energy density of 70.78Wh/kg was achieved at a power density of 0.29kW/kg, and the excellent performance at an energy density of 24.24Wh/kg was maintained at a high power density of 9.94kW/kg, so the rGO/Co of the present invention3O4@Fe2O3The hybrid network is a promising cathode material with a three-dimensional electrode structure in a high-performance energy storage device.
Drawings
FIG. 1 is rGO/Co3O4@Fe2O3A schematic diagram of a forming process of the hybrid network structure;
FIG. 2 shows rGO/Co obtained in example 13O4@Fe2O3High magnification scanning electron microscope photographs;
FIG. 3 is the rGO/Co prepared in example 13O4@Fe2O3Discharge curves of the electrode material at different current densities.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Three-dimensional network structure rGO/Co3O4@Fe2O3The preparation method of the composite material specifically comprises the following steps:
1) 30ml of concentrated H are measured2SO4Placing in a beaker and in an ice-water bath until the temperature is reduced to 0 ℃;
2) 2g of natural graphite powder is added into concentrated H2SO4In the middle, stirring vigorously;
3) 5g of KMnO4Slowly adding the mixture into a reaction beaker, and placing the mixed solution containing the reaction mixture into a water bath at 40 ℃;
4) dropwise adding 100ml of deionized water, and violently stirring;
5) 10ml of 30% H was added2O2Finally obtaining a yellow dispersion liquid;
6) repeatedly washing with water and 5% dilute hydrochloric acid solution to completely remove residual salts and acids;
7) graphene oxide was dispersed in deionized water to prepare a suspension at a concentration of 1 mg/mL. Ultrasonically stripping graphene oxide for 1 h;
8) pouring the solution into a reaction kettle, and reacting for 12H at 200 ℃ by using a solvothermal method to obtain the final product of rGO/H2O solution;
9) 2mL of CoCl at a concentration of 0.5mol/L2·6H2O aqueous solution is dispersed in rGO/H under ultrasonic treatment2O solution (2mg/mL) to form a homogeneous mixture;
10) mixing 95mg of urea and 350mg of NH4The mixed solution of F was dissolved in 10ml of ethanol. Magnetically stirring for 10min, dispersing the mixed solution in the solution obtained in the step (8), and stirring for 15min at room temperature;
11) transferring the solution into a Teflon lining autoclave, and reacting for 12 hours at the temperature of 200 ℃;
12) centrifugal separation of rGO/Co3O4Precipitating the precursor, washing with deionized water for several times, and then carrying out rGO/Co3O4The precursor is stored in a PSS solution (1g/L) to prepare a suspension;
13) 540.6mgFeCl3·6H2O, 95mg Urea and 350mg NH4F in rGO/Co3O4Stirring and dissolving the precursor suspension vigorously;
14) dripping 10ml ethanol into the solution, and stirring vigorously for 15 min;
15) the resulting solution was transferred to a 50ml autoclave and maintained at 200 ℃ for 24 h;
16) naturally cooling the high-pressure kettle to room temperature, centrifugally separating the precipitate, washing with deionized water and ethanol for several times, and drying at 60 ℃ overnight in vacuum to obtain rGO/Co3O4@Fe2O3A composite material.
