CN110176358B - Phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode and preparation method thereof - Google Patents
Phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode and preparation method thereof Download PDFInfo
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 82
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 82
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229960003638 dopamine Drugs 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 42
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 16
- 239000004917 carbon fiber Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 82
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 59
- 238000009987 spinning Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 17
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 16
- 238000010041 electrostatic spinning Methods 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 8
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 208000012886 Vertigo Diseases 0.000 claims 9
- 238000001523 electrospinning Methods 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 37
- 239000003990 capacitor Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 6
- 229920001690 polydopamine Polymers 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000006258 conductive agent Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000008098 formaldehyde solution Substances 0.000 description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910003266 NiCo Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007227 biological adhesion Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 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
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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
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode and a preparation method thereof (@ denotes coating, the same applies below), and belongs to the technical field of supercapacitors. The phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material is synthesized by a one-step method, nickel cobaltate is loaded on the phenolic resin-based carbon nanofiber through a hydrothermal reaction under an alkaline condition, and a layer of polydopamine is coated on the surface of the phenolic resin-based carbon nanofiber. The invention has simple manufacturing process, can be directly used as an electrode without a binder and a conductive agent when loaded on a carbon fiber substrate, greatly improves the capacitance performance by compounding an electric double layer and a pseudo capacitor, has higher specific capacitance, increases the adhesion of an electrode material on the carbon fiber by introducing dopamine, effectively improves the stability of the electrode by introducing N atoms, and has good development prospect in the future energy storage field.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to a phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode and a preparation method thereof.
Background
Supercapacitors, also known as electrochemical capacitors, are a new type of energy storage device that is interposed between a conventional capacitor and a rechargeable battery, and therefore combine the advantages of both conventional capacitors and rechargeable batteries. In many electrochemical energy storage devices, supercapacitors have attracted much attention in various fields due to their characteristics of high power density, high charge-discharge efficiency, long cycle life, and the like.
Nickel cobaltate (NiCo)2O4) Due to the synergistic effect of Ni and Co ions, the nickel-cobalt composite material has high theoretical specific capacitance and electrochemical activity, is simple to prepare and low in cost, and is considered to be a promising electrode material. However, nickel cobaltate electrodes still have many drawbacks, such as poor cycle performance, poor conductivity, and capacityEasy to agglomerate. Dopamine is used as a biological adhesion protein, has strong adhesion and is rich in various functional groups, and meanwhile, the dopamine can undergo self-polymerization under alkaline conditions to form polydopamine. The structure of polydopamine contains a large amount of amino (-NH)2) And active groups such as hydroxyl (-OH) and the like, wherein the groups not only can play a role of improving specific capacitance, but also can chelate metal ions to anchor the metal ions on the carbon fibers, so that the mechanical adhesion of the material is enhanced, and the cycle performance of the material is further improved. In addition, polydopamine and carbon fiber have good conductivity, and the conductivity of the material can be enhanced. Meanwhile, the interaction among the three composite materials can greatly reduce the agglomeration of the nickel cobaltate, thereby improving the specific capacitance of the material.
The Chinese patent application with the application number of 201810436644.3 discloses a method for preparing a nickel cobaltate/carbon fiber flexible electrode material by an electrostatic spinning double-spraying method, wherein a mixed solution of nickel salt and cobalt salt with the molar ratio of 1: 2 is prepared, urea is used as a precipitator, and hydrothermal reaction is carried out to obtain NiCo2O4Precursor microspheres; then preparing PAN solution and PVP solution, adding NiCo after PVP solution is dissolved2O4The precursor microspheres are uniformly mixed, then the fibers are obtained by spinning through an electrostatic spinning double-jet method, and finally the nickel cobaltate/carbon fiber flexible electrode material is obtained by two heat treatments of pre-oxidation and carbonization. The electron microscope image of the patent can see that large particles still exist and are seriously agglomerated; the carbon fiber and the nickel cobaltate cannot be compounded well, and the nickel cobaltate has the risk of being reduced after the carbon fiber and the nickel cobaltate are pre-oxidized and carbonized through spinning.
