CN109962209A - Preparation method of high-efficiency oxygen catalytic active carbon fiber electrode - Google Patents
Preparation method of high-efficiency oxygen catalytic active carbon fiber electrode Download PDFInfo
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- CN109962209A CN109962209A CN201711405248.6A CN201711405248A CN109962209A CN 109962209 A CN109962209 A CN 109962209A CN 201711405248 A CN201711405248 A CN 201711405248A CN 109962209 A CN109962209 A CN 109962209A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 123
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 123
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 123
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000001301 oxygen Substances 0.000 title claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 47
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 230000003647 oxidation Effects 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000009467 reduction Effects 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 21
- 230000005611 electricity Effects 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 241000108463 Hygrophila <snail> Species 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 239000013535 sea water Substances 0.000 abstract description 26
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 150000002825 nitriles Chemical class 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000010165 autogamy Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
Abstract
The invention relates to a preparation method of a high-efficiency oxygen catalytic active carbon fiber electrode. The invention belongs to the technical field of electric energy materials. A preparation method of a high-efficiency oxygen catalytic active carbon fiber electrode is characterized by comprising the following steps: the preparation method of the high-efficiency oxygen catalytic active carbon fiber electrode comprises the following process steps: twisting and bundling polyacrylonitrile carbon fibers into a brush, taking the polyacrylonitrile carbon fiber brush as an electrode, taking the same carbon fiber brush as an auxiliary electrode, and continuously performing oxidation and reduction alternate treatment in a sulfuric acid electrolyte solution under constant current density to obtain the polyacrylonitrile carbon fiber brush electrode subjected to electrochemical modification treatment. The carbon fiber cathode of the seawater dissolved oxygen battery prepared by the method has the advantages of high catalytic activity, good electrochemical performance, simple process, low cost and the like.
Description
Technical field
The invention belongs to electric energy field of material technology, more particularly to a kind of efficient oxygen catalytic activity carbon fiber electrode
Preparation method.
Background technique
Carbon fiber is due to low-density, high specific strength, high-low temperature resistant, anticorrosive and excellent conduction and thermal conductivity
The features such as energy, it is known as the king of new material, it is each to can be widely applied to the army and the people such as space flight, aviation, traffic, automobile, electric energy
Field.
Be commercialized at present Kongsberg Simrad company, Norway production SWB1200 seawater dissolved oxygen battery, be exactly
Anode of the carbon fiber brush of use as seawater battery.The carbon fiber electrode used due to it without surface modification treatment,
Surface inertness is larger, active function groups are few, electro catalytic activity site is few, causes Dissolved Oxygen in Seawater cathodic reduction reaction electro-catalysis
Performance is low, can only work under extremely low current density, is unable to the higher current density of load, and the power density of battery is caused to export
Characteristic is poor, needs just to be able to satisfy the power demand of seawater battery with a large amount of carbon fibre material, certainly will increase battery volume and
Weight.
In order to improve carbon fiber electrode to the catalytic activity of Dissolved Oxygen in Seawater, it is necessary to be carried out to it at surface active modification
Reason.The surface modifying treatment of carbon fibre material mainly has gas phase and liquid phase oxidizing process, electrochemical oxidation process, microwave thermal at present
Facture, plasma method etc..Wherein, adulterated by electrochemical surface redox processing, heat treatment nitrogen etc., change carbon fiber
Surface atom state, carbon fibre material can be obviously improved to the electro catalytic activity of oxygen.
CN203960365U discloses a kind of carbon fiber anodic oxidation surface processing device, and the invention is using carbon fiber as sun
Pole, for graphite plate as cathode, electrolyte is ammonium hydrogen carbonate, is handled under DC electric field effect carbon fiber surface.The hair
The parameters such as the bright electrolyte concentration for being not directed to surface treatment, temperature, oxidation current, processing time.Furthermore the invention uses graphite
Plate polarizes larger as cathode auxiliary electrode when will lead to oxidation, and carbon fibre anode surface treatment properties are not high.
