CN101290836A - Method for enhancing specific capacitance of phenolic resin based activated carbon fiber - Google Patents
Method for enhancing specific capacitance of phenolic resin based activated carbon fiber Download PDFInfo
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Abstract
The invention discloses a method for improving specific capacitance of phenolic resin-based activated carbon fiber, which comprises the following process steps that: the phenolic resin-based activated carbon fiber is subject to the oxidation treatment and is washed and dried, and the capacitance performance of the oxidized phenolic resin-based activated carbon fiber is detected. The invention adopts oxidant to perform oxidation treatment to the phenolic resin-based activated carbon fiber in inorganic acid medium to prepare an acid material of electrodes of a high-capacity electrochemical capacitor. The mass specific capacitance of the phenolic resin-based activated carbon fiber treated by the method is 2.2 times of that of the phenolic resin-based activated carbon fiber without the oxidation treatment. Compared with the prior method, the method has the advantages of simple method, easily-obtained raw materials, low product cost and so on; and the mass specific capacitance of the material treated by the method is effectively improved.
Description
Technical field
The invention belongs to the absorbent charcoal material technical field, be specifically related to adopt oxidant and inorganic acid, improve the method for phenolic resin based activated carbon fiber than electric capacity to the phenolic resin based activated carbon fiber oxidation processes.
Background technology
Phenolic resin based activated carbon fiber (ACF) specific area height, pore-size distribution is narrow and controlled, and the adsorption desorption function admirable can be widely used in the absorption of multiple material in the gas, liquid.Because the purity height of phenolic resin based activated carbon fiber, content of heteroatoms is few, and especially metallic atom content is few, can be used as catalyst carrier; In addition, because its unique three-dimensional crosslinking structure makes its carbon residue amount height, excellent conductivity is the desirable electrode material of super electrochemical capacitor.The energy storage of super electrochemical capacitor in the inorganic electrolyte liquid not only pore structure with porous material is relevant, and relevant with hole surface quinonyl oxygen-containing functional group.The former gives the electrode material electric double layer capacitance, and the latter gives the electrochemistry fake capacitance.Method by regulation activity raw material of wood-charcoal material pore structure, can improve its electric double layer capacitance amount in inorganic electrolyte liquid, but limited (Carbon 44 (2006) 2360-2367 of increase rate, Electrochimica Acta 50 (2005) 1197-1206, Journal of Power Sources 161 (2006) 730-736).If handle absorbent charcoal material by chemical method, make its surface contain quinones functional group, can not only improve the polarizable degree of electrode, also can improve the wettability of electrolyte and electrode material, and then obtain the electrochemistry fake capacitance, improve the energy density of electrochemical capacitor.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of method is easy, product cost is low, effectively improve the method for phenolic resin based activated carbon fiber than electric capacity.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
1, to the phenolic resin based activated carbon fiber oxidation processes
Be added to phenolic resin based activated carbon fiber, deionized water, oxidant, inorganic acid in the container successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, oxidant, inorganic acid is 1: 200: 20～45: 20～70, stir, heating, 35～95 ℃ to phenolic resin based activated carbon fiber oxidation processes 3～12 hours.
Above-mentioned phenolic resin based activated carbon fiber is that 3714111 the disclosed method of United States Patent (USP) prepares according to the patent No.; Above-mentioned inorganic acid is hydrochloric acid or nitric acid or sulfuric acid, and oxidant is potassium chlorate or potassium permanganate or potassium hyperchlorate.
2, washing is dry
The taking-up of phenolic resin based activated carbon fiber after the oxidation is washed till neutrality with deionized water, puts into 90～130 ℃ of dryings of air dry oven.