The Chinese patent application with the application number of 201810081472.2 discloses a preparation method of a carbon fiber/NiCo 2O 4/graphene composite material, and belongs to the technical field of nano materials. The method adopts structural carbon fiber as a substrate, and synthesizes NiCo on the surface of the carbon fiber in situ by a hydrothermal method2O4The multi-stage micro-nano structure is formed by mutually interlacing and mutually inserting the nano wires and the porous graphene. In the patent, after nickel cobaltate is loaded on the surface of the carbon fiber, graphene is added, so that the performance is further improved, but the graphene is high in price, and compared with the dopamine, the dopamine is not only low in price, but also can be doped by introducing N atomsThe pseudo capacitance is increased, and the performance is better.
Disclosure of Invention
The invention provides a preparation method of a phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode, and aims to solve the technical problems of low specific capacity and poor cycle performance of a super capacitor in the prior art.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode is prepared by the following preparation method:
(1) preparing a phenolic resin spinning solution;
(2) performing electrostatic spinning, curing and carbonization on the phenolic resin spinning stock solution to obtain phenolic resin-based carbon nanofibers;
(3) soaking the phenolic resin-based carbon nanofibers in 4-6mol/L hydrochloric acid solution for 3-5h, and washing to obtain activated phenolic resin-based carbon nanofibers;
(4) immersing the activated phenolic resin-based carbon nanofiber into a hydrothermal reaction solution, and reacting for 12-36h at the temperature of 100-150 ℃ to obtain a precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material; the hydrothermal reaction solution is formed by mixing 2 solutions, wherein the solution A is prepared by dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in deionized water and then stirring for 10-20min, wherein the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea is (1-3) to 1: 12; dissolving dopamine hydrochloride and trihydroxymethyl aminomethane in deionized water, and magnetically stirring for 5-7 h, wherein the molar ratio of the dopamine hydrochloride to the trihydroxymethyl aminomethane is (3-4)): 1; mixing the two solutions A and B under stirring, and magnetically stirring for 20-40 min to obtain a hydrothermal reaction solution, wherein the solution A and the solution B are mixed in equal volume;
(5) and heating the precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material to 200-400 ℃ at a speed of 3-5 ℃/min, roasting, and keeping the temperature for 60-180min to obtain the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite electrode.
Further, the specific steps for preparing the phenolic resin spinning solution in the step (1) are as follows:
(a) mixing phenol, a catalyst NaOH and a binder polyvinyl alcohol, wherein the mass ratio of the phenol to the NaOH to the polyvinyl alcohol is (280-320) to 25: 126; heating to 90-100 ℃, keeping the temperature for 50-70min, adding formaldehyde again, keeping the temperature for 160-260min, wherein the molar ratio of the formaldehyde to the phenol is 3.5: 1-4.5: 1, and cooling the product to room temperature after the reaction is finished to obtain the phenolic resin;
(b) preparing the obtained phenolic resin into an aqueous solution with the mass percent of 15-20% to obtain the phenolic resin spinning solution.
Furthermore, the mass ratio of the formaldehyde added twice in the step (a) is (3-5) to 1.
Further, the electrostatic spinning process in the step (2) is to spin the phenolic resin spinning solution under the conditions that the spinning voltage is 18KV-28KV and the spinning distance is 15-30 cm.
Further, the solidification process in the step (2) is to treat the primary spun fiber obtained by electrostatic spinning at the temperature of 100 ℃ and 200 ℃ for 1-3 h.
Further, the carbonization process in the step (2) is to heat up to 700-.
