CN113470981B - Preparation method of porous carbon fiber/metal oxide composite material and graphene-based conductive ink and application of porous carbon fiber/metal oxide composite material and graphene-based conductive ink in supercapacitor - Google Patents
Preparation method of porous carbon fiber/metal oxide composite material and graphene-based conductive ink and application of porous carbon fiber/metal oxide composite material and graphene-based conductive ink in supercapacitor Download PDFInfo
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- CN113470981B CN113470981B CN202110590195.XA CN202110590195A CN113470981B CN 113470981 B CN113470981 B CN 113470981B CN 202110590195 A CN202110590195 A CN 202110590195A CN 113470981 B CN113470981 B CN 113470981B
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 121
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 121
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 239000003990 capacitor Substances 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 239000002184 metal Substances 0.000 claims abstract description 15
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
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- 238000002156 mixing Methods 0.000 claims description 10
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- 239000011230 binding agent Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011245 gel electrolyte Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
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- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
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- 238000002484 cyclic voltammetry Methods 0.000 description 6
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000000840 electrochemical analysis Methods 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Images
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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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- 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
-
- 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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
- H01G11/40—Fibres
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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
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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
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Abstract
The invention provides a preparation method of a porous carbon fiber/metal oxide composite material and graphene-based conductive ink and application of the composite material in a super capacitor, wherein the preparation method of the composite material comprises the following steps: (1) carrying out high-temperature carbonization treatment on the absorbent cotton at 900-1200 ℃, and grinding the absorbent cotton into porous carbon fibers after cooling; (2) placing the porous carbon fiber in a metal salt aqueous solution, stirring at constant temperature, centrifuging, and drying to obtain a porous carbon fiber/metal salt composite material; (3) and (3) roasting the composite material under a protective atmosphere, and then cooling and grinding the composite material. The invention can prepare the porous carbon fiber/metal oxide composite material with uniform composition, large metal oxide loading capacity, strong binding force and excellent electrochemical energy storage performance; in order to realize the ink printing of the composite electrode material, a small amount of graphene is added to serve as a conductive channel between carbon fibers, and a screen printing method is utilized to prepare the water system flexible supercapacitor based on the graphene-coated three-dimensional porous carbon fiber/metal oxide composite material.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a preparation method of a porous carbon fiber/metal oxide composite material and graphene-based conductive ink and application of the porous carbon fiber/metal oxide composite material and the graphene-based conductive ink in a super capacitor.
Background
With the rapid development of the field of intelligent wearable electronics, the demand for light, thin, flexible and intelligent energy storage devices has increased. The flexible super capacitor has the advantages of rapid charge and discharge, large capacity, long service life, flexibility, safety and the like, and has wide development prospect in the field of portable wearable electronics. The novel electronic printing preparation technology (such as ink-jet printing, silk screen printing, 3D printing and the like) developed in recent years has the advantages of simplicity in operation, capability of patterning, strong adaptability to flexible substrates and the like. The flexible super capacitor can be prepared rapidly in large scale and at low cost particularly by a screen printing technology, and is suitable for large-scale production.
The electrode material is used as a core component of the flexible super capacitor, and directly determines the energy storage performance of the device. The commonly used active electrode materials mainly include carbon materials, metal oxides, and conductive polymers. Carbon materials have excellent conductivity and stable electric double layer capacitance, but their limited specific surface area results in low charge storage capacity; the metal oxide has high theoretical specific capacitance, is an important pseudocapacitance electrode material, and faces the problem of poor intrinsic conductivity of the material.
In recent years, a large number of researchers compound the graphene with high conductivity and the nano-scale metal oxide, and improve the mass specific capacitance, the cycling stability and the power multiplying power of the composite material by utilizing the advantages of the graphene and the nano-scale metal oxide, so that the prepared flexible super capacitor shows good mechanical flexibility. However, graphene-based composite materials also suffer from a series of problems such as easy agglomeration and difficult dispersion of graphene, limited availability of sites for compounding with metal oxides, and high cost. The three-dimensional biomass porous carbon structure not only has high specific surface area and excellent conductivity, but also can provide more abundant and diversified composite sites (surface and bulk phase) and relatively low preparation cost, thereby effectively making up the defects of graphene. Therefore, the development of the three-dimensional biomass porous carbon/metal oxide composite material with uniform metal oxide composite, high loading capacity and strong binding force has important significance for preparing the flexible supercapacitor in a large scale by screen printing.