Example 2
Three-dimensional network structure rGO/Co3O4@Fe2O3The preparation method of the composite material specifically comprises the following steps:
1) 30ml of concentrated H are measured2SO4Placing in a beaker and in an ice-water bath until the temperature is reduced to 0 ℃;
2) 2g of natural graphite powder is added into concentrated H2SO4In the middle, stirring vigorously;
3) 5g of KMnO4Slowly adding the mixture into a reaction beaker, and placing the mixed solution containing the reaction mixture into a water bath at 40 ℃;
4) dropwise adding 100ml of deionized water, and violently stirring;
5) 10ml of 30% H was added2O2Finally obtaining a yellow dispersion liquid;
6) repeatedly washing with water and 5% dilute hydrochloric acid solution to completely remove residual salts and acids;
7) graphene oxide was dispersed in deionized water to prepare a suspension at a concentration of 1 mg/mL. Ultrasonically stripping graphene oxide for 1 h;
8) pouring the solution into a reaction kettle, and reacting for 12H at 200 ℃ by using a solvothermal method to obtain the final product of rGO/H2O solution;
9) 4mL of CoCl at a concentration of 0.5mol/L2·6H2O aqueous solution is dispersed in rGO/H under ultrasonic treatment2O solution (2mg/mL) to form a homogeneous mixture;
10) 190mg of urea and 700mg of NH were added4The mixed solution of F was dissolved in 20ml of ethanol. Magnetically stirring for 10min, dispersing the mixed solution in the solution obtained in the step (8), and stirring for 15min at room temperature;
11) transferring the solution into a Teflon lining autoclave, and reacting for 18h at 100 ℃;
12) centrifugal separation of rGO/Co3O4The precursor is precipitated and washed several times with deionized water. Then rGO/Co3O4The precursor is stored in a PSS solution (1g/L) to prepare a suspension;
13) 1081.2mgFeCl3·6H2O, 190mg Urea and 700mg NH4F in rGO/Co3O4Stirring and dissolving the precursor suspension vigorously;
14) dropwise adding 20ml of ethanol into the solution, and stirring vigorously for 15 min;
15) the resulting solution was transferred to a 100ml autoclave and maintained at 200 ℃ for 24 h;
16) naturally cooling the high-pressure kettle to room temperature, centrifugally separating the precipitate, washing with deionized water and ethanol for several times, and drying at 60 ℃ overnight in vacuum to obtain rGO/Co3O4@Fe2O3A composite material.
Example 3
Three-dimensional network structure rGO/Co3O4@Fe2O3The preparation method of the composite material specifically comprises the following steps:
1) 60ml of concentrated H are measured2SO4Placing in a beaker and in an ice-water bath until the temperature is reduced to 0 ℃;
2) will be provided with4g of natural graphite powder is added into concentrated H2SO4In the middle, stirring vigorously;
3) mixing 10g KMnO4Slowly adding the mixture into a reaction beaker, and placing the mixed solution containing the reaction mixture into a water bath at 40 ℃;
4) dropwise adding 200ml of deionized water, and violently stirring;
5) 20ml of 30% H was added2O2Finally obtaining a yellow dispersion liquid;
6) repeatedly washing with water and 5% dilute hydrochloric acid solution to completely remove residual salts and acids;
7) dispersing graphene oxide in deionized water, preparing a suspension with the concentration of 1mg/mL, and ultrasonically stripping the graphene oxide for 2 hours;
8) pouring the solution into a reaction kettle, and reacting for 12H at 200 ℃ by using a solvothermal method to obtain the final product of rGO/H2O solution;
9) 4mL of CoCl at a concentration of 0.5mol/L2·6H2O aqueous solution is dispersed in rGO/H under ultrasonic treatment2O solution (2mg/mL) to form a homogeneous mixture;
10) 190mg of urea and 700mg of NH were added4Dissolving the mixed solution of F in 20ml of ethanol, magnetically stirring for 10min, dispersing the mixed solution in the solution obtained in the step (8), and stirring for 15min at room temperature;
11) transferring the solution into a Teflon lining autoclave, and reacting for 12 hours at 300 ℃;
12) centrifugal separation of rGO/Co3O4Precipitating the precursor, washing with deionized water for several times, and then carrying out rGO/Co3O4The precursor is stored in a PSS solution (1g/L) to prepare a suspension;
13) 1081.2mgFeCl3·6H2O, 190mg Urea and 700mg NH4F in rGO/Co3O4Stirring and dissolving the precursor suspension vigorously;
14) dropwise adding 20ml of ethanol into the solution, and stirring vigorously for 15 min;
15) the resulting solution was transferred to a 100ml autoclave and maintained at 300 ℃ for 24 h;
16) naturally cooling the high-pressure kettle to room temperature, centrifugally separating the precipitate, washing with deionized water and ethanol for several times, and drying at 60 ℃ overnight in vacuum to obtain rGO/Co3O4@Fe2O3A composite material.