CN103361768A discloses a kind of polypropylene-base carbon fiber surface modification method, and this method is by carbon fiber first
Matrix high temperature cabonization at 1500 ゜ C, corona treatment is then carried out in atmosphere of inert gases, next passes through atomization again
Device carries out atomization process.This method complex process, it is cumbersome, it is at high cost；The high requirements on the equipment；The method increase materials
The interlaminar shear strength of material does not have the electro catalytic activity to oxygen.
CN103137943B discloses a kind of seawater dissolved oxygen anode and the seawater dissolved oxygen battery using the anode, should
Method is that carbon materials surface is made to form one layer of active layer using oxidation processes, and wherein electrochemicial oxidation is by carbon materials
It is placed in the mixed aqueous solution of sulfuric acid, perchloric acid and phosphoric acid, oxidation processes is carried out using constant potential control mode.The electricity of this method
Tri- kinds of sour mixed aqueous solutions of Xie Zhiwei, it is more complicated, it prepares also more troublesome；Furthermore this method is not directed to anodic oxidation
Auxiliary electrode used when processing.
Summary of the invention
The present invention is to solve technical problem present in well-known technique and provide a kind of efficient oxygen catalytic activity carbon fiber electricity
The preparation method of pole.
The object of the present invention is to provide one kind to have good catalytic activity height, chemical property, simple process, low in cost etc.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode of feature.
The present invention is that continuous oxidation-reduction replaces in a kind of acid solution using novel auxiliary electrode, constant current density
The novel processing step of the modified preparation seawater dissolved oxygen battery carbon fiber electrode of processing.
A kind of preparation method of efficient oxygen catalytic activity carbon fiber electrode, steps are as follows:
The torsion of commercialized polyacrylonitrile carbon fiber is bundled into brush, using polyacrylonitrile carbon fiber brush as Electrode, with same
Sample carbon fiber brush is as auxiliary electrode, in electrolyte sulfuric acid solution, is carried out continuously oxidation and reduction under constant current density
The polyacrylonitrile carbon fiber brush electrode of electrochemical modification processing can be obtained in alternate treatment.Polyacrylonitrile carbon after obtained processing
Fiber brush electrode is fixed in U-shaped sink, carries out the test of three electrode constant-current discharges.
Carbon fiber brush is all made of polyacrylonitrile carbon fiber strand material, and single synnema is 1000~3000, untreated.According to
It needs, various shape can be made in the shape of the electrode, it is preferable that the shape of the electrode is to turn round brush.Binding material is titanium silk,
Titanium silk binding screw thread wants compact.It, can be according to the occasion of battery applications and the needs of watt level for the size of electrode
It is designed and selects.
When oxidations and reduction alternate treatment, constant-current charge oxidation processes are first carried out, carry out constant-current discharge reduction treatment later,
Oxidation and reduction treatment be single treatment, number of processes 2~5 times.Three kinds of processing methods: identical oxidation and reduction treatment electric current,
Identical oxidation and reduction treatment time；Difference oxidation and reduction treatment electric current, identical oxidation and reduction treatment time；Identical oxidation
With reduction treatment electric current, difference oxidation and reduction treatment time.Oxidation and reduction treatment time are respectively 10~15min.Sulfuric acid
Concentration of electrolyte solutions is 0.5M~3M.Constant current density is 0.5A/g~3A/g.