A preparation method of the phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode comprises the following steps:
(1) preparing a phenolic resin spinning solution;
(2) performing electrostatic spinning, curing and carbonization on the phenolic resin spinning stock solution to obtain phenolic resin-based carbon nanofibers;
(3) soaking the phenolic resin-based carbon nanofibers in 4-6mol/L hydrochloric acid solution for 3-5h, and washing to obtain activated phenolic resin-based carbon nanofibers;
(4) immersing the activated phenolic resin-based carbon nanofiber into a hydrothermal reaction solution, and reacting for 12-36h at the temperature of 100-150 ℃ to obtain a precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material; the hydrothermal reaction solution is formed by mixing 2 solutions, wherein the solution A is prepared by dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in deionized water and then stirring for 10-20min, wherein the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea is (1-3) to 1: 12; dissolving dopamine hydrochloride and trihydroxymethyl aminomethane in deionized water, and magnetically stirring for 5-7 h, wherein the molar ratio of the dopamine hydrochloride to the trihydroxymethyl aminomethane is (3-4)): 1; mixing the two solutions A and B under stirring, and magnetically stirring for 20-40 min to obtain a hydrothermal reaction solution, wherein the solution A and the solution B are mixed in equal volume;
(5) and heating the precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material to 200-400 ℃ at a speed of 3-5 ℃/min, roasting, and keeping the temperature for 60-180min to obtain the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite electrode.
The invention has the beneficial effects that:
compared with the prior art, the invention has remarkable technical progress. The electrode material of the super capacitor has the double electric layer capacitance effect and the pseudo-capacitance effect, overcomes the defect that the similar material is low in specific capacitance only depending on the double electric layer capacitance effect, and effectively improves the specific capacity of the electrode material; meanwhile, the addition of dopamine increases the adhesion of nickel cobaltate and matrix carbon fiber, and the stability is also improved, so that the nickel cobaltate has better electrochemical performance.
Drawings
FIG. 1 is a scanning electron microscope image of the phenolic resin-based nano-carbon fiber @ nickel cobaltate/dopamine composite material prepared in example 3.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
Mixing 12.6g of PVA, 96g of distilled water, 2.5g of NaOH and 32g of phenol (the mass ratio of phenol to NaOH to polyvinyl alcohol is 320: 25: 126), heating to 90 ℃ under stirring, stirring at constant temperature for 70min, adding formaldehyde solution (analytically pure), and reacting at constant temperature for 50min under stirring. Adding formaldehyde solution (analytically pure) again, wherein the mass ratio of the formaldehyde added for the first time to the formaldehyde added for the second time is 5: 1, the molar ratio of the total amount of the formaldehyde to the phenol is 3.5: 1, and reacting for 260 min. Preparing the phenolic resin into a 20% aqueous solution, and uniformly stirring to obtain the spinning solution.
Carrying out electrostatic spinning on the spinning solution, wherein the spinning parameters are as follows: the spinning voltage interval is 18KV, and the spinning distance is 30 cm. And curing the obtained spun fiber at 100 ℃ for 3h to obtain the cured fiber. And (3) placing the cured fiber in a carbonization furnace, heating to 900 ℃ at the speed of 1 ℃/min under the protection of nitrogen, and keeping the temperature for 0.5h, thereby obtaining the phenolic resin-based carbon nanofiber.
And (3) soaking the phenolic resin-based carbon nanofibers in 4mol/L hydrochloric acid solution for 5 hours, and then washing the phenolic resin-based carbon nanofibers with absolute ethyl alcohol and clear water to obtain the activated phenolic resin-based carbon nanofibers.