Example 4
Three-dimensional network structure rGO/Co3O4@Fe2O3The preparation method of the composite material specifically comprises the following steps:
1) 30ml of concentrated H are measured2SO4Placing in a beaker and in an ice-water bath until the temperature is reduced to 0 ℃;
2) 2g of natural graphite powder is added into concentrated H2SO4In the middle, stirring vigorously;
3) 5g of KMnO4Slowly adding the mixture into a reaction beaker, and placing the mixed solution containing the reaction mixture into a water bath at 40 ℃;
4) dropwise adding 100ml of deionized water, and violently stirring;
5) 10ml of 30% H was added2O2Finally obtaining a yellow dispersion liquid;
6) repeatedly washing with water and 5% dilute hydrochloric acid solution to completely remove residual salts and acids;
7) dispersing graphene oxide in deionized water, preparing a suspension with the concentration of 1mg/mL, and ultrasonically stripping the graphene oxide for 1 h;
8) pouring the solution into a reaction kettle, and reacting for 12H at 200 ℃ by using a solvothermal method to obtain the final product of rGO/H2O solution;
9) 2mL of CoCl at a concentration of 0.5mol/L2·6H2O aqueous solution is dispersed in rGO/H under ultrasonic treatment2O solution (1mg/mL) to form a homogeneous mixture;
10) mixing 95mg of urea and 350mg of NH4The mixed solution of F was dissolved in 10ml of ethanol. Magnetically stirring for 10min, dispersing the mixed solution in the solution obtained in the step (8), and stirring for 15min at room temperature;
11) transferring the solution into a Teflon lining autoclave, and reacting for 12 hours at 400 ℃;
12) centrifugal separation of rGO/Co3O4Precipitating the precursor, washing with deionized water for several times, and then carrying out rGO/Co3O4The precursor is stored in a PSS solution (1g/L) to prepare a suspension;
13) 540.6mgFeCl3·6H2O, 95mg Urea and 350mg NH4F in rGO/Co3O4Stirring and dissolving the precursor suspension vigorously;
14) dripping 10ml ethanol into the solution, and stirring vigorously for 15 min;
15) the resulting solution was transferred to a 50ml autoclave and maintained at 400 ℃ for 24 h;
16) naturally cooling the high-pressure kettle to room temperature, centrifugally separating the precipitate, washing with deionized water and ethanol for several times, and drying at 60 ℃ overnight in vacuum to obtain rGO/Co3O4@Fe2O3A composite material.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (10)
1. Three-dimensional network structure rGO/Co3O4@Fe2O3The composite material is characterized in that the three-dimensional network structure rGO/Co3O4@Fe2O3The composite material is prepared by Co3O4Nanowire-interconnected rGO thin plate connection to form network-shaped rGO/Co3O4Post-embedded Fe2O3Nanosphere pair rGO/Co3O4Modification to produce rGO/Co3O4@Fe2O3A composite material;
the three-dimensional network structure rGO/Co3O4@Fe2O3A method for preparing a composite material, comprising the followingThe method comprises the following steps:
s1, modifying graphene oxide GO: pouring the stripped graphene oxide GO into a reaction kettle, and reacting for 8-48H at the temperature of 100 ℃ and 400 ℃ by using a thermal reduction method to obtain rGO/H with the concentration of 0.5-3mg/mL2O solution;
s2 preparation of rGO/Co by hydrothermal method3O4: dispersing a cobalt salt aqueous solution and a mixed solution of urea and ammonium fluoride dissolved in ethanol in rGO/H2In O solution, the mixed solution of cobalt salt, urea dissolved in ethanol and ammonium fluoride and rGO/H2The ratio of the amounts of O substances is (0.5-2): 180: (40-800), uniformly mixing, transferring the mixture into an autoclave for reaction at the temperature of 180 ℃ and 220 ℃ for 10-14h, and then centrifugally separating out rGO/Co3O4Precipitating and washing the precursor to prepare rGO/Co3O4A suspension;
S3:rGO/Co3O4@Fe2O3preparing a composite material: mixing iron or ferrous salt, urea and NH4F addition of rGO/Co3O4Stirring and dissolving the suspension vigorously, and then dripping ethanol, wherein the adding amount of the ferric salt or ferrous salt is equivalent to that of rGO/Co3O41-4 times of the total amount of the components, transferring the mixture into an autoclave for reaction at the temperature of 180-220 ℃ for 22-26h, performing precipitation centrifugal separation, washing for a plurality of times, and drying to obtain the rGO/Co3O4@Fe2O3A composite material.
