CN108630445A - A kind of method and its application preparing ultracapacitor carbon material by alkali activation nitrogen heterocyclic ring metal complexes - Google Patents
A kind of method and its application preparing ultracapacitor carbon material by alkali activation nitrogen heterocyclic ring metal complexes Download PDFInfo
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- CN108630445A CN108630445A CN201810449271.3A CN201810449271A CN108630445A CN 108630445 A CN108630445 A CN 108630445A CN 201810449271 A CN201810449271 A CN 201810449271A CN 108630445 A CN108630445 A CN 108630445A
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- nitrogen heterocyclic
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 25
- 230000004913 activation Effects 0.000 title claims abstract description 20
- 239000003513 alkali Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000010453 quartz Substances 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- JIRCUPJLJRJZNT-UHFFFAOYSA-N N1=C(C=NC=C1)C1=NC(=CC(=C1)C1=CC=C(C=C1)C1=NN=NN1)C1=NC=CN=C1 Chemical compound N1=C(C=NC=C1)C1=NC(=CC(=C1)C1=CC=C(C=C1)C1=NN=NN1)C1=NC=CN=C1 JIRCUPJLJRJZNT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- -1 Zinc salt Chemical class 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 206010013786 Dry skin Diseases 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 35
- 238000001994 activation Methods 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 230000005611 electricity Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010218 electron microscopic analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of methods preparing ultracapacitor carbon material by alkali activation nitrogen heterocyclic ring metal complexes comprising following steps：1. nitrogen heterocyclic ring class organic ligand is dissolved in organic solvent, zinc salt is 2. dissolved completely in deionized water, zinc solution is slowly dropped into the solution of step 1. and is stirred, 3. configures the mixed solution of absolute ethyl alcohol and deionized water, is 10 100 by molar ratio：1 alkali (alkali：Zinc salt) it is added to ultrasonic dissolution in the mixed solution; solution after ultrasonic dissolution pours into step 2. in mixed solution; continue to stir and be evaporated; 4. the solid product after being evaporated is added in quartz boat; in vacuum tube furnace under nitrogen protection, 700 DEG C, after naturally cooling to room temperature are warming up to the heating rate of 5 DEG C/min; obtained black product is repeatedly washed with the hydrochloric acid solution of 2mol/L, deionized water, absolute ethyl alcohol, in constant temperature ten hours of 80 DEG C of dryings after washes clean.This method has many advantages, such as yield height, favorable repeatability, stable reaction.
Description
Technical field
The invention belongs to electrode material for super capacitor technical fields, especially a kind of to activate nitrogen heterocyclic ring metalloid by alkali
Complex prepares the method and its application of ultracapacitor carbon material.
Background technology
Ultracapacitor, also referred to as electric chemical super capacitor or excessively capacitor, since it possesses high power density,
Big specific capacitance, can fast charging and discharging, long service life cycle (can reach 100000cycle), and equipment is simple, can big electricity
The advantages that banishing electricity and low self discharge, application industrially are also all the more extensive；Such as make for portable device
With, many hand-helds and portable product, such as electronic toy, portable cameras, camera, digital table, even mobile phone, just
Formula computer is taken, in the ultracapacitor using 5F or more.
Current ultracapacitor is a kind of energy storage device between battery and traditional capacitor.Opposite battery comes
It says, ultracapacitor has higher power density；And for traditional ultracapacitor, ultracapacitor again can
Store more energy.Although the energy density (be less than 10Wh/Kg) of many commercially available ultracapacitors is more super than traditional
Capacitor is high, but for opposite lithium ion battery and fuel cell, the energy density of ultracapacitor is still too low.With complete
The fast development of ball warp Ji, the ultracapacitor that can store more energy is researched and developed out there is an urgent need to us.
The structure of ultracapacitor includes mainly collector, electrode material and electrolyte.Since ultracapacitor is that have
The energy storage device of high power density, their internal resistance have to it is sufficiently small, especially between active electrode material and collector
Contact impedance more should be sufficiently small, because just from the point of view of current research, it is main outside collector or electrode and ultracapacitor
Physical connection device.In order to reach contact impedance small as possible, a most efficient method is to make active electrode material
It is covered on metal collector (due to its low impedance).Generally, the combination quality of active material and collector,
It is that impedance increases a how many main causes in the long-term loop test of ultracapacitor.
For ultracapacitor, active electrode material plays very important work in terms of influencing super capacitor performance
With.And as one of big main research material of three in electrode material for super capacitor, carbon material has studied many by everybody
Year.Nowadays, various carbon materials appear in everybody at the moment, are received than activated carbon, carbon aerogels, carbon as is well known
The ratio that mitron, carbon ball, graphene etc., wherein reference area be bigger, is also everybody studies earlier activated carbon also already by
Commercial applications.
Hot spot of the carbon material as research, everybody puts into a large amount of man power and material and it is modified or is improved one after another,
Or the carbon material that research is novel.It has been found that carbon material has many advantages, for example specific surface area is larger, and electric conductivity compares
Good, service life is long, and cyclical stability is relatively good, but keeps on improving, and to carbon material improve again or modified
It gives no cause for much criticism to the better carbon material of performance.Wherein, it is a kind of important improvement means to carry out activation to obtained carbon material.Closely
A little years mainly there are physical activation method and chemical activation method, physical activation method mainly to use carbon dioxide the activation of carbon material,
The gases such as vapor are activated；Chemical activation method mainly passes through some activators, such as potassium hydroxide, zinc chloride and phosphorus
The chemical reagent such as acid are activated, and have to be post-processed after the completion of activating, mainly seek to wash activator or
Some sundries generated.But although these activation methods can carry out some improvement to carbon material, for example increase its specific surface
Product, but the behavior for making carbon material Mass lost due to there is etching etc. in activation process, what often we obtained is productivity ratio
Lower porous carbon materials.