3, the ratio electric capacity of phenolic resin based activated carbon fiber after the detection oxidation processes
(1) preparation electrode slice
Phenolic resin based activated carbon fiber after the oxidation processes is ground to particle diameter less than 0.075mm, adding superconduct acetylene carbon black, mass concentration are 60% ptfe emulsion, the phenolic resin based activated carbon fiber of oxidation and superconduct acetylene carbon black, mass concentration are that the mass ratio of 60% ptfe emulsion is 87: 12: 1, stirring and evenly mixing, depressing to diameter with tablet press machine at 0.2 MPa pressure is that 9mm, thickness are the electrode slice of 0.3mm.
The specification of above-mentioned superconduct acetylene carbon black is 50% compression, is produced by Shanghai Rong Zhong Industrial Co., Ltd.; Mass concentration is 60% ptfe emulsion, and model is SFN-1, is produced by Sichuan morning twilight chemical research institute.
(2) preparation analog capacitor
Electrode slice is put into vacuum drying chamber, 125 ℃ of vacuumize 5 hours, immersing concentration is in the KOH solution of 7mol/L,-0.09MPa vacuum state soaked 1 hour down, at two electrode slice therebetween one layer thicknesses is the polypropylene diaphragm of 25 μ m, the nickel foam film that with thickness is 0.9mm is made collector electrode, packs in the analog capacitor of being made by polytetrafluoroethylene, is prepared into analog capacitor.
(3) the capacitive property parameter of test simulation capacitor
Capacitive property parameter with battery test system and test analog capacitor.
Of the present invention phenolic resin based activated carbon fiber is carried out in the oxidation processing technique step 1, phenolic resin based activated carbon fiber is 1: 200: 25～45: 30～60 with preferred weight part ratio of deionized water, oxidant, inorganic acid, stir, heating, preferred 45～75 ℃ to phenolic resin based activated carbon fiber oxidation processes 3～9 hours.
Of the present invention phenolic resin based activated carbon fiber is carried out in the oxidation processing technique step 1, phenolic resin based activated carbon fiber is 1: 200: 40 with optimum weight part ratio of deionized water, oxidant, inorganic acid: 40, stir, heating, best 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.
The present invention adopts oxidant oxidation processes phenolic resin based activated carbon fiber in inorganic acid medium, is prepared into high-capacity electrochemical capacitor electrode carbon material.The analog capacitor that the inventor will be prepared into through the phenolic resin based activated carbon fiber after the oxidation processes of the present invention has carried out contrast test with the analog capacitor that the phenolic resin based activated carbon fiber of oxidation processes not is prepared into, the result shows, the phenolic resin based activated carbon fiber specific discharge capacity after oxidation processes is 2.2 times of phenolic resin based activated carbon fiber specific discharge capacity of not oxidation processes.The present invention compares with existing method, has advantages such as method simply, raw materials used is easy to get, product cost is low, can be used for the phenolic resin based activated carbon fiber oxidation processes.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
1, to the phenolic resin based activated carbon fiber oxidation processes
Getting phenolic aldehyde base active glimmering fiber 1g, deionized water 200g, potassium permanganate 40g, mass concentration and be 68% salpeter solution 58.82g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 40: 40, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.
Above-mentioned phenolic resin based activated carbon fiber is that 3714111 the disclosed method of United States Patent (USP) prepares according to the patent No..
2, washing is dry
The taking-up of phenolic resin based activated carbon fiber after the oxidation is washed till neutrality with deionized water, puts into 120 ℃ of dryings of air dry oven, baking temperature can be chosen arbitrarily at 65～130 ℃, to the not influence of performance of phenolic resin based activated carbon fiber after the oxidation.
3, the capacitive property of phenolic resin based activated carbon fiber after the detection oxidation
(1) preparation electrode slice
Phenolic resin based activated carbon fiber behind the oxidation drying is ground to particle diameter less than 0.075mm, adding superconduct acetylene carbon black, mass concentration are 60% ptfe emulsion, the phenolic resin based activated carbon fiber of oxidation and superconduct acetylene carbon black, mass concentration are that the mass ratio of 60% ptfe emulsion is 87: 12: 1, stirring and evenly mixing, being pressed into diameter with tablet press machine 0.2MPa pressure is that 9mm, thickness are the electrode slice of 0.3mm.
