CN111063547A - Rod-shaped polyaniline/wood electrode material and preparation method and application thereof - Google Patents
Rod-shaped polyaniline/wood electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111063547A CN111063547A CN201911330706.3A CN201911330706A CN111063547A CN 111063547 A CN111063547 A CN 111063547A CN 201911330706 A CN201911330706 A CN 201911330706A CN 111063547 A CN111063547 A CN 111063547A
- Authority
- CN
- China
- Prior art keywords
- wood
- polyaniline
- rod
- electrode material
- aniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002023 wood Substances 0.000 title claims abstract description 149
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 76
- 239000007772 electrode material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 238000011049 filling Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000005457 ice water Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
- 238000004108 freeze drying Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229960000583 acetic acid Drugs 0.000 claims description 16
- 239000012362 glacial acetic acid Substances 0.000 claims description 16
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 16
- 229960002218 sodium chlorite Drugs 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000007710 freezing Methods 0.000 claims description 10
- 230000008014 freezing Effects 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 31
- 239000011148 porous material Substances 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- 238000003760 magnetic stirring Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- 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
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a rod-shaped polyaniline/wood electrode material and a preparation method and application thereof, wherein the method comprises the following steps of 1, adjusting the pH value of an aniline aqueous solution to 1-2 by using acid to obtain a mixed solution A, filling the mixed solution A into delignified wood after the mixed solution A is placed in an ice-water bath, and drying to obtain the wood containing aniline; and 2, placing the ammonium persulfate aqueous solution in an ice-water bath, filling the ammonium persulfate aqueous solution in the aniline-containing wood, and drying the ammonium persulfate aqueous solution, wherein the molar ratio of aniline in the aniline aqueous solution to ammonium persulfate in the ammonium persulfate aqueous solution is 1: (1-2) obtaining the rod-like polyaniline/wood electrode material. According to the invention, the rod-shaped polyaniline can be uniformly grown on the pore channels and the surfaces of the wood to obtain the composite material with the polyaniline wood, so that the transmission quantity of electrons is increased, the electrochemical performance of the material is improved, the conductivity and the structural stability of the material are improved, the internal resistance of the material is reduced, the conductivity of the material is improved, and the energy storage characteristic of the material is improved.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to a rod-shaped polyaniline/wood electrode material and a preparation method and application thereof.
Background
In recent years, petroleum crisis has been developed for many times globally, so that many countries make a decision to develop their own resource development strategy. Compared with petroleum-based materials, the bio-based materials have the advantages of abundant reserves, wide sources, reproducibility, degradability and the like; meanwhile, the production process of the bio-based material is green and environment-friendly, the emission of carbon dioxide is relatively low, and the requirement of people in the twenty-first century on environmental protection is met. Wood has long received considerable attention from researchers as one of the most abundant biobased materials in nature. Wood is the only renewable, recyclable and naturally degradable material in four major materials in the world today, namely steel, cement, wood and plastic. The wood has a fixed space for accommodating other particles or powder, polymers and other structural units, which are mostly caused by the conduits and the sieve pipes left by the life activities of the wood, and a great development space is provided for the performance improvement and the functionalization of the wood.
It is very important to find a conductive material which has good compatibility with wood and can be closely adhered to the wood. Conductive polymers, such as polyaniline or polypyrrole, are very potential materials, have inherent fast redox ability, high conductivity, and can form chemical bonding with cellulose in wood matrix to generate strong adhesion. In addition, the poor cycling stability of polyaniline is caused by shrinkage, expansion and the like of the volume in the charging and discharging processes, so that the commercialization of the polyaniline is limited, and the pore channels of wood can reduce the shrinkage and expansion of the volume of the polyaniline and enhance the stability of the polyaniline, but the preparation of the conductive material by attaching the polyaniline to the wood is not reported at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a rod-shaped polyaniline/wood electrode material, a preparation method and application thereof, which are simple in synthesis, low in cost and environment-friendly, improve the conductivity and structural stability of the material, and improve the conductivity and energy storage characteristics of the material.