Disclosure of Invention
The invention aims to solve the technical problems, overcome the defects and defects in the background technology and provide a preparation method of a porous carbon fiber/metal oxide composite material and graphene-based conductive ink and application of the porous carbon fiber/metal oxide composite material in a super capacitor. Meanwhile, in order to realize the ink printing of the composite electrode material, a small amount of graphene is added to be used as a conductive channel between carbon fibers, and the asymmetric water system flexible supercapacitor based on the graphene-coated three-dimensional porous carbon fiber/metal oxide composite material is prepared by a screen printing method.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a porous carbon fiber/metal oxide composite material for a super capacitor comprises the following steps:
(1) heating the absorbent cotton to 900-1200 ℃ under a protective atmosphere, carrying out high-temperature carbonization treatment, cooling, and grinding to obtain porous carbon fibers;
(2) placing the porous carbon fiber in a metal salt aqueous solution, stirring at a constant temperature, centrifuging, and drying to obtain a porous carbon fiber/metal salt composite material;
(3) and roasting the porous carbon fiber/metal salt composite material in a protective atmosphere, and cooling and grinding the roasted porous carbon fiber/metal salt composite material to obtain the porous carbon fiber/metal oxide composite material.
In the preparation method, the high-temperature carbonization treatment temperature is limited to 900-1200 ℃, and at the temperature, the formed carbon fiber has a large number of pore structures, so that the subsequent metal oxide loading capacity is conveniently increased, and the ion transport capacity can be improved. According to the invention, the porous carbon fiber/metal salt composite material is roasted in a protective atmosphere (argon or nitrogen), so that the structural integrity of the porous carbon fiber during roasting can be ensured, the loss of the carbon material in an aerobic environment is avoided, and the internal structure of the porous carbon fiber is easy to collapse in the aerobic environment, so that the performance of the product is influenced.
According to the invention, cheap biomass carbon source absorbent cotton is adopted, a porous hollow fiber structure is obtained after high-temperature carbonization, and then a plurality of porous carbon fiber/metal oxide composite materials with uniform composition, large metal oxide loading capacity, strong binding force and excellent electrochemical energy storage performance are prepared by simple adsorption of metal salt solution and subsequent heat treatment.
The porous carbon fiber/metal oxide composite material makes up the defect of the conductivity of the metal oxide by utilizing the excellent ion and electron transport capacity of the porous carbon fiber; meanwhile, the large specific surface area and the pore channel structure of the porous carbon can increase the loading capacity of metal oxides and bring more reactive active sites. The porous carbon fiber/metal oxide has both the electric double layer capacitance of the porous carbon and the pseudo capacitance of the metal oxide, which can greatly increase the charge storage capacity of the material.
In the preparation method, preferably, in the step (1), the temperature is increased to 900-1200 ℃ at a temperature increase rate of 2-20 ℃/min for high-temperature carbonization treatment, and the heat preservation time is 0.5-4 h.
Preferably, in the step (2), the concentration of the metal salt aqueous solution is 10 g/L-saturated solution, and the mass ratio of the porous carbon fiber to the metal salt is 1: 10-1: 1000.
Preferably, in the step (2), the metal salt is a metal salt that can be pyrolyzed to form a metal oxide, and specifically, the metal salt is at least one of an iron metal salt, a nickel metal salt, a manganese metal salt, and a molybdenum metal salt. Such as iron nitrate, nickel nitrate, cobalt nitrate, manganese nitrate, ammonium molybdate, and the like.
Preferably, in the step (2), the constant-temperature stirring temperature is 10-70 ℃, and the constant-temperature stirring time is 0.5-10 hours.
Preferably, in the step (3), the roasting specifically comprises the following steps: heating to 300-700 ℃ at a heating rate of 2-20 ℃/min under a protective atmosphere, and then roasting at a constant temperature for 0.5-4 h.