Invention content
For overcome the deficiencies in the prior art, the present invention provides one kind activating nitrogen heterocyclic ring metal complexes system by alkali
The method of standby ultracapacitor carbon material, this method have synthesized a kind of uniqueness by the coordination between cvdmetallorganiccvd ligand
Metal organic complex, and activated by potassium hydroxide, using heat treatment, obtained a kind of novel porous carbon
There is the hole that many size shapes differ in material, the carbon material surface, this should be exactly potassium hydroxide etching as a result, this
Sample just considerably increases the specific surface area of carbon material, by carrying out electro-chemical test to the electrode material, it has been found that the electrode
While material has excellent electric conductivity, also there is bigger specific capacitance, and by the cycle up to 1000 circles
After life test, capacity retention can also reach nearly 95%, and chemical property is more excellent.
To achieve the goals above, the technical solution adopted by the present invention is：One kind is matched by alkali activation nitrogen heterocyclic ring metalloid
Close the method that object prepares ultracapacitor carbon material, which is characterized in that include the following steps：
1. nitrogen heterocyclic ring class organic ligand is dissolved in organic solvent, stirring is until be completely dissolved, the nitrogen heterocyclic ring
Class organic ligand uses 2,6-bis (2-pyrazinyl) -4- (4- (tetrazol-5-yl) phenyl)
Pyridine, structural formula
It is as follows：
The organic solvent uses DMF,
2. zinc salt is dissolved completely in deionized water, then, which is slowly dropped into the solution of step 1.,
It is stirred, wherein the molar ratio of nitrogen heterocyclic ring class organic ligand and zinc salt is 2:1,
3. by absolute ethyl alcohol and deionized water by volume 4:1 configuration mixed solution, alkali is added in the mixed solution,
The molar ratio of ultrasonic dissolution, alkali and zinc salt is 10-100：1, the solution obtained after ultrasonic dissolution is fallen
Enter in the solution 2. step is stirred after, continue to stir and heat to be evaporated solution,
4. the solid product obtained after being evaporated is added in quartz boat, in vacuum tube furnace under the protection of nitrogen,
It is warming up to 650-750 DEG C with the heating rate of 5 DEG C/min, after naturally cooling to room temperature, the black that will obtain
Product uses the hydrochloric acid solution of 2mol/L, deionized water, absolute ethyl alcohol repeatedly to be washed respectively, finally will
The product of washes clean ten hours of 80 DEG C of dryings in thermostatic drying chamber, obtain carbon material.
Further, the zinc salt includes Zn (NO3)2·6H2O, zinc chloride.
Further, the alkali includes sodium hydroxide, potassium hydroxide.
Goal of the invention two：The present invention also provides a kind of ultracapacitor carbon materials, it is characterised in that：According to the method described above
It is prepared.
Goal of the invention three：The present invention provides a kind of applications of ultracapacitor carbon material, which is characterized in that including as follows
Step：1. carbon material is made using the method as described in claim 1, by carbon material, acetylene black, PTFE in mass ratio 8:1:1
In the agate mortar, a small amount of ethyl alcohol is added in mixing, and being sufficiently stirred makes them be uniformly mixed pulp, 2. by uniformly mixed prize
On shape applying material to processed foamed nickel current collector, in air dry oven dry after under infrared tablet press machine 10MPa
Tabletting after impregnating 10h, obtains target electricity then by the electrode tabletting prepared bubble in the potassium hydroxide solution of 3mol/L
Pole.
Using the above scheme, the present invention has selected a kind of i.e. 2, the 6-bis of nitrogen heterocyclic ring class organic ligand (2-
Pyrazinyl) -4- (4- (tetrazol-5-yl) phenyl) pyridine selects zinc salt to provide source metal (because of the boiling of zinc
Point is relatively low, can be flowed out with inert gas in heat treatment, and can also be cleaned and be removed with hydrochloric acid, and does not stay in most
In final product), using a kind of method that simple solution directly mixes, closed by the coordination between cvdmetallorganiccvd ligand
It at a kind of unique metal organic complex, and is activated by potassium hydroxide, using heat treatment, has obtained one kind
Novel porous carbon materials.Physical characterization has been carried out to obtained carbon material, it is found that many sizes occurs in the carbon material surface
The hole that shape differs, this should be exactly potassium hydroxide etching as a result, thus considerably increasing the specific surface area of carbon material.
By carrying out electro-chemical test to the electrode material, it has been found that while the electrode material has excellent electric conductivity, also have
There is bigger specific capacitance, and after the cycle life test up to 1000 circles, capacity retention can also reach
Nearly 95%, chemical property is more excellent.
The specific reaction mechanism of the above method：Present invention employs ligands appropriate and low-boiling metal zinc ion, lead to
It is activated under parlkaline, forms the complex after a kind of activation.The complex is suitable temperature (being most preferably 700 degrees Celsius)
Under, it is carbonized, is flowed away together with inert gas wherein low-boiling zinc ion forms gas under inert gas protection, or
It is reduced into zinc metal, or part is oxidized to zinc oxide by a small amount of oxygen, however, being metallic zinc or zinc oxide, all last
Pickling (hydrochloric acid) and water-washing process in be removed.Carbon, hydrogen and nitrogen are mainly contained in above-mentioned ligand, in inert gas high temperature
Lower carbonization is at the carbon material mixed up containing hydrogen and nitrogen.