The invention is realized by the following technical scheme:
a preparation method of a rod-shaped polyaniline/wood electrode material comprises the following steps,
and 2, placing the ammonium persulfate aqueous solution in an ice-water bath, filling the ammonium persulfate aqueous solution in the aniline-containing wood, and drying the ammonium persulfate aqueous solution, wherein the molar ratio of aniline in the aniline aqueous solution to ammonium persulfate in the ammonium persulfate aqueous solution is 1: (1-2) obtaining the rod-like polyaniline/wood electrode material.
Preferably, in step 1, the acid is hydrochloric acid, sulfuric acid or nitric acid.
Preferably, in the step 1, the pH of the aniline aqueous solution is adjusted by acid, and then the aniline aqueous solution is magnetically stirred for 3-5 min to obtain a mixed solution A.
Preferably, in the step 1, the mixed solution A is filled in delignified wood and then is frozen and dried for 10-12 hours at the temperature of-50 to-40 ℃ to obtain wood containing aniline;
in the step 2, ammonium persulfate aqueous solution is filled in the aniline-containing wood and then is frozen and dried for 10-12 hours at the temperature of-50 to-40 ℃ to obtain the rod-shaped polyaniline/wood electrode material.
Preferably, in step 1, said delignified wood is obtained by,
step 1a, soaking wood in a mixed aqueous solution of sodium chlorite and glacial acetic acid, and taking out the wood after the wood lasts for 12-18 hours at the temperature of 80-90 ℃;
and step 1b, freezing the wood obtained in the step 1a at the temperature of between 20 ℃ below zero and 15 ℃ below zero for 4 to 12 hours, and then carrying out freeze drying at the temperature of between 50 ℃ below zero and 40 ℃ below zero for 10 to 12 hours to obtain delignified wood.
Further, in the step 1a, the wood is in a cuboid shape, the length is 1-4 cm, the width is 0.5-1 cm, and the thickness is 1-5 mm;
and soaking the wood in a mixed aqueous solution of sodium chlorite and glacial acetic acid at a rotating speed of 100-200 rpm.
Further, in the step 1a, in the mixed aqueous solution of sodium chlorite and glacial acetic acid, the ratio of the sodium chlorite to the glacial acetic acid to the deionized water is (0.2-0.4) g: (1-1.5) ml: (25-50) ml.
A rod-like polyaniline/wood electrode material obtained by the method for preparing the rod-like polyaniline/wood electrode material.
A super capacitor containing the rodlike polyaniline/wood electrode material.
An electronic device driven by the super capacitor.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which adopts an in-situ chemical polymerization method to prepare a polyaniline/wood composite material, selects aniline as a monomer, acid as a proton dopant and ammonium persulfate as an oxidant, uniformly grows rod-shaped polyaniline on pore canals and surfaces of wood, and the rod-shaped polyaniline is uniformly grown on the pore canals and the surfaces of the wood by finely regulating and controlling the polymerization of the aniline to obtain the composite material with polyaniline wood; the polyaniline prepared by the method improves the transmission quantity of electrons, the electrochemical performance of the material, the conductivity and the structural stability of the material, reduces the internal resistance of the material, improves the conductivity of the material and improves the energy storage characteristic of the material.
Furthermore, a large amount of space structures generated after delignification treatment is carried out on wood by sodium chlorite and glacial acetic acid provide more effective micro-pore structures for the material.
The rod-shaped polyaniline/wood electrode material prepared by the invention is a wood porous electrode for a super capacitor electrode, and the wood porous electrode with light weight and good conductivity can be obtained by filling conductive polymer monomers in the wood porous electrode and carrying out oxidative polymerization reaction in pore channels; the porous holes of the wood not only increase the specific surface area of the active substance, but also can be used as a storage warehouse of the electrolyte, and meanwhile, the cellular porous structure of the wood also has the energy absorption/release performance, so that the stress generated in the repeated doping/dedoping process of the conductive polymer can be absorbed and released, and the super capacitor is ensured to have good cycling stability.
Drawings
FIG. 1 is a scanning electron micrograph of lignin-removed wood of example 1 of the present invention at 100 μm.