As a general inventive concept, the present invention discloses a method for preparing graphene-based conductive ink, comprising the steps of:
(1) preparing a porous carbon fiber/metal oxide composite material by adopting the preparation method;
(2) adding graphene into the binder water diluent while stirring, and uniformly dispersing to obtain a mixed solution; uniformly mixing the porous carbon fiber/metal oxide composite material prepared in the step (1) with acetylene black, adding the mixture into the mixed solution, and stirring to prepare the graphene-based conductive ink;
the mass ratio of the porous carbon fiber/metal oxide composite material to the graphene to the acetylene black to the binder is (70-79): 1-10): 5-15.
Preferably, the binder is LA 133.
As a general inventive concept, the invention discloses an application of the graphene-based conductive ink prepared by the preparation method in a super capacitor, which specifically comprises the following steps: and sequentially superposing and printing silver paste, the graphene-based conductive ink and PVA gel electrolyte on a PET (polyethylene terephthalate) plate by a screen printing method to form a super capacitor pattern, and drying to prepare the flexible super capacitor.
Preferably, the drying temperature is 60-80 ℃, and the drying time is 10-60 min.
Compared with a symmetrical water system flexible super capacitor, the asymmetrical water system flexible super capacitor obtained by printing silver paste, graphene-based conductive ink and PVA gel electrolyte on a PET (polyethylene terephthalate) plate through screen printing has the advantages that the voltage window and the energy density of the capacitor are greatly improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention directly uses the biomass carbon source with low price, thereby reducing the manufacturing cost of the super capacitor. When the absorbent cotton is used as the biomass carbon source, the carbonized absorbent cotton is micron-sized porous carbon fibers, has good flexibility and is favorable for ion transmission. A large number of mesoporous pipelines are arranged in the carbon fiber wall, so that the charge storage and ion transport capacity of the porous carbon is further improved.
(2) The preparation method of the composite material is simple, and the porous carbon fiber/metal oxide composite material which is uniform in composition, large in metal oxide loading capacity, strong in binding force and excellent in electrochemical energy storage performance can be prepared by adsorbing the metal salt solution and combining with subsequent heat treatment.
(3) According to the invention, various anode and cathode materials can be prepared by the same porous carbon fiber and metal oxide compounding method, and the printed asymmetric water system flexible super capacitor has a large voltage window, energy density and power density.
(4) The porous carbon fiber/metal oxide composite material, a small amount of graphene, acetylene black and a binder are uniformly mixed to prepare the multi-channel electron and ion conducting conductive ink. The porous carbon fiber structure in the porous carbon fiber/metal oxide has good ion transmission capability and space stability, and excellent conductivity; a small amount of graphene may increase the conductive path between the porous carbon fibers. Meanwhile, the porous carbon fiber/metal oxide can be used as a support to effectively prevent graphene from agglomerating, and the acetylene black particles with the nanometer size can fill gaps among materials, so that the conductivity of the composite material is further enhanced.
(5) The graphene-based conductive ink disclosed by the invention has good screen printing printability, and can be used for quickly preparing flexible supercapacitors in a large area and in a large batch by combining a screen printing technology.
(6) The flexible supercapacitor printed by adopting the screen printing technology and based on the graphene/porous carbon fiber/metal oxide composite material has a voltage window of 1.8V and a power density of 18mW/cm 2 The energy density can reach 0.035mWh/cm 2 And after the mechanical bending is carried out for 1000 times, the capacitance retention rate reaches 94%, and 2.8V purple LED lamp beads can be lightened by serially connecting two devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of hollow porous carbon fibers and a porous carbon fiber/metal oxide composite prepared in example 1 of the present invention; wherein a, b and c are SEM images of the hollow porous carbon fiber under different magnifications respectively, and d is the SEM image of the porous carbon fiber/metal oxide composite material.
FIG. 2 is an SEM image of porous carbon fibers and a porous carbon fiber/metal oxide composite prepared according to comparative example 1 of the present invention; wherein a and b are SEM images of the porous carbon fiber under different magnifications, and c and d are SEM images of the porous carbon fiber/metal oxide composite material.
FIG. 3 is a plot of cyclic voltammetry at a sweep rate of 50mV/s for various porous carbon fiber/metal oxide composites prepared in examples 1-4 of the present invention.
FIG. 4 is a 1X 1cm section prepared in example 7 of the present invention 2 Picture of flexible supercapacitor.