The specification of above-mentioned superconduct acetylene carbon black is 50% compression powder, and mass concentration is 60% ptfe emulsion, and model is SFN-1.
(2) preparation analog capacitor
Electrode slice is put into vacuum drying chamber, 125 ℃ of vacuumize 5 hours, immersing concentration is in the KOH solution of 7mol/L,-0.09MPa vacuum state soaked 1 hour down, at two electrode slice therebetween one layer thicknesses is the polypropylene diaphragm of 25 μ m, the nickel foam film that with thickness is 0.9mm is made collector electrode, packs in the analog capacitor of being made by polytetrafluoroethylene, is prepared into analog capacitor.
(3) the capacitive property parameter of test simulation capacitor
With the capacitive property parameter of battery test system and test analog capacitor, the quality of phenolic resin based activated carbon fiber is 308F/g than electric capacity after the oxidation after testing.
Embodiment 2
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 29.41g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 45: 20, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 262F/g than electric capacity.
Embodiment 3
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 20g, mass concentration and be 68% salpeter solution 58.82g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 20: 40, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 261F/g than electric capacity.
Embodiment 4
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 20g, mass concentration and be 68% salpeter solution 29.41g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 20: 20, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.Other processing step is identical with embodiment 1.
Embodiment 5
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 102.94g is added in the 500mL there-necked flask successively, phenolic resin based activated carbon fiber is 1: 200: 45 with the weight part ratio of, deionized water, potassium permanganate, nitric acid: 70, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 271F/g than electric capacity.
Embodiment 6
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 58.82g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 45: 40, stir, heating, 35 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 278F/g than electric capacity.
Embodiment 7
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 58.82g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 45: 40, stir, heating, 95 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 268F/g than electric capacity.
Embodiment 8
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 58.82g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 45: 40, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 3 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 260F/g than electric capacity.
Embodiment 9
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
Present embodiment in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, nitric acid is inorganic acid, getting phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 58.82g is added in the 500mL there-necked flask successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, potassium permanganate, nitric acid is 1: 200: 45: 40, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 12 hours.Other processing step is identical with embodiment 1.Phenolic resin based activated carbon fiber after oxidation processes is prepared into analog capacitor, and with the capacitive property parameter of battery test system and test analog capacitor, quality is 272F/g than electric capacity.
Embodiment 10
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium chlorate is oxidant, nitric acid is inorganic acid, the consumption of nitric acid is identical with respective embodiments, the potassium chlorate quality is 45g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium chlorate, nitric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 11
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium hyperchlorate is an oxidant, nitric acid is inorganic acid, the consumption of nitric acid is identical with respective embodiments, the quality of potassium hyperchlorate is 45g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium hyperchlorate, nitric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 12
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, sulfuric acid is inorganic acid, the consumption of potassium permanganate is identical with respective embodiments, mass concentration is 98% sulfuric acid solution 40.82g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate, sulfuric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 13
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium chlorate is oxidant, sulfuric acid is inorganic acid, the consumption of potassium chlorate is 45g, mass concentration is 98% sulfuric acid solution 40.82g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium chlorate, sulfuric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 14
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium hyperchlorate is an oxidant, sulfuric acid is inorganic acid, the consumption of potassium hyperchlorate is 45g, mass concentration is that 98% sulfuric acid solution is 40.82g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium hyperchlorate, sulfuric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 15
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium permanganate is oxidant, hydrochloric acid is inorganic acid, the consumption of potassium permanganate is identical with respective embodiments, mass concentration is 37% hydrochloric acid solution 108.11g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium permanganate, hydrochloric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 16
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium chlorate is oxidant, hydrochloric acid is inorganic acid, the consumption of potassium chlorate is 45g, mass concentration is 37% hydrochloric acid solution 108.11g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium chlorate, hydrochloric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
Embodiment 17
With oxidized material phenolic resin based activated carbon fiber 1g is example, and other used material and proportioning and preparation method are as follows:
At above embodiment 1～9 in to phenolic resin based activated carbon fiber oxidation processing technique step 1, potassium hyperchlorate is an oxidant, hydrochloric acid is inorganic acid, the consumption of potassium hyperchlorate is 45g, mass concentration is 37% hydrochloric acid solution 108.11g, gets phenolic resin based activated carbon fiber 1g, deionized water 200g, potassium hyperchlorate, hydrochloric acid is added in the 500mL there-necked flask successively, stirs, heating, identical with respective embodiments to the phenolic resin based activated carbon fiber oxidation temperature with oxidization time.Other processing step is identical with embodiment 1.