Polyacrylonitrile carbon fiber brush constant-current discharge performance test that treated, test electric current are 10~100mA/g, reference electricity
Extremely saturated calomel electrode (SCE), electrolyte are the simulated seawater that sea salt is prepared, seawater velocity 2cm/s~6cm/s, test temperature
Spend room temperature.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode of the present invention is adopted the technical scheme that:
A kind of preparation method of efficient oxygen catalytic activity carbon fiber electrode, its main feature is that: efficient oxygen catalytic activity carbon fiber
The technical process of the preparation method of electrode are as follows: polyacrylonitrile carbon fiber torsion is bundled into brush, using polyacrylonitrile carbon fiber brush as electricity
Pole in electrolyte sulfuric acid solution, is carried out continuously oxidation using same carbon fiber brush as auxiliary electrode under constant current density
With reduction alternate treatment, the polyacrylonitrile carbon fiber brush electrode of electrochemical modification processing is made.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode of the present invention can also adopt the following technical scheme that
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode, its main feature is that: carbon fiber brush is all made of poly- third
Alkene nitrile carbon fiber wire beam material, single synnema are 1000~3000；The shape of electrode is to turn round brush, and binding material is titanium silk.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode, its main feature is that: oxidation and reduction alternate treatment
When, constant-current charge oxidation processes are first carried out, carry out constant-current discharge reduction treatment later, oxidation and reduction treatment are single treatment,
Number of processes 2-5 times；Three kinds of processing methods: identical oxidation and reduction treatment electric current, identical oxidation and reduction treatment time；It is different
Oxidation and reduction treatment electric current, identical oxidation and reduction treatment time；Identical oxidation and reduction treatment electric current, difference are aoxidized and are gone back
Manage the time in original place.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode, its main feature is that: oxidation and reduction treatment time
Respectively 10~15min.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode, its main feature is that: electrolyte sulfuric acid solution concentration
For 0.5M~3M.
The preparation method of the efficient oxygen catalytic activity carbon fiber electrode, its main feature is that: the constant current density is
0.5A/g~3A/g.
The advantages and positive effects of the present invention are:
The preparation method of efficient oxygen catalytic activated carbon fiber brush electrode due to using the completely new technical solution of the present invention, with
The prior art is compared, the preparation method of seawater dissolved oxygen battery polyacrylonitrile carbon fiber brush electrode of the present invention, this method it is excellent
Point is: preparing seawater dissolved oxygen battery polyacrylonitrile carbon fiber brush electrode simple process, low in cost, preparation by this method
Obtained polyacrylonitrile carbon fiber brush electrode is high to the catalytic activity of Dissolved Oxygen in Seawater, electric discharge polarization is small, discharge performance is stablized
The features such as.
Detailed description of the invention
The untreated polyacrylonitrile carbon fiber brush discharge performance map of Fig. 1；
Fig. 2 redox current is identical, processing time identical carbon fiber brush discharge performance map；
Fig. 3 redox current is different, processing time identical carbon fiber brush discharge performance map；
Fig. 4 redox current is identical, processing time different carbon fiber brush discharge performance map；
Fig. 5 polyacrylonitrile carbon fiber brush redox processing schematic；
Fig. 6 treated polyacrylonitrile carbon fiber brush discharge performance testing device schematic diagram；
In figure, 1, water inlet, 2, seawater dissolved oxygen battery cathode, 3, polyacrylonitrile carbon fiber brush, 4, reference electrode, 5, go out
The mouth of a river.
Fig. 7 carbon fiber spiral is bundled into torsion wire brush electrode schematic diagram.
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and cooperate attached drawing
Detailed description are as follows:
Refering to attached drawing 1 to Fig. 7.