Fig. 5 is an SEM picture of the electrode of the flexible supercapacitor made in example 7 of the present invention at different magnifications.
FIG. 6 is a 1X 1cm slice prepared in example 7 of the present invention 2 The cyclic voltammetry curve graph a and the constant current charging and discharging curve graph b of the flexible supercapacitor.
Fig. 7 is a graph of power density versus energy density for a supercapacitor made in accordance with example 7 of the present invention.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
porous carbon fiber/Fe 2 O 3 The preparation method of the composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, placing the square boat into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min in an Ar gas atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fibers (hollow porous carbon fibers), wherein SEM pictures of the porous carbon fibers are shown as a, b and c in figure 1;
(2) 9g of Fe (NO) are weighed out 3 ) 3 ·9H 2 Dissolving O in 10ml deionized water, and stirring to obtain Fe (NO) 3 ) 3 A solution;
(3) 100mg of porous carbon fiber is weighed and placed in Fe (NO) 3 ) 3 Stirring and dispersing uniformly in the solution, performing ultrasonic treatment for 30min, stirring at 25 deg.C for 10h, centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6h to obtain porous carbon fiber/Fe (NO) 3 ) 3 Powder;
(4) mixing porous carbon fiber/Fe (NO) 3 ) 3 Placing the powder in a square boat, placing in a tube furnace, heating to 450 deg.C at a heating rate of 5 deg.C/min under Ar atmosphere, maintaining for 60min, cooling, and grinding to obtain porous carbon fiber/Fe 2 O 3 The SEM image of the composite material is shown in d of fig. 1.
Comparative example 1:
porous carbon fiber/Fe 2 O 3 The preparation method of the composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, placing the square boat into a tube furnace, heating to 800 ℃ at a heating rate of 10 ℃/min in an Ar gas atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fibers (hollow porous carbon fibers), wherein SEM images of the porous carbon fibers are shown as a and b in figure 2;
(2) 9g of Fe (NO) are weighed out 3 ) 3 ·9H 2 Dissolving O in 10ml deionized water, and stirring to obtain Fe: (NO 3 ) 3 A solution;
(3) 100mg of porous carbon fiber is weighed and placed in Fe (NO) 3 ) 3 Stirring and dispersing uniformly in the solution, performing ultrasonic treatment for 30min, stirring at 25 deg.C for 10h, centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6h to obtain porous carbon fiber/Fe (NO) 3 ) 3 Powder;
(4) mixing porous carbon fiber/Fe (NO) 3 ) 3 Placing the powder in a square boat, placing in a tube furnace, heating to 450 deg.C at a heating rate of 5 deg.C/min under Ar atmosphere, maintaining for 60min, cooling, and grinding to obtain porous carbon fiber/Fe 2 O 3 The SEM images of the composite materials are shown as c and d in FIG. 2.
When the porous carbon fiber was carbonized at 800 ℃ compared to example 1, the generated pores were much less abundant than at 1000 ℃.
The abundant hierarchical pore channels in example 1 facilitate rapid ion transport, and facilitate large-scale loading of metal oxides.
Example 2:
the preparation method of the porous carbon fiber/NiO composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, then placing the square boat into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min in an Ar gas atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fiber;
(2) weighing 5g of Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 10ml deionized water, and stirring to obtain Ni (NO) 3 ) 2 A solution;
(3) 100mg of porous carbon fiber is weighed and placed on Ni (NO) 3 ) 2 Stirring and dispersing uniformly in the solution, performing ultrasonic treatment for 30min, stirring at 25 deg.C for 10h, centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6h to obtain porous carbon fiber/Ni (NO) 3 ) 2 Powder;
(4) mixing porous carbon fiber/Ni (NO) 3 ) 2 Placing the powder in a square boat, and heating in a tube furnace under Ar atmosphere at a heating rate of 5 deg.C/minAnd (3) heating to 450 ℃, keeping the temperature for 60min, and cooling and grinding after roasting to obtain the porous carbon fiber/NiO composite material.