In order to determine the processing step of the best of the present invention, the inventor has carried out a large amount of laboratory research tests, and various test situation are as follows:
Experiment material: phenolic resin based activated carbon fiber is the disclosed method self-control of 3714111 United States Patent (USP) according to the patent No.; The specification of superconduct acetylene carbon black is 50% compression, is produced by Shanghai Rong Zhong Industrial Co., Ltd.; Mass concentration is 60% ptfe emulsion, and model is SFN-1, is produced by Sichuan morning twilight chemical research institute; Polypropylene diaphragm, thickness are 25 μ m, are produced by Ji Mei Electronics Co., Ltd..
Laboratory apparatus: battery test system, model are CT2001A LAND, are produced by LAND Wuhan Jin Nuo Electronics Co., Ltd.; Tablet press machine, model are FW-4, are produced by the optical instrument factory, Tianjin.
1, sour kind is selected
Selection potassium permanganate is oxidant, get phenolic resin based activated carbon fiber 1g at every turn, water 200g, potassium permanganate 45g is encased in the there-necked flask, add acetate more respectively, formic acid, nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, carry out 6 experiments, oxidant is 1: 1.125 with the mass ratio of acid, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours, phenolic resin based activated carbon fiber after the oxidation is made electrode slice, at two electrode slice therebetween one layer thicknesses is the polypropylene diaphragm of 25 μ m, the nickel foam film that with thickness is 0.9mm is made collector electrode, pack in the analog capacitor of making by polytetrafluoroethylene, be prepared into analog capacitor, with the capacitive property of battery test system and test analog capacitor.Test result sees Table 1.
The different acid of table 1 to quality after the phenolic resin based activated carbon fiber oxidation processes than the influence of electric capacity
| Acid | Acetate | Formic acid | Nitric acid | Sulfuric acid | Phosphoric acid | Hydrochloric acid |
| Than electric capacity (F/g) | 140 | 150 | 278 | 273 | 135 | 271 |
By table 1 as seen, under the same conditions, during as acid medium, the phenolic resin based activated carbon fiber quality after the oxidation processes is all more higher than electric capacity with nitric acid, sulfuric acid, hydrochloric acid, and the present invention selects this three kinds of acid mediums that acid is used as activate.
2, the selection of oxidant kind
With nitric acid is acid medium, potassium chromate, potassium permanganate, potassium chlorate, postassium hypochlorite, potassium hyperchlorate, potassium nitrate is oxidant, get phenolic resin based activated carbon fiber 6g, water 1200g, be divided into 6 groups, every group of phenolic resin based activated carbon fiber 1g, water 200g is encased in the there-necked flask, add the oxidant potassium chromate respectively, potassium permanganate, potassium chlorate, postassium hypochlorite, potassium hyperchlorate, potassium nitrate, adding mass concentration at every group is 68% salpeter solution 58.82g, the mass ratio of oxidant and nitric acid is 1: 1.125, carry out 6 experiments, 65 ℃ were carried out oxidation processes 6 hours to phenolic resin based activated carbon fiber.The method for preparing analog capacitor is identical with experiment 1, is prepared into analog capacitor, with the capacitive property of battery test system and test analog capacitor.Test result sees Table 2.