Preparation of a hydrothermal reaction solution: 0.1455g of cobalt nitrate hexahydrate, 0.1454g of nickel nitrate hexahydrate and 0.36g of urea (the molar ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea is 1: 12) are dissolved in 10mL of deionized water and then magnetically stirred for 10min to obtain a solution A. 0.2g of dopamine hydrochloride and tris (hydroxymethyl) aminomethane (the molar ratio of dopamine hydrochloride to tris (hydroxymethyl) aminomethane is 4: 1) are dissolved in 10mL of deionized water and then stirred magnetically for 5 hours to obtain a solution B. And magnetically stirring the two solutions A and B for 40min, and mixing to obtain a hydrothermal reaction solution. And (3) putting the activated phenolic resin-based carbon nanofibers into a liner of a reaction kettle containing hydrothermal reaction liquid, and reacting for 12 hours at 150 ℃ to obtain a precursor of the phenolic resin-based carbon nanofibers @ nickel cobaltate/dopamine composite material. And (3) roasting the precursor in a muffle furnace, heating to 400 ℃ at a speed of 3 ℃/min, and keeping the temperature for 1h, thereby obtaining the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material.
Electrochemical tests show that the specific capacitance of the phenolic resin based carbon nanofiber/nickel cobaltate composite material prepared in the embodiment is 685F/g at a current density of 1A/g; the capacity retention rate after 1000 cycles at a current density of 10A/g is 92.32% or more, and the capacity retention rate after 3000 cycles is 88.03% or more.
Example 2
Mixing 12.6g of PVA, 96g of distilled water, 2.5g of NaOH and 30g of phenol (the mass ratio of phenol to NaOH to polyvinyl alcohol is 300: 25: 126), heating to 96 ℃ under stirring, stirring at constant temperature for 60min, adding a formaldehyde solution (analytically pure), and reacting at constant temperature for 60min under stirring. Adding formaldehyde solution (analytically pure) again, wherein the mass ratio of the formaldehyde added for the first time to the formaldehyde added for the second time is 4: 1, the molar ratio of the total amount of the formaldehyde to the phenol is 3.92: 1, and reacting for 180 min. Preparing the phenolic resin into a 16% aqueous solution, and uniformly stirring to obtain the spinning solution.
Carrying out electrostatic spinning on the spinning solution, wherein the spinning parameters are as follows: the spinning voltage interval is 25KV, and the spinning distance is 18 cm. And curing the obtained spun fiber at 150 ℃ for 2h to obtain the cured fiber. And (3) placing the cured fiber in a carbonization furnace, heating to 800 ℃ at a speed of 3 ℃/min under the protection of nitrogen, and keeping the temperature for 1h, thereby obtaining the phenolic resin-based carbon nanofiber.
And (3) soaking the phenolic resin-based carbon nanofibers in 5mol/L hydrochloric acid solution for 4 hours, and then washing the phenolic resin-based carbon nanofibers with absolute ethyl alcohol and clear water to obtain the activated phenolic resin-based carbon nanofibers.
Preparation of a hydrothermal reaction solution: 0.291g of cobalt nitrate hexahydrate, 0.1454g of nickel nitrate hexahydrate and 0.36g of urea (the molar ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea is 2: 1: 12) were dissolved in 10mL of deionized water and then magnetically stirred for 15min to obtain solution A. 0.2g of dopamine hydrochloride and tris (hydroxymethyl) aminomethane (molar ratio of dopamine hydrochloride to tris (hydroxymethyl) aminomethane is 3.5: 1) are dissolved in 10mL of deionized water and then stirred magnetically for 6h to obtain solution B. And magnetically stirring the two solutions A and B for 30min, and mixing to obtain a hydrothermal reaction solution. And (3) putting the activated phenolic resin-based carbon nanofibers into a liner of a reaction kettle containing hydrothermal reaction liquid, and reacting for 12 hours at 120 ℃ to obtain a precursor of the phenolic resin-based carbon nanofibers @ nickel cobaltate/dopamine composite material. And (3) roasting the precursor in a muffle furnace, heating to 300 ℃ at a speed of 3 ℃/min, and keeping the temperature for 2 hours, thereby obtaining the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material.
Electrochemical tests show that the specific capacitance of the phenolic resin-based carbon nanofiber/nickel cobaltate composite material prepared in the embodiment is 758F/g at a current density of 1A/g; the capacity retention rate after 1000 cycles under the current density of 10A/g is 92.57% or more, and the capacity retention rate after 3000 cycles is 88.98% or more.