Example 3:
the preparation method of the porous carbon fiber/CoO composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, then placing the square boat into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min in an Ar gas atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fiber;
(2) weighing 5g of Co (NO) 3 ) 2 ·6H 2 Dissolving O in 10ml deionized water, and stirring to obtain Co (NO) 3 ) 2 A solution;
(3) weighing 100mg of porous carbon fiber and placing the porous carbon fiber on Co (NO) 3 ) 2 Stirring and dispersing uniformly in the solution, performing ultrasonic treatment for 30min, keeping stirring at 25 deg.C for 10h, centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6h to obtain porous carbon fiber/Co (NO) 3 ) 2 Powder;
(4) mixing porous carbon fiber/Co (NO) 3 ) 2 And putting the powder into a square boat, heating to 450 ℃ at a heating rate of 5 ℃/min in a tubular furnace under the atmosphere of Ar, keeping for 60min, cooling after roasting, and grinding to obtain the porous carbon fiber/CoO composite material.
Example 4:
porous carbon fiber/MnO 2 The preparation method of the composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, then placing the square boat into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min in an Ar gas atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fiber;
(2) 5g of Mn (NO) are weighed 3 ) 2 Dissolving in 10ml deionized water, and stirring to obtain Mn (NO) 3 ) 2 A solution;
(3) weighing 100mg of porous carbon fiber and placing the porous carbon fiber on Mn (NO) 3 ) 2 Stirring and dispersing in the solution uniformly, performing ultrasonic treatment for 30min, keeping stirring at 25 ℃ for 10h,centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6 hr to obtain porous carbon fiber/Mn (NO) 3 ) 2 Powder;
(4) porous carbon fiber/Mn (NO) 3 ) 2 Placing the powder in a square boat, heating to 450 ℃ at a heating rate of 5 ℃/min in a tubular furnace under the atmosphere of Ar, keeping for 60min, cooling and grinding after roasting is finished to obtain the porous carbon fiber/MnO 2 A composite material.
Example 5:
porous carbon fiber/Fe 2 O 3 The preparation method of the composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, then placing the square boat into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min in an Ar gas atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fibers (hollow porous carbon fibers);
(2) 1g of Fe (NO) is weighed 3 ) 3 ·9H 2 Dissolving O in 10ml deionized water, and stirring to obtain Fe (NO) 3 ) 3 A solution;
(3) 100mg of porous carbon fiber is weighed and placed in Fe (NO) 3 ) 3 Stirring and dispersing uniformly in the solution, performing ultrasonic treatment for 30min, stirring at 25 deg.C for 10h, centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6h to obtain porous carbon fiber/Fe (NO) 3 ) 3 Powder;
(4) mixing porous carbon fiber/Fe (NO) 3 ) 3 Placing the powder in a square boat, placing in a tube furnace, heating to 450 deg.C at a heating rate of 5 deg.C/min under Ar atmosphere, maintaining for 60min, cooling, and grinding to obtain porous carbon fiber/Fe 2 O 3 A composite material.
Example 6:
porous carbon fiber/Fe 2 O 3 The preparation method of the composite material comprises the following steps:
(1) cutting 2g of absorbent cotton into a square boat, placing the square boat into a tube furnace, heating to 1000 ℃ at a heating rate of 10 ℃/min in an Ar atmosphere, keeping the temperature for 120min, cooling, and grinding into powder to obtain porous carbon fibers (hollow porous carbon fibers);
(2) 13g of Fe (NO) are weighed out 3 ) 3 ·9H 2 Dissolving O in 10ml deionized water, and stirring to obtain Fe (NO) 3 ) 3 A solution;
(3) 100mg of porous carbon fiber is weighed and placed in Fe (NO) 3 ) 3 Stirring and dispersing in solution, performing ultrasonic treatment for 30min, stirring at 25 deg.C for 10 hr, centrifuging at 12000r/min for 5min, and drying at 70 deg.C for 6 hr to obtain porous carbon fiber/Fe (NO) 3 ) 3 Powder;
(4) mixing porous carbon fiber/Fe (NO) 3 ) 3 Placing the powder in a square boat, placing in a tube furnace, heating to 450 deg.C at a heating rate of 5 deg.C/min under Ar atmosphere, maintaining for 60min, cooling, and grinding to obtain porous carbon fiber/Fe 2 O 3 A composite material.