The different oxidants of table 2 to the phenolic resin based activated carbon fiber oxidation processes after quality than the influence of electric capacity
| Oxidant | Potassium chromate | Potassium permanganate | Potassium chlorate | Postassium hypochlorite | Potassium hyperchlorate | Potassium nitrate |
| Quality is than electric capacity (F/g) | 195 | 278 | 272 | 190 | 269 | 209 |
By table 2 as seen, under identical experiment condition, select for use potassium permanganate, potassium chlorate, potassium hyperchlorate as oxidant phenolic resin based activated carbon fiber to be carried out oxidation, the phenolic resin based activated carbon fiber quality after the oxidation processes is more higher than electric capacity.The present invention selects potassium permanganate, potassium chlorate, the potassium hyperchlorate oxidant as the phenolic resin based activated carbon fiber oxidation processes.
3, oxidizing temperature determines
Get phenolic resin based activated carbon fiber 1g, water 200g, potassium permanganate 45g, mass concentration and be 68% salpeter solution 58.82g, be added to successively in the there-necked flask, heating, stir, adopt different oxidizing temperature constant temperature oxidation 6 hours.The method for preparing analog capacitor is identical with experiment 1, is prepared into analog capacitor, with the capacitive property of battery test system and test analog capacitor.Test result sees Table 3.
The different oxidation temperatures of table 3 to the phenolic resin based activated carbon fiber oxidation processes after quality than the influence of electric capacity
| Temperature (℃) | 25 | 35 | 45 | 55 | 65 | 75 | 85 | 95 | 105 | 115 |
| Quality is than electric capacity (F/g) | 255 | 260 | 263 | 269 | 278 | 273 | 271 | 268 | 202 | 176 |
By table 3 as seen, under identical experiment condition, the quality after the phenolic resin based activated carbon fiber oxidation processes increases along with the increase of oxidation temperature than electric capacity, but when temperature was higher than 95 ℃, quality descended than the increase of electric capacity with temperature.Selective oxidation treatment temperature of the present invention is 35～95 ℃, and the optimum oxidation treatment temperature is 65 ℃.
4, oxidation treatment time determines
Get phenolic resin based activated carbon fiber 1g, water 200g, mass concentration and be 68% salpeter solution 58.82g, potassium permanganate 45g, be added in the there-necked flask successively, stir, heating, the bottle interior reaction temperature remains on 65 ℃, at 1,2,3,6,9,12,15,18 hour phenolic resin based activated carbon fiber is carried out oxidation processes respectively.The method for preparing analog capacitor is identical with experiment 1, is prepared into analog capacitor, with the capacitive property of battery test system and test analog capacitor.Test result sees Table 4.
The different oxidation treatment times of table 4 to the phenolic resin based activated carbon fiber oxidation processes after quality than the influence of electric capacity
| Time (h) | 1 | 2 | 3 | 6 | 9 | 12 | 15 | 18 | 17 | 18 |
| Quality is than electric capacity (F/g) | 180 | 230 | 260 | 278 | 275 | 272 | 247 | 202 | 198 | 152 |
By table 4 as seen, under identical condition, the quality after the phenolic resin based activated carbon fiber oxidation processes increases along with the prolongation of oxidation treatment time than electric capacity, but oxidation treatment time is greater than 12 hours, and the quality of phenolic resin based activated carbon fiber is than the obvious decline of electric capacity.It is 3～12 hours that the present invention selects the oxidation treatment time to phenolic resin based activated carbon fiber, and the optimum oxidation time is 6 hours.
5, the selection of sour consumption
Branch is got phenolic resin based activated carbon fiber 1g, potassium permanganate 45g respectively 8 times, water 200g joins in the there-necked flask, add mass concentration respectively and be 68% salpeter solution 14.71g, 29.41g, 44.12g, 58.82g, 73.53g, 88.24g, 102.94g, 117.65g, 65 ℃ of constant temperature oxidation processes 6 hours.The method for preparing analog capacitor is identical with experiment 1, is prepared into analog capacitor, with the capacitive property of battery test system and test analog capacitor.Test result sees Table 5.