Fig. 2 is a scanning electron microscope image of the polyaniline/wood electrode material of example 1 of the present invention at 10 μm.
Fig. 3 is a scanning electron microscope image of the polyaniline/wood electrode material of example 1 of the present invention at 400 μm.
FIG. 4 is a transmission electron micrograph of the polyaniline/wood electrode material of example 1 of the present invention at 1 μm.
Fig. 5 is a cyclic voltammogram of the polyaniline/wood electrode material in example 1 of the present invention.
Fig. 6 is a constant current charging and discharging graph of the polyaniline/wood electrode material in example 1 of the present invention.
Fig. 7 is an electrochemical impedance diagram of the polyaniline/wood electrode material in examples 1, 2 and 3 of the present invention.
Fig. 8 is a graph of current density, specific capacitance and energy efficiency of the polyaniline/wood electrode material in example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Polyaniline has the advantages of unique doping mechanism, excellent physical and chemical properties, good environmental stability, cheap raw materials, convenient synthesis and the like, and has wide application prospect in the fields of energy sources, electromagnetic shielding, biosensors, photoelectronic devices and the like. The polyaniline has simple preparation process, and has the characteristics of environmental friendliness and low cost compared with most metal-based electrode materials. The method for synthesizing polyaniline is various, the main methods are chemical oxidative polymerization and electrochemical polymerization, the yield of products prepared by the chemical oxidative polymerization is high, the process flow is simple, and the method is suitable for industrial production; the polyaniline obtained by the electrochemical polymerization method has high purity and simpler synthesis, but is not beneficial to mass production, so the invention adopts the chemical oxidative polymerization method to synthesize the polyaniline.
The invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which aims to solve the problems of high preparation cost, low energy efficiency and poor conductivity of a biomass energy storage material and comprises the following steps,
cutting wood into slices with the length of 1-4 cm, the width of 0.5-1 cm and the thickness of 1-5 mm, weighing 0.2-0.4 g of sodium chlorite and 1-1.5 ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the slices in 25-50 ml of deionized water, putting the prepared wood into the beaker, freezing the wood at the temperature of 80-90 ℃ and the rotating speed of 100-200 rpm for 12-18 h to obtain delignified wood, freezing the delignified wood at the temperature of-20 to-15 ℃ for 4-12 h in a refrigerator, and then freezing and drying the delignified wood at the temperature of-50 to-40 ℃ for 10-12 h to obtain dried delignified wood;
weighing 2-11 g of ammonium persulfate, adding 10-20 ml of deionized water, stirring until the ammonium persulfate is dissolved to obtain an ammonium persulfate solution,
the molar ratio of aniline in the hydrochloric acid and aniline mixed solution to ammonium persulfate in the ammonium persulfate solution is 1: (1-2);
the invention arranges the diaphragm between the two electrode materials which are both rod-shaped polyaniline/wood, and assembles the brand new super capacitor.
The invention provides electronic equipment with the super capacitor, wherein the electronic equipment is an electric automobile, a mobile phone and the like, and can be stably powered.
According to the method, firstly, lignin of the wood is removed, the time required by the lignin removing process can be reduced by enlarging the ratio of sodium chlorite to glacial acetic acid, and the lignin is removed more thoroughly, so that the wood containing a large number of pore channels is obtained; the polyaniline/wood composite material with the rod-like structure is obtained by blowing mixed aqueous solution of aniline and hydrochloric acid and then blowing ammonium persulfate to carry out oxidative polymerization on aniline monomers; on one hand, the removal of lignin provides a large amount of effective pore structures for the growth of polyaniline, and a good conductive network is constructed for the material; on the other hand, the poor circulation stability of polyaniline due to shrinkage, expansion and the like of the volume in the charging and discharging processes limits the commercialization of the polyaniline, and the pore channels of wood can reduce the shrinkage and expansion of the volume of the polyaniline and enhance the stability of the polyaniline.