The porous carbon fiber/metal oxide composite materials prepared in the embodiments 1 to 4 are respectively used as electrode materials of a supercapacitor, and specifically, the porous carbon fiber/metal oxide composite materials, acetylene black and PVDF are mixed according to a mass ratio of 75: 15: 10, mixing, adding the mixture into a solvent NMP to prepare a uniform solution, wherein the concentration of the prepared solution is 0.053 g/ml; then the solution was uniformly applied to 1cm 2 And dried in a drying oven at 70 ℃ for 4 hours, and after drying, the nickel foam coated with the test material was subjected to a tabletting treatment (6MPa for 10 seconds). Finally, electrochemical tests are carried out on a CHI760 electrochemical workstation by using a three-electrode system, FIG. 3 is a Cyclic Voltammogram (CV) of each electrode material at a scanning rate of 50mV/s, and from FIG. 3, porous carbon fiber/Fe can be calculated 2 O 3 The composite material is suitable for being used as a super capacitor cathode material, and the mass specific capacitance of the composite material is 277F/g; in the anode material, the area surrounded by the cyclic voltammetry curves of the porous carbon fiber/NiO composite material is the largest, and the specific capacitance of the porous carbon fiber/NiO composite material is 260F/g.
Example 7:
this example uses porous carbon fiber/Fe prepared in example 1 2 O 3 Composite as a negative electrode Material, the composite prepared in example 2The porous carbon fiber/NiO composite material is used as a positive electrode material and is respectively prepared into conductive ink capable of being subjected to screen printing, and patterned flexible supercapacitors are printed on a large scale, wherein the preparation process specifically comprises the following steps:
(1) negative ink (graphene/porous carbon fiber/Fe) 2 O 3 Composite conductive ink) is prepared by the following steps:
firstly, diluting 15% of LA133 with water to 5%, then weighing 1.42g of 5% of LA133 (with the solid content of 71mg) into a beaker, adding a magnet and stirring;
secondly, weighing 71mg of graphene (Gs), adding the graphene (Gs) into the beaker, and stirring for 30min to uniformly disperse the graphene (Gs) to obtain a mixed solution;
③ then 0.5g of porous carbon fiber/Fe is weighed 2 O 3 And grinding and uniformly mixing the composite material powder and 71mg of acetylene black in a mortar, gradually adding the mixture into the mixed solution obtained in the step II, and stirring to prepare the negative ink with the viscosity of 0.2Pa & s.
(2) The preparation method of the positive electrode ink (graphene/porous carbon fiber/NiO composite conductive ink) comprises the following steps:
firstly, diluting 15% of LA133 with water to 5%, then weighing 1.42g of 5% of LA133 (with the solid content of 71mg) into a beaker, adding a magnet and stirring;
secondly, weighing 71mg of graphene (Gs), adding the graphene (Gs) into the beaker, and stirring for 30min to uniformly disperse the graphene (Gs) to obtain a mixed solution;
thirdly, 0.5g of porous carbon fiber/NiO composite material powder and 71mg of acetylene black are weighed, ground and mixed uniformly in a mortar, and then gradually added into the mixed liquid obtained in the second step, and stirred to prepare the positive ink with the viscosity of 0.2 Pa.s.
(3) The preparation method of the flexible supercapacitor comprises the following specific preparation steps:
sequentially printing silver paste, negative ink and PVA alkaline gel electrolyte on PET by a 200-mesh screen printing plate to form a pattern of a super capacitor, and drying at 70 ℃ for 10min to obtain a negative plate;
secondly, sequentially printing silver paste, positive printing ink and PVA alkaline gel electrolyte on another PET plate through a 200-mesh screen printing plate to form a super capacitor pattern, and drying at 70 ℃ for 10min to obtain a positive plate;
and thirdly, the negative plate and the positive plate are assembled together just opposite to each other, and the negative plate and the positive plate are separated by the soaked diaphragm to prevent the positive plate and the negative plate from being in direct contact with each other, so that the flexible supercapacitor is formed, and is particularly shown in figure 4.
Specifically, the number of times of printing can be selected according to actual requirements, as shown in fig. 5 (the positive electrode and the negative electrode are similar in shape), the flexible supercapacitor is very compact and uniform in printing, and the porous carbon fiber/metal oxide composite material and the graphene are connected with each other, so that a very excellent channel is provided for conduction of current carriers. After 2 times of printing, the thickness of the active material layer can reach 20-30 mu m, and the area specific capacitance of the flexible super capacitor can be increased by further increasing the printing thickness.