The modified method in polyacrylonitrile carbon fiber surface, includes the following steps: commercialized polyacrylonitrile carbon fiber brush
Torsion is bundled into brush (such as Fig. 7), using polyacrylonitrile carbon fiber brush as Electrode, using same carbon fiber brush as auxiliary electrode, such as
Fig. 5 carries out redox alternate treatment under constant current density, compound electrification can be obtained in electrolyte sulfuric acid solution
Learn the polyacrylonitrile carbon fiber brush electrode of modification.The polyacrylonitrile carbon fiber brush electrode that obtains that treated is fixed on U-shaped
In sink (such as Fig. 6), constant-current discharge test is carried out.The polyacrylonitrile carbon fiber brush working electrode and auxiliary electrode using
Polyacrylonitrile carbon fiber strand material, single synnema are 1000~3000.As needed, the shape of the electrode can be made various
Shape, it is preferable that the shape of the electrode is to turn round brush.Binding material is titanium silk, and titanium silk binding screw thread wants compact.For electrode
Size can be designed and select according to the occasion of battery applications and the needs of watt level.It is 25 DEG C of temperature room temperature, dense
Degree is to carry out redox alternate treatment to working electrode in the electrolyte sulfuric acid solution of 0.5M~3M.Handling current density is
0.5A/g~3A/g, oxidation and reduction treatment time are respectively 10~15min, and oxidation and reduction treatment are single treatment, processing
Number 2~5 times.Obtaining treated, polyacrylonitrile carbon fiber brush carries out three electrode constant-current discharge performance tests in U-type groove,
Test electric current is 10~100mA/g, and reference electrode is saturated calomel electrode, and electrolyte is the simulated seawater that sea salt is prepared, simulation
The flowing velocity of seawater is 2~6cm/s, test temperature room temperature.
Comparative example 1
It is bundled into brush (being named as CFB0) with the torsion of commercialized polyacrylonitrile carbon fiber brush, the diameter 3cm of carbon fiber brush, length
10cm, long time without surface modification put it into fixed progress discharge performance test in U-shaped sink, directly with the simulated seawater of autogamy
For electrolyte, selected simulated seawater flow velocity 3cm/s and 20 DEG C of temperature three electrode discharge performance tests of progress, discharge current are
10mA/g, such as Fig. 1.
Embodiment 1
Polyacrylonitrile carbon fiber torsion is bundled into brush, with polypropylene by the preparation method of efficient oxygen catalytic activity carbon fiber electrode
Nitrile carbon fiber brush is as electrode, using same carbon fiber brush as auxiliary electrode, in electrolyte sulfuric acid solution, in identical constant electricity
It is carried out continuously the oxidation and reduction alternate treatment of same time under current density, the polyacrylonitrile carbon fiber of electrochemical modification processing is made
Tie up brush electrode.Specifically match technical process are as follows:
Brush, the diameter 3cm of carbon fiber brush, length 10cm, with poly- third are bundled into the torsion of commercialized polyacrylonitrile carbon fiber brush
Alkene nitrile carbon fiber brush is as Electrode, using same carbon fiber brush as auxiliary electrode, in 2M electrolyte sulfuric acid solution, in perseverance
Alternate treatment is aoxidized and restored under constant current density 1.0A/g, oxidization time and recovery time are 15min, it handles 3 times,
The polyacrylonitrile carbon fiber brush electrode (being named as CFB1) of composite electrochemical modification can be obtained.Poly- third after obtained processing
Alkene nitrile carbon fiber brush electrode is fixed in U-shaped sink, using the simulated seawater of autogamy as electrolyte, selectes simulated seawater flow velocity 3cm/
S and 20 DEG C of temperature three electrode constant-current discharges of progress tests, discharge current are 50mA/g and 100mA/g, such as Fig. 2.
Embodiment 2
Polyacrylonitrile carbon fiber torsion is bundled into brush, with polypropylene by the preparation method of efficient oxygen catalytic activity carbon fiber electrode
Nitrile carbon fiber brush is as electrode, using same carbon fiber brush as auxiliary electrode, in electrolyte sulfuric acid solution, in different constant electricity
It is carried out continuously the oxidation and reduction alternate treatment of same time under current density, the polyacrylonitrile carbon fiber of electrochemical modification processing is made
Tie up brush electrode.Specifically match technical process are as follows:
Brush, the diameter 3cm length 10cm of carbon fiber brush, with polypropylene are bundled into the torsion of commercialized polyacrylonitrile carbon fiber brush
Nitrile carbon fiber brush is as Electrode, using same carbon fiber brush as auxiliary electrode, in 2M electrolyte sulfuric acid solution, constant
Alternate treatment is aoxidized and restored under current density, and the time is 10min, oxidate current 1.7A/g, reduction current
Density is 1.1A/g, handles 3 circulations, and the polyacrylonitrile carbon fiber brush electrode (life of composite electrochemical modification can be obtained
Entitled CFB2).Polyacrylonitrile carbon fiber brush electrode is fixed in U-shaped sink after obtained processing, is with the simulated seawater of autogamy
Electrolyte selectes simulated seawater flow velocity 3cm/s and 20 DEG C of temperature three electrode constant-current discharges of progress tests, carries out constant-current discharge survey
Examination, discharge current are 50mA/g and 100mA/g, such as Fig. 3.