Example 3
Mixing 12.6g of PVA, 96g of distilled water, 2.5g of NaOH and 30g of phenol (the mass ratio of phenol to NaOH to polyvinyl alcohol is 300: 25: 126), heating to 96 ℃ under stirring, stirring at constant temperature for 60min, adding a formaldehyde solution (analytically pure), and reacting at constant temperature for 60min under stirring. Adding formaldehyde solution (analytically pure) again, wherein the mass ratio of the formaldehyde added for the first time to the formaldehyde added for the second time is 4: 1, the molar ratio of the total amount of the formaldehyde to the phenol is 3.92: 1, and reacting for 180 min. Preparing the phenolic resin into a 16% aqueous solution, and uniformly stirring to obtain the spinning solution.
Carrying out electrostatic spinning on the spinning solution, wherein the spinning parameters are as follows: the spinning voltage interval is 25KV, and the spinning distance is 18 cm. And curing the obtained spun fiber at 150 ℃ for 2h to obtain the cured fiber. And (3) placing the cured fiber in a carbonization furnace, heating to 800 ℃ at a speed of 3 ℃/min under the protection of nitrogen, and keeping the temperature for 1h, thereby obtaining the phenolic resin-based carbon nanofiber.
And (3) soaking the phenolic resin-based carbon nanofibers in 5mol/L hydrochloric acid solution for 4 hours, and then washing the phenolic resin-based carbon nanofibers with absolute ethyl alcohol and clear water to obtain the activated phenolic resin-based carbon nanofibers.
Preparation of a hydrothermal reaction solution: 0.291g of cobalt nitrate hexahydrate, 0.1454g of nickel nitrate hexahydrate and 0.36g of urea (the molar ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea is 2: 1: 12) were dissolved in 10mL of deionized water and then magnetically stirred for 15min to obtain solution A. 0.2g of dopamine hydrochloride and tris (hydroxymethyl) aminomethane (molar ratio of dopamine hydrochloride to tris (hydroxymethyl) aminomethane is 3.5: 1) are dissolved in 10mL of deionized water and then stirred magnetically for 6h to obtain solution B. And magnetically stirring the two solutions A and B for 30min, and mixing to obtain a hydrothermal reaction solution. And (3) putting the activated phenolic resin-based carbon nanofibers into a liner of a reaction kettle containing hydrothermal reaction liquid, and reacting for 24 hours at 120 ℃ to obtain a precursor of the phenolic resin-based carbon nanofibers @ nickel cobaltate/dopamine composite material. And (3) roasting the precursor in a muffle furnace, heating to 300 ℃ at a speed of 5 ℃/min, and keeping the temperature for 2 hours, thereby obtaining the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material.
Electrochemical tests show that the specific capacitance of the phenolic resin-based carbon nanofiber/nickel cobaltate composite material prepared in the embodiment is 832F/g at a current density of 1A/g; the capacity retention rate after 1000 cycles at a current density of 10A/g is 93.72% or more, and the capacity retention rate after 3000 cycles is 89.86% or more.
Example 4
Mixing 12.6g of PVA, 96g of distilled water, 2.5g of NaOH and 28g of phenol (the mass ratio of phenol to NaOH to polyvinyl alcohol is 280: 25: 126), heating to 96 ℃ under stirring, stirring at constant temperature for 50min, adding a formaldehyde solution (analytically pure), and reacting at constant temperature for 70min under stirring. Adding formaldehyde solution (analytically pure) again, wherein the mass ratio of the formaldehyde added for the first time to the formaldehyde added for the second time is 3: 1, the molar ratio of the total amount of the formaldehyde to the phenol is 4.5: 1, and reacting for 160 min. Preparing the phenolic resin into a 15% aqueous solution, and uniformly stirring to obtain the spinning solution.