As shown in a in fig. 6, the voltage window of the water system asymmetric flexible supercapacitor of the cyclic voltammogram reaches 1.8V, which is much larger than that of a general water system symmetric supercapacitor; and obvious double-electric-layer capacitance part and oxidation reduction peak can be seen, which shows that the porous carbon fiber/metal oxide has both double-electric-layer capacitance and pseudo capacitance, and the energy density and the power density of the composite material are greatly improved.
As shown in FIG. 7, the area is 1X 1cm 2 The current density of the flexible super capacitor is 2mA/cm under constant current charging and discharging 2 The area specific capacitance can reach 77.4F/cm 2 The power density reaches 4.5mW/cm 2 When the corresponding energy density is 0.031mWh/cm 2 (ii) a And the maximum power density can reach 18mW/cm 2 The maximum energy density can reach 0.035mWh/cm 2 。
In this embodiment, the retention rate of capacitance of the flexible supercapacitor reaches 94% after the flexible supercapacitor is mechanically bent 1000 times. By connecting two flexible supercapacitors in series at the same time, a purple 2.8V LED lamp can be lighted, and therefore the LED lamp can be used as a portable energy storage system in the field of future wearable electronic equipment.
Claims (9)
1. A preparation method of graphene-based conductive ink is characterized by comprising the following steps:
1) preparing a porous carbon fiber/metal oxide composite material;
the preparation method of the porous carbon fiber/metal oxide composite material comprises the following steps:
(1) heating the absorbent cotton to 900-1200 ℃ under a protective atmosphere, carrying out high-temperature carbonization treatment, cooling, and grinding to obtain porous carbon fibers;
(2) placing the porous carbon fiber in a metal salt aqueous solution, stirring at a constant temperature, centrifuging, and drying to obtain a porous carbon fiber/metal salt composite material;
(3) roasting the porous carbon fiber/metal salt composite material in a protective atmosphere, and cooling and grinding the roasted porous carbon fiber/metal salt composite material to obtain a porous carbon fiber/metal oxide composite material;
2) adding graphene into the binder water diluent while stirring, and uniformly dispersing to obtain a mixed solution; uniformly mixing the porous carbon fiber/metal oxide composite material prepared in the step (1) with acetylene black, adding the mixture into the mixed solution, and stirring to prepare the graphene-based conductive ink;
the mass ratio of the porous carbon fiber/metal oxide composite material to the graphene to the acetylene black to the binder is (70-79): 1-10): 5-15.
2. The preparation method according to claim 1, wherein in the step (1), the temperature is raised to 900-1200 ℃ at a temperature rise rate of 2-20 ℃/min, and the high-temperature carbonization treatment is carried out, wherein the heat preservation time is 0.5-4 h.
3. The preparation method according to claim 1, wherein in the step (2), the concentration of the metal salt aqueous solution is 10g/L to a saturated solution, and the mass ratio of the porous carbon fibers to the metal salt is 1:10 to 1: 1000.
4. The method according to claim 1, wherein in the step (2), the metal salt is at least one of an iron metal salt, a nickel metal salt, a manganese metal salt, and a molybdenum metal salt.
5. The preparation method according to any one of claims 1 to 4, wherein in the step (2), the stirring temperature at constant temperature is 10 to 70 ℃ and the stirring time at constant temperature is 0.5 to 10 hours.
6. The preparation method according to any one of claims 1 to 4, wherein in the step (3), the roasting specifically comprises the following steps: heating to 300-700 ℃ at a heating rate of 2-20 ℃/min under a protective atmosphere, and then roasting at a constant temperature for 0.5-4 h.
7. The method of claim 1, wherein the binder is LA 133.
8. The application of the graphene-based conductive ink prepared by the preparation method of any one of claims 1 to 7 in a supercapacitor is characterized by specifically comprising the following steps: and sequentially superposing and printing silver paste, the graphene-based conductive ink and PVA gel electrolyte on a PET (polyethylene terephthalate) plate by a screen printing method to form a super capacitor pattern, and drying to prepare the flexible super capacitor.
9. The use according to claim 8, wherein the drying temperature is 60-80 ℃ and the drying time is 10-60 min.
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