The different sour consumptions of table 5 to the phenolic resin based activated carbon fiber oxidation processes after quality than the influence of electric capacity
| Nitric acid dosage (g) | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 |
| Quality is than electric capacity (F/g) | 232 | 262 | 266 | 278 | 286 | 283 | 271 | 223 |
By table 5 as seen, under identical experiment condition, along with the increase of acid amount, the quality of phenolic resin based activated carbon fiber also increases than electric capacity thereupon, and when acid added greater than 70g, quality descended fairly obvious than electric capacity, and it is 20～70g that the present invention selects the nitric acid addition.
6, the selection of oxidant consumption
With nitric acid is medium, is oxidant with potassium permanganate.Getting phenolic resin based activated carbon fiber 1g, water 200g, mass concentration is 68% salpeter solution 58.82g, the potassium permanganate of different amounts, is added to respectively in the there-necked flask, and 65 ℃ of constant temperature oxidation processes 6 hours are carried out oxidation processes to phenolic resin based activated carbon fiber.The method for preparing analog capacitor is identical with experiment 1, is prepared into analog capacitor, with the capacitive property of battery test system and test analog capacitor.Test result sees Table 6.
The different oxidant consumptions of table 6 to the phenolic resin based activated carbon fiber oxidation processes after quality than the influence of electric capacity
| Oxidant content (g) | 15 | 20 | 25 | 30 | 35 | 40 | 45 | 55 |
| Quality is than electric capacity (F/g) | 187 | 261 | 265 | 273 | 279 | 308 | 278 | 221 |
By table 6 as seen, under identical experiment condition, along with the increase of oxidant addition, the quality of phenolic resin based activated carbon fiber also increases than electric capacity thereupon, and when oxidant consumption 45g, quality is than the obvious decline of electric capacity.The addition of oxidant of the present invention is selected 20～45g.
In order to verify beneficial effect of the present invention, the inventor adopts the phenolic resin based activated carbon fiber of the embodiment of the invention 1 after oxidation processes to be prepared into analog capacitor and is prepared into analog capacitor with the phenolic resin based activated carbon fiber of oxidation processes not and has carried out contrast test, with the capacitive property of battery test system and test analog capacitor.The result shows that the phenolic resin based activated carbon fiber specific discharge capacity of oxidation processes is not 140F/g, and the phenolic resin based activated carbon fiber specific discharge capacity after oxidation processes is 2.2 times of phenolic resin based activated carbon fiber specific discharge capacity of not oxidation processes.
Claims (3)
1, a kind of method that improves phenolic resin based activated carbon fiber than electric capacity is characterized in that it comprises the steps:
(1) phenolic resin based activated carbon fiber is carried out oxidation processes
Be added to phenolic resin based activated carbon fiber, deionized water, oxidant, inorganic acid in the container successively, the weight part ratio of phenolic resin based activated carbon fiber and deionized water, oxidant, inorganic acid is 1: 200: 20～45: 20～70, stir, heating, 35～95 ℃ to phenolic resin based activated carbon fiber oxidation processes 3～12 hours;
Above-mentioned inorganic acid is hydrochloric acid or nitric acid or sulfuric acid, and oxidant is potassium chlorate or potassium permanganate or potassium hyperchlorate;
(2) washing is dry
The taking-up of phenolic resin based activated carbon fiber after the oxidation is washed till neutrality with deionized water, puts into 65～130 ℃ of dryings of air dry oven;
(3) capacitive property of phenolic resin based activated carbon fiber after the detection oxidation
1. prepare electrode slice
Phenolic resin based activated carbon fiber behind the oxidation drying is ground to particle diameter less than 0.075mm, adding superconduct acetylene carbon black, mass concentration are 60% ptfe emulsion, the phenolic resin based activated carbon fiber of oxidation and superconduct acetylene carbon black, mass concentration are that the mass ratio of 60% ptfe emulsion is 87: 12: 1, stirring and evenly mixing, being pressed into diameter with tablet press machine 0.2MPa pressure is that 9mm, thickness are the thick electrode slice of 0.3mm;
2. prepare analog capacitor
Electrode slice is put into vacuum drying chamber, 125 ℃ of vacuumize 5 hours, immersing concentration is in the KOH solution of 7mol/L,-0.09MPa vacuum state soaked 1 hour down, at two electrode slice therebetween one layer thicknesses is the polypropylene diaphragm of 25 μ m, the nickel foam film that with thickness is 0.9mm is made collector electrode, packs in the analog capacitor of being made by polytetrafluoroethylene, is prepared into analog capacitor;
3. the capacitive property parameter of test simulation capacitor
Capacitive property parameter with battery test system and test analog capacitor.