The polyaniline material has wide sources and simple preparation process, and the formed rod-shaped structure provides effective pore channels for the infiltration of electrolyte and the storage and transmission of electrons, thereby improving the electrochemical performance of the material; the wood with the lignin removed is used for growing polyaniline, so that the conductivity and electrochemical performance of the material are greatly improved; in addition, due to the introduction of a large amount of biomass energy, a new thought and an example are provided for the development of novel energy materials.
Example 1
The invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which comprises the following steps,
and 3, placing the prepared mixed solution of hydrochloric acid and aniline in an ice water bath, pumping the mixed solution into the wood by adopting a repeated vacuumizing and nitrogen filling mode, performing freeze drying for 48 hours at the temperature of minus 45 ℃, filling ammonium persulfate into the surfaces and pore channels of the wood samples after freeze drying in the ice water bath by adopting the same vacuumizing and nitrogen filling mode, and performing freeze drying for 48 hours at the temperature of minus 45 ℃.
Example 2
The invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which comprises the following steps,
and 3, placing the prepared mixed solution of hydrochloric acid and aniline in an ice water bath, pumping the mixed solution into the wood by adopting a repeated vacuumizing and nitrogen filling mode, performing freeze drying for 48 hours at the temperature of minus 45 ℃, filling ammonium persulfate into the surface and pore channels of the wood sample after freeze drying in the ice water bath by adopting the same vacuumizing and nitrogen filling mode, and performing freeze drying for 48 hours at the temperature of minus 45 ℃.
Example 3
The invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which comprises the following steps,
and 3, placing the prepared mixed solution of hydrochloric acid and aniline in an ice water bath, pumping the mixed solution into the wood by adopting a repeated vacuumizing and nitrogen filling mode, performing freeze drying for 48 hours at the temperature of minus 45 ℃, filling ammonium persulfate into the surface and pore channels of the wood sample after freeze drying in the ice water bath by adopting the same vacuumizing and nitrogen filling mode, and performing freeze drying for 48 hours at the temperature of minus 45 ℃.
Example 4
The invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which comprises the following steps,
and 3, placing the prepared mixed solution of hydrochloric acid and aniline in an ice water bath, pumping the mixed solution into the wood by adopting a repeated vacuumizing and nitrogen filling mode, performing freeze drying for 10 hours at the temperature of minus 50 ℃, filling ammonium persulfate into the surface and pore channels of the wood sample after freeze drying in the ice water bath by adopting the same vacuumizing and nitrogen filling mode, and performing freeze drying for 30 hours at the temperature of minus 40 ℃.
Example 5
The invention relates to a preparation method of a rod-shaped polyaniline/wood electrode material, which comprises the following steps,
and 3, placing the prepared mixed solution of hydrochloric acid and aniline in an ice water bath, pumping the mixed solution into the wood by adopting a repeated vacuumizing and nitrogen filling mode, carrying out freeze drying for 25 hours at the temperature of minus 40 ℃, filling ammonium persulfate into the surface and pore channels of the wood sample after freeze drying in the ice water bath by adopting the same vacuumizing and nitrogen filling mode, and carrying out freeze drying for 10 hours at the temperature of minus 50 ℃.
Fig. 1 shows that the wood without lignin contains a large number of 3D pore structures, and it can be seen from fig. 2 that polyaniline is generated in the pores of the wood. From fig. 3, polyaniline having a rod-like structure can be found. The rod-like structure of polyaniline can be seen from fig. 4 and stacked on each other.
Fig. 5 shows that the curve has obvious oxidation-reduction peaks, wherein the ordinate current density is calculated by the mass and area of the measured material, and the area of the closed curve is gradually increased along with the increase of the sweep rate, which indicates that the material has stable cyclic voltammetry characteristics under different sweep rates.
Fig. 6 shows that the curve is not a regular triangle, because polyaniline has capacitance and thus redox reaction, and it can conduct electricity by redox reaction, so the rod-like electrode material obtained by the present invention has longer discharge time and higher specific capacitance.