2. The three-dimensional network structure rGO/Co of claim 13O4@Fe2O3Composite material, characterized in that said rGO/Co3O4At the network of (A) is Fe2O3Nucleation sites of nanospheres, the Fe2O3The nanospheres are prepared by in situ synthesis.
3. rGO/Co based on three-dimensional network structure3O4@Fe2O3The preparation method of the composite material is characterized by comprising the following steps:
s1, modifying graphene oxide GO: stripping the graphite oxidePouring the alkene GO into a reaction kettle, and reacting for 8-48H at the temperature of 100 ℃ and 400 ℃ by using a thermal reduction method to obtain the rGO/H with the concentration of 0.5-3mg/mL2O solution;
s2 preparation of rGO/Co by hydrothermal method3O4: dispersing a cobalt salt aqueous solution and a mixed solution of urea and ammonium fluoride dissolved in ethanol in rGO/H2In O solution, the mixed solution of cobalt salt, urea dissolved in ethanol and ammonium fluoride and rGO/H2The ratio of the amounts of O substances is (0.5-2): 180: (40-800), uniformly mixing, transferring the mixture into an autoclave for reaction at the temperature of 180 ℃ and 220 ℃ for 10-14h, and then centrifugally separating out rGO/Co3O4Precipitating and washing the precursor to prepare rGO/Co3O4A suspension;
S3:rGO/Co3O4@Fe2O3preparing a composite material: mixing iron or ferrous salt, urea and NH4F addition of rGO/Co3O4Stirring and dissolving the suspension vigorously, and then dripping ethanol, wherein the adding amount of the ferric salt or ferrous salt is equivalent to that of rGO/Co3O41-4 times of the total amount of the components, transferring the mixture into an autoclave for reaction at the temperature of 180-220 ℃ for 22-26h, performing precipitation centrifugal separation, washing for a plurality of times, and drying to obtain the rGO/Co3O4@Fe2O3A composite material.
4. The three-dimensional network structure rGO/Co of claim 33O4@Fe2O3The preparation method of the composite material is characterized in that the graphene oxide GO prepared in the step S1 comprises the following specific steps:
s1-1, adding concentrated H of 15-90ml at the temperature below 5 DEG C2SO4Adding 1-5g of natural graphite powder, stirring vigorously to obtain KMnO powder 0.5-15 times of natural graphite powder4Slowly adding the mixture into a water bath at the temperature of between 10 and 80 ℃, dropwise adding deionized water which is 10 to 300 times of the natural graphite powder, violently stirring the mixture, and continuously adding H2O2To obtain a yellow dispersion, repeatedly washing with water and an acid solution;
s1-2, repeatedly washing and dispersing the graphene oxide GO in deionized water to obtain a graphene oxide suspension liquid with the concentration of 0.5-2.0mg/ml, and ultrasonically stripping for 0.5-3h to obtain stripped graphene oxide GO.
5. The three-dimensional network structure rGO/Co of claim 43O4@Fe2O3The preparation method of the composite material is characterized in that the H is2O2The mass fraction is 20-30%.
6. The three-dimensional network structure rGO/Co of claim 33O4@Fe2O3The preparation method of the composite material is characterized in that the cobalt salt aqueous solution in the step S2 is CoF2，CoCl2，CoBr2，CoI2，CoOCo(OH)2Or Co (NO)3)2The concentration of the formed solution is 0.1-4 mol/L.
7. The three-dimensional network structure rGO/Co of claim 33O4@Fe2O3The preparation method of the composite material is characterized in that the mass ratio of the ethanol, the urea and the ammonium fluoride added in the steps S2 and S3 is (10-328): 1: (0.5-17).
8. The three-dimensional network structure rGO/Co of claim 33O4@Fe2O3The preparation method of the composite material is characterized in that the rGO/Co in the step S23O4The suspension is rGO/Co3O4The suspension formed in the PSS solution has a concentration of 0.5-2.0 g/L.
9. The three-dimensional network structure rGO/Co of claim 33O4@Fe2O3The preparation method of the composite material is characterized in that the ferric salt or ferrous salt is FeCl3·6H2O、Fe2(SO4)3、FeCl2Or FeSO4。
10. The three-dimensional network structure rGO/Co of any of claims 1-93O4@Fe2O3The composite material is applied to the cathode material of the super capacitor.
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