2, according to the method for the described raising phenolic resin based activated carbon fiber of claim 1 than electric capacity, it is characterized in that: phenolic resin based activated carbon fiber is being carried out in the oxidation processing technique step (1), wherein the weight part ratio of phenolic resin based activated carbon fiber and deionized water, oxidant, inorganic acid is 1: 200: 25～45: 30～60, stir, heating, 45～75 ℃ to phenolic resin based activated carbon fiber oxidation processes 3～9 hours.
3, according to the method for the described raising phenolic resin based activated carbon fiber of claim 1 than electric capacity, it is characterized in that: phenolic resin based activated carbon fiber is carried out in the oxidation processing technique step (1) of the present invention, wherein phenolic resin based activated carbon fiber is 1: 200: 40 with the weight part ratio of, deionized water, oxidant, inorganic acid: 40, stir, heating, 65 ℃ to phenolic resin based activated carbon fiber oxidation processes 6 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021678A (en) * | 2010-09-16 | 2011-04-20 | 中国科学院西安光学精密机械研究所 | Method for surface treatment of carbon fiber |
| CN105047433A (en) * | 2015-06-30 | 2015-11-11 | 西安理工大学 | Method for preparing super-capacitor electrode |
| CN105895380A (en) * | 2016-04-12 | 2016-08-24 | 齐鲁工业大学 | Three-dimensional reticular polyaniline/phenolic resin-based carbon sphere composite material and preparation method thereof |
| CN110993375A (en) * | 2019-12-02 | 2020-04-10 | 山东理工大学 | Method for preparing compact-structure RGO/MXene-sulfuric acid supercapacitor flexible electrode in one step and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US3714111A (en) * | 1970-08-31 | 1973-01-30 | Carborundum Co | Ablative composites containing novolac fibers |
| JP2674057B2 (en) * | 1988-02-05 | 1997-11-05 | 松下電器産業株式会社 | Method of manufacturing polarizable electrodes |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021678A (en) * | 2010-09-16 | 2011-04-20 | 中国科学院西安光学精密机械研究所 | Method for surface treatment of carbon fiber |
| CN105047433A (en) * | 2015-06-30 | 2015-11-11 | 西安理工大学 | Method for preparing super-capacitor electrode |
| CN105895380A (en) * | 2016-04-12 | 2016-08-24 | 齐鲁工业大学 | Three-dimensional reticular polyaniline/phenolic resin-based carbon sphere composite material and preparation method thereof |
| CN105895380B (en) * | 2016-04-12 | 2018-09-04 | 齐鲁工业大学 | A kind of three-dimensional netted polyaniline/phenolic resin base carbon ball composite material and preparation method |
| CN110993375A (en) * | 2019-12-02 | 2020-04-10 | 山东理工大学 | Method for preparing compact-structure RGO/MXene-sulfuric acid supercapacitor flexible electrode in one step and application thereof |
| CN110993375B (en) * | 2019-12-02 | 2021-11-26 | 山东理工大学 | Method for preparing compact-structure RGO/MXene-sulfuric acid supercapacitor flexible electrode in one step and application thereof |
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