Figure 7 shows that the internal resistance of the composite is significantly reduced by polymerization of aniline. Wood, Wood @ PANI 1 ', Wood @ PANI 2 ', Wood @ PANI 3 ' in the legend are Wood materials obtained under the conditions of lignin-removed Wood, application example 1, application example 2, and application example 3, respectively. Compared with wood, the semi-circular arcs of other curves with the abscissa of 0-25 ohm are smaller and smaller, the slope of the oblique line behind the semi-circular arc is higher and higher, and the internal resistance of the material is smaller. The radius of the semicircular arc of the curve of application example 3 is minimum, and the slope of the semicircular rear slope is maximum, which shows that the internal resistance of application example 3 is minimum and the conductivity is good.
Fig. 8 shows that when the current density is 10A/g, the specific capacitance of the prepared electrode material can reach more than 800F/g when viewed from the left ordinate, and when the current density is 40A/g, the energy efficiency can reach 80% when viewed from the right ordinate, so that the electrode material has a good practical application value. Under different current densities, the specific capacitance is over 500F/g, and the larger the specific capacitance value is, the better the conductivity of the material is. In addition, in the specific application of the energy storage material, energy loss is inevitably caused, the energy efficiency shows the capability of the material for converting chemical energy into electric energy, the energy efficiency is already good at more than 60%, and when the current density is 40A/g, the energy efficiency is as high as 80%, shows the good energy conversion performance of the material and has higher practical application value.
Claims (10)
1. A preparation method of a rod-shaped polyaniline/wood electrode material is characterized by comprising the following steps,
step 1, adjusting the pH value of an aniline aqueous solution to 1-2 by using acid to obtain a mixed solution A, filling the mixed solution A into delignified wood after the mixed solution A is placed in an ice water bath, and drying to obtain the wood containing aniline;
and 2, placing the ammonium persulfate aqueous solution in an ice-water bath, filling the ammonium persulfate aqueous solution in the aniline-containing wood, and drying the ammonium persulfate aqueous solution, wherein the molar ratio of aniline in the aniline aqueous solution to ammonium persulfate in the ammonium persulfate aqueous solution is 1: (1-2) obtaining the rod-like polyaniline/wood electrode material.
2. The method for preparing a rod-shaped polyaniline/wood electrode material as claimed in claim 1, wherein in step 1, the acid is hydrochloric acid, sulfuric acid or nitric acid.
3. The method for preparing a rod-shaped polyaniline/wood electrode material as claimed in claim 1, wherein in step 1, the pH of the aniline aqueous solution is adjusted by acid, and then the mixture is magnetically stirred for 3-5 min to obtain a mixed solution A.
4. The preparation method of the rod-shaped polyaniline/wood electrode material as claimed in claim 1, wherein in step 1, the mixed solution A is filled in delignified wood and then is freeze-dried for 10-12 h at-50 to-40 ℃ to obtain wood containing aniline;
in the step 2, ammonium persulfate aqueous solution is filled in the aniline-containing wood and then is frozen and dried for 10-12 hours at the temperature of-50 to-40 ℃ to obtain the rod-shaped polyaniline/wood electrode material.
5. The method for preparing a rod-shaped polyaniline/wood electrode material as claimed in claim 1, wherein in step 1, the delignified wood is obtained by the steps of,
step 1a, soaking wood in a mixed aqueous solution of sodium chlorite and glacial acetic acid, and taking out the wood after the wood lasts for 12-18 hours at the temperature of 80-90 ℃;
and step 1b, freezing the wood obtained in the step 1a at the temperature of between 20 ℃ below zero and 15 ℃ below zero for 4 to 12 hours, and then carrying out freeze drying at the temperature of between 50 ℃ below zero and 40 ℃ below zero for 10 to 12 hours to obtain delignified wood.
6. The preparation method of the rod-shaped polyaniline/wood electrode material as claimed in claim 5, wherein in step 1a, the wood is cuboid, 1-4 cm long, 0.5-1 cm wide and 1-5 mm thick;
and soaking the wood in a mixed aqueous solution of sodium chlorite and glacial acetic acid at a rotating speed of 100-200 rpm.
7. The method for preparing a rod-shaped polyaniline/wood electrode material as claimed in claim 5, wherein in the step 1a, the ratio of sodium chlorite to glacial acetic acid to deionized water in the mixed aqueous solution of sodium chlorite and glacial acetic acid is (0.2-0.4) g: (1-1.5) ml: (25-50) ml.