Embodiment 3
Polyacrylonitrile carbon fiber torsion is bundled into brush, with polypropylene by the preparation method of efficient oxygen catalytic activity carbon fiber electrode
Nitrile carbon fiber brush is as electrode, using same carbon fiber brush as auxiliary electrode, in electrolyte sulfuric acid solution, in identical constant electricity
It is carried out continuously time different oxidation under current density and restores alternate treatment, the polyacrylonitrile carbon fiber of electrochemical modification processing is made
Tie up brush electrode.Specifically match technical process are as follows:
Brush, the diameter 3cm of carbon fiber brush, length 10cm, with poly- third are bundled into the torsion of commercialized polyacrylonitrile carbon fiber brush
Alkene nitrile carbon fiber brush is as Electrode, using same carbon fiber brush as auxiliary electrode, such as Fig. 1, in 2M electrolyte sulfuric acid solution
In, alternate treatment, oxidization time 17min are aoxidized and restored at constant current density 1.0A/g, and the recovery time is
11min handles 3 times, the polyacrylonitrile carbon fiber brush electrode (being named as CFB3) of composite electrochemical modification can be obtained.?
To processing after polyacrylonitrile carbon fiber brush electrode be fixed in U-shaped sink, using the simulated seawater of autogamy as electrolyte, select mould
Quasi- seawater velocity 3cm/s and 20 DEG C of temperature three electrode constant-current discharges of progress tests, carry out constant-current discharge test, discharge current is
50mA/g and 100mA/g, such as Fig. 4.
The performance test results of comparative example and embodiment, acquisition are as follows:
As can be seen from the table, the commercialization carbon fiber brush without surface activation process is under 10mA/g low current density
Polarization reaches -0.52V, polarizes larger, performance is undesirable.It is modified to carry out surface active by above method, in 50mA/g and
It discharges under 100mA/g larger current density, CFB1, CFB2, CFB3 polarization of electrode voltage are than under CFB0 lower current densities
Polarizing voltage also want low, illustrate that above method can significantly improve carbon fiber brush electrode and polarize big problem.Compare CFB1,
CFB2, CFB3 are it is found that the processing method of CFB3 electrode is best, and electrode polarization is minimum, electro-catalysis of the carbon fiber electrode to dissolved oxygen
Active highest.It is modified by above method, the pasting on commercialization carbon fiber brush surface can not only be removed, additionally it is possible to increase carbon fiber
The oxygen-containing functional group type and quantity in dimension table face, such as hydroxyl, carboxyl, acid anhydrides are built conducive to the absorption and being dissociated into of dissolved oxygen, also
Hydrophily can be improved, be conducive to molecular transport, electronics transfer etc..The lone pair electrons of nitrogen-atoms and the carbon of sp2 hydridization formed from
Domain conjugated system is conducive to the progress of catalysis reaction.
The present invention is for the first time using electrode identical with working electrode as auxiliary electrode, constant current density, in a kind of acid
Property solution in continuous electrochemical modification repeatedly handle polyacrylonitrile carbon fiber brush electrode, obtained carbon fiber brush is used as seawater dissolution
Oxygen cell anode.There is oxygen catalytic activity height, electrochemistry by the polyacrylonitrile carbon fiber brush anode that this method is prepared
Can be excellent the advantages that.It is this method simple process, easy to operate, it is low in cost the features such as.