Carrying out electrostatic spinning on the spinning solution, wherein the spinning parameters are as follows: the spinning voltage interval is 28KV, and the spinning distance is 15 cm. And curing the obtained spun fiber at 200 ℃ for 1h to obtain the cured fiber. And (3) placing the cured fiber in a carbonization furnace, heating to 700 ℃ at a speed of 2 ℃/min under the protection of nitrogen, and keeping the temperature for 1.5h, thereby obtaining the phenolic resin-based carbon nanofiber.
And (3) soaking the phenolic resin-based carbon nanofibers in 6mol/L hydrochloric acid solution for 3h, and then washing the phenolic resin-based carbon nanofibers with absolute ethyl alcohol and clear water to obtain the activated phenolic resin-based carbon nanofibers.
Preparation of a hydrothermal reaction solution: 0.4365g of cobalt nitrate hexahydrate, 0.1454g of nickel nitrate hexahydrate and 0.36g of urea (the molar ratio of cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea is 3: 1: 12) are dissolved in 10mL of deionized water and then stirred magnetically for 20min to obtain a solution A. 0.2g of dopamine hydrochloride and tris (hydroxymethyl) aminomethane (the molar ratio of dopamine hydrochloride to tris (hydroxymethyl) aminomethane is 3: 1) are dissolved in 10mL of deionized water and then stirred magnetically for 7h to obtain a solution B. And magnetically stirring the two solutions A and B for 20min, and mixing to obtain a hydrothermal reaction solution. And (3) putting the activated phenolic resin-based carbon nanofibers into a liner of a reaction kettle containing hydrothermal reaction liquid, and reacting for 36 hours at 100 ℃ to obtain a precursor of the phenolic resin-based carbon nanofibers @ nickel cobaltate/dopamine composite material. And (3) roasting the precursor in a muffle furnace, heating to 200 ℃ at a speed of 4 ℃/min, and keeping the temperature for 3 hours, thereby obtaining the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material.
Electrochemical tests show that the specific capacitance of the phenolic resin-based carbon nanofiber/nickel cobaltate composite material prepared in the embodiment is 659F/g at a current density of 1A/g; the capacity retention rate after 1000 cycles at a current density of 10A/g is 92.65% or more, and the capacity retention rate after 3000 cycles is 88.52% or more.
Comparative example
Comparative example: 0.291g of cobalt nitrate hexahydrate, 0.1454g of nickel nitrate hexahydrate and 0.36g of urea are dissolved in 20mL of deionized water, and the mixture is magnetically stirred for 15min to prepare a hydrothermal reaction solution. And (3) putting the hydrothermal reaction liquid into an inner container of a reaction kettle, and reacting for 24 hours at 120 ℃ to obtain a precursor cobalt nickel hydroxide. And (3) roasting the precursor in a muffle furnace, heating to 300 ℃ at a speed of 5 ℃/min, and keeping the temperature for 2 hours, thereby obtaining the nickel cobaltate material.
Electrochemical tests show that the specific capacitance of the nickel cobaltate material prepared in the embodiment is 364F/g at a current density of 1A/g. The capacity retention rate after 1000 cycles at a current density of 10A/g is 85.12% or more, and the capacity retention rate after 3000 cycles is 74.12% or more.
Claims (4)
1. The phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode is characterized by being prepared by the following preparation method:
(1) preparing a phenolic resin spinning solution;
(2) performing electrostatic spinning, curing and carbonization on the phenolic resin spinning stock solution to obtain phenolic resin-based carbon nanofibers;
(3) soaking the phenolic resin-based carbon nanofibers in 4-6mol/L hydrochloric acid solution for 3-5h, and washing to obtain activated phenolic resin-based carbon nanofibers;
(4) immersing the activated phenolic resin-based carbon nanofiber into a hydrothermal reaction solution, and reacting for 12-36h at the temperature of 100-150 ℃ to obtain a precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material; the hydrothermal reaction solution is formed by mixing 2 solutions, wherein the solution A is prepared by dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in deionized water and then stirring for 10-20min, wherein the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea is (1-3) to 1: 12; dissolving dopamine hydrochloride and trihydroxymethyl aminomethane in deionized water, and magnetically stirring for 5-7 h, wherein the molar ratio of the dopamine hydrochloride to the trihydroxymethyl aminomethane is (3-4)): 1; mixing the two solutions A and B under stirring, and magnetically stirring for 20-40 min to obtain a hydrothermal reaction solution, wherein the solution A and the solution B are mixed in equal volume;
(5) and heating the precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material to 200-400 ℃ at a speed of 3-5 ℃/min, roasting, and keeping the temperature for 60-180min to obtain the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite electrode.