8. A rod-like polyaniline/wood electrode material obtained by the method for preparing a rod-like polyaniline/wood electrode material according to any one of claims 1 to 7.
9. A supercapacitor comprising the rod-shaped polyaniline/wood electrode material of claim 8.
10. An electronic device driven by the supercapacitor of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911330706.3A CN111063547B (en) | 2019-12-20 | 2019-12-20 | Rod-shaped polyaniline/wood electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911330706.3A CN111063547B (en) | 2019-12-20 | 2019-12-20 | Rod-shaped polyaniline/wood electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111063547A true CN111063547A (en) | 2020-04-24 |
| CN111063547B CN111063547B (en) | 2021-12-07 |
Family
ID=70300822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911330706.3A Active CN111063547B (en) | 2019-12-20 | 2019-12-20 | Rod-shaped polyaniline/wood electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111063547B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002946A (en) * | 2020-08-06 | 2020-11-27 | 山东科技大学 | Preparation method and application of polyaniline zinc ion battery of high-voltage platform |
| CN114102776A (en) * | 2021-12-03 | 2022-03-01 | 东北林业大学 | Preparation method of flame-retardant wood by in-situ polymerization of aniline |
| CN115304121A (en) * | 2022-06-27 | 2022-11-08 | 河海大学 | Preparation method and application of polyaniline-wood double-layer evaporation material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006027262A (en) * | 2004-06-15 | 2006-02-02 | Kosaka Sangyo Kk | Lignin-free wood chip, its manufacturing method and garbage decomposition assistant using this wood chip |
| CN103745832A (en) * | 2013-12-11 | 2014-04-23 | 中国林业科学研究院木材工业研究所 | A wooden flexible supercapacitor and a preparation method of wooden flexible porous electrodes thereof |
| CN107742583A (en) * | 2017-09-28 | 2018-02-27 | 中国林业科学研究院木材工业研究所 | A kind of wooden based combined electrode material and preparation method thereof |
| CN110256733A (en) * | 2019-06-26 | 2019-09-20 | 广西大学 | The preparation method of cellulose network polyaniline composite material and supercapacitor |
| CN110253703A (en) * | 2019-05-07 | 2019-09-20 | 杭州电子科技大学 | A kind of preparation method and the antibacterial timber of high intensity of the antibacterial timber of high intensity |
| CN110416479A (en) * | 2019-07-31 | 2019-11-05 | 东华大学 | A kind of multichannel carbide wood interlayer and its preparation and application with orientation |
-
2019
- 2019-12-20 CN CN201911330706.3A patent/CN111063547B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006027262A (en) * | 2004-06-15 | 2006-02-02 | Kosaka Sangyo Kk | Lignin-free wood chip, its manufacturing method and garbage decomposition assistant using this wood chip |
| CN103745832A (en) * | 2013-12-11 | 2014-04-23 | 中国林业科学研究院木材工业研究所 | A wooden flexible supercapacitor and a preparation method of wooden flexible porous electrodes thereof |
| CN107742583A (en) * | 2017-09-28 | 2018-02-27 | 中国林业科学研究院木材工业研究所 | A kind of wooden based combined electrode material and preparation method thereof |
| CN110253703A (en) * | 2019-05-07 | 2019-09-20 | 杭州电子科技大学 | A kind of preparation method and the antibacterial timber of high intensity of the antibacterial timber of high intensity |
| CN110256733A (en) * | 2019-06-26 | 2019-09-20 | 广西大学 | The preparation method of cellulose network polyaniline composite material and supercapacitor |
| CN110416479A (en) * | 2019-07-31 | 2019-11-05 | 东华大学 | A kind of multichannel carbide wood interlayer and its preparation and application with orientation |
Non-Patent Citations (1)
| Title |
|---|
| SHUAI YU ET AL.: "Synthesis of wood derived nitrogen-doped porous carbon–polyaniline composites for supercapacitor electrode materials", 《RSC ADVANCES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002946A (en) * | 2020-08-06 | 2020-11-27 | 山东科技大学 | Preparation method and application of polyaniline zinc ion battery of high-voltage platform |
| CN112002946B (en) * | 2020-08-06 | 2022-04-15 | 山东科技大学 | Preparation method and application of polyaniline zinc ion battery of high-voltage platform |