Claims (6)
1. a kind of preparation method of efficient oxygen catalytic activity carbon fiber electrode, it is characterized in that: efficiently oxygen catalytic activity carbon fiber electricity
The technical process of the preparation method of pole are as follows: polyacrylonitrile carbon fiber torsion is bundled into brush, using polyacrylonitrile carbon fiber brush as electrode,
Using same carbon fiber brush as auxiliary electrode, in electrolyte sulfuric acid solution, be carried out continuously under constant current density oxidation and
Alternate treatment is restored, the polyacrylonitrile carbon fiber brush electrode of electrochemical modification processing is made.
2. the preparation method of efficient oxygen catalytic activity carbon fiber electrode according to claim 1, it is characterized in that: carbon fiber brush
It is all made of polyacrylonitrile carbon fiber strand material, single synnema is 1000~3000；The shape of electrode is to turn round brush, binding material
For titanium silk.
3. the preparation method of efficient oxygen catalytic activity carbon fiber electrode according to claim 1, it is characterized in that: aoxidizing and going back
When former alternate treatment, constant-current charge oxidation processes are first carried out, carry out constant-current discharge reduction treatment later, oxidation and reduction treatment are
Single treatment, number of processes 2~5 times；Three kinds of processing methods: identical oxidation and reduction treatment electric current, identical oxidation and also original place
Manage the time；Difference oxidation and reduction treatment electric current, identical oxidation and reduction treatment time；Identical oxidation and reduction treatment electric current,
Difference oxidation and reduction treatment time.
4. the preparation method of efficient oxygen catalytic activity carbon fiber electrode according to claim 1, it is characterized in that: aoxidizing and going back
The original place reason time is respectively 10~15min.
5. the preparation method of efficient oxygen catalytic activity carbon fiber electrode according to claim 1, it is characterized in that: sulphuric acid electrolyte
Matter solution concentration is 0.5M~3M.
6. the preparation method of efficient oxygen catalytic activity carbon fiber electrode according to claim 1, it is characterized in that: constant current
Density is 0.5A/g~3A/g.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004176232A (en) * | 2002-11-29 | 2004-06-24 | Toho Tenax Co Ltd | Polyacrylonitrile-based carbon fiber fabric |
| CN1555340A (en) * | 2001-08-02 | 2004-12-15 | 等离子体溶胶公司 | Chemical processing using non-thermal discharge plasma |
| US20050181269A1 (en) * | 2004-02-13 | 2005-08-18 | Microcell Corporation | Microfibrous fuel cell assemblies comprising fiber-supported electrocatalyst layers, and methods of making same |
| CN101066802A (en) * | 2007-06-15 | 2007-11-07 | 北京化工大学 | Prepn and application in industrial effluent treatment of biomembrane carrier |
| CN104838051A (en) * | 2013-02-19 | 2015-08-12 | 中国海洋大学 | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
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2017
- 2017-12-22 CN CN201711405248.6A patent/CN109962209A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555340A (en) * | 2001-08-02 | 2004-12-15 | 等离子体溶胶公司 | Chemical processing using non-thermal discharge plasma |
| JP2004176232A (en) * | 2002-11-29 | 2004-06-24 | Toho Tenax Co Ltd | Polyacrylonitrile-based carbon fiber fabric |
| US20050181269A1 (en) * | 2004-02-13 | 2005-08-18 | Microcell Corporation | Microfibrous fuel cell assemblies comprising fiber-supported electrocatalyst layers, and methods of making same |
| CN101066802A (en) * | 2007-06-15 | 2007-11-07 | 北京化工大学 | Prepn and application in industrial effluent treatment of biomembrane carrier |
| CN104838051A (en) * | 2013-02-19 | 2015-08-12 | 中国海洋大学 | Oxygen and nitrogen co-doped polyacrylonitrile-based carbon fiber and preparation method thereof |
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