2. The phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode as claimed in claim 1, wherein the specific steps of preparing the phenolic resin spinning solution in step (1) are as follows:
(a) mixing phenol, a catalyst NaOH and a binder polyvinyl alcohol, wherein the mass ratio of the phenol to the NaOH to the polyvinyl alcohol is (280-320) to 25: 126; heating to 90-100 ℃, keeping the temperature for 50-70min, adding formaldehyde again, keeping the temperature for 260min, adding formaldehyde twice according to the mass ratio of (3-5) to 1, and finally cooling the product to room temperature after the reaction is finished, thereby obtaining the phenolic resin;
(b) preparing the obtained phenolic resin into an aqueous solution with the mass percent of 15-20% to obtain the phenolic resin spinning solution.
3. The phenolic resin based carbon nanofiber @ nickel cobaltate/dopamine composite electrode as claimed in claim 1, wherein the electrospinning process in step (2) is to spin the phenolic resin spinning solution at a spinning voltage of 18KV-28KV and a spinning distance of 15-30 cm; the solidification process is that the primary spun fiber obtained by electrostatic spinning is treated for 1-3h at the temperature of 100-200 ℃; the carbonization process is that the temperature of the solidified fiber is raised to 700-900 ℃ at the speed of 1-3 ℃/min under the protection of inert gas, and the temperature is kept for 30-90min, thereby obtaining the phenolic resin-based nano carbon fiber.
4. A method for preparing the phenolic resin based nano carbon fiber @ nickel cobaltate/dopamine composite electrode as claimed in any one of claims 1-3, wherein the method is carried out according to the following steps:
(1) preparing a phenolic resin spinning solution;
(2) performing electrostatic spinning, curing and carbonization on the phenolic resin spinning stock solution to obtain phenolic resin-based carbon nanofibers;
(3) soaking the phenolic resin-based carbon nanofibers in 4-6mol/L hydrochloric acid solution for 3-5h, and washing to obtain activated phenolic resin-based carbon nanofibers;
(4) immersing the activated phenolic resin-based carbon nanofiber into a hydrothermal reaction solution, and reacting for 12-36h at the temperature of 100-150 ℃ to obtain a precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material; the hydrothermal reaction solution is formed by mixing 2 solutions, wherein the solution A is prepared by dissolving cobalt nitrate hexahydrate, nickel nitrate hexahydrate and urea in deionized water and then stirring for 10-20min, wherein the molar ratio of the cobalt nitrate hexahydrate, the nickel nitrate hexahydrate and the urea is (1-3) to 1: 12; dissolving dopamine hydrochloride and trihydroxymethyl aminomethane in deionized water, and magnetically stirring for 5-7 h, wherein the molar ratio of the dopamine hydrochloride to the trihydroxymethyl aminomethane is (3-4)): 1; mixing the two solutions A and B under stirring, and magnetically stirring for 20-40 min to obtain a hydrothermal reaction solution, wherein the solution A and the solution B are mixed in equal volume;
(5) and heating the precursor of the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite material to 200-400 ℃ at a speed of 3-5 ℃/min, roasting, and keeping the temperature for 60-180min to obtain the phenolic resin-based carbon nanofiber @ nickel cobaltate/dopamine composite electrode.
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