| CN114102776A (en) * | 2021-12-03 | 2022-03-01 | 东北林业大学 | Preparation method of flame-retardant wood by in-situ polymerization of aniline |
| CN115304121A (en) * | 2022-06-27 | 2022-11-08 | 河海大学 | Preparation method and application of polyaniline-wood double-layer evaporation material |
| CN115304121B (en) * | 2022-06-27 | 2023-11-17 | 河海大学 | Preparation method and application of polyaniline-wood double-layer evaporation material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111063547B (en) | 2021-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111063547B (en) | Rod-shaped polyaniline/wood electrode material and preparation method and application thereof | |
| Wang et al. | Recent progress in carbonyl-based organic polymers as promising electrode materials for lithium-ion batteries (LIBs) | |
| Yang et al. | Self-healing strategy for Si nanoparticles towards practical application as anode materials for Li-ion batteries | |
| CN107017091B (en) | Nitrogenous multistage porous carbon/graphene composite material and its preparation method and application | |
| CN105609720B (en) | A kind of preparation method of NiPC@CNTs/S composites and application | |
| CN103985840A (en) | Lithium negative electrode with functional protective layer and lithium sulfur battery | |
| CN110336037B (en) | Water-based binder for lithium ion battery cathode material and preparation method thereof | |
| CN108832126B (en) | Polycarboxylic acid aqueous binder containing coupling amido bond, preparation method and application thereof in lithium ion battery | |
| CN110190284B (en) | Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof | |
| CN112500563B (en) | Synthesis method of three-dimensional conjugated conductive polyaniline and application of three-dimensional conjugated conductive polyaniline as negative electrode binder of lithium ion battery | |
| CN105355876B (en) | Composite conductive polymer coats the preparation method and its usage of elemental sulfur | |
| CN111224097B (en) | Lead paste, battery plate and preparation method and application thereof | |
| CN113658806B (en) | Gel electrode doped with polyaniline in situ and preparation method and application thereof | |
| Zhang et al. | Advances in polymer electrolytes for solid-state zinc–air batteries | |
| CN108831749B (en) | Electrochemical energy storage composite material and preparation method thereof | |
| CN110581210B (en) | Preparation method of PPy-SWCNTs nano composite thermoelectric film and nano composite thermoelectric film | |
| CN108390011B (en) | Lithium manganate, graphene oxide and carbon nanotube composite aerogel as well as preparation method and application thereof | |
| CN115424867B (en) | Flexible super capacitor and preparation method thereof | |
| KR20180130477A (en) | Method for preparing polyaniline gel for super capacitor electrode, method for preparing polyaniline fiber for super capacitor electrode using thereof and application thereof | |
| CN108538646B (en) | Preparation method and application of nanometer flower-like polypyrrole manganese oxide composite material | |
| CN113248672A (en) | Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof | |
| KR20180016054A (en) | Method for preparing polyaniline gel for super capacitor electrode, method for preparing polyaniline fiber for super capacitor electrode using thereof and application thereof | |
| Su et al. | Preparation of the nanocarbon/polypyrrole composite electrode by in situ electrochemical polymerization and its electrochemical performances as the cathode of the lithium ion battery | |
| CN114361391B (en) | Polymer modified nano silicon negative electrode material and preparation method and application thereof | |
| Guo et al. | Synthesis of Organic Acid Doped Polypyrrole and Its Evaluationas a Novel Cathode Material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220822 Address after: No. 5A-06, 5th Floor, Hesheng International Commodity Trading Center, Weiyang District, Xi'an City, Shaanxi Province 710016 Patentee after: Xi'an Ruilijie Experimental Instrument Co.,Ltd. Address before: 710021 Shaanxi province Xi'an Weiyang University Park Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
|
| TR01 | Transfer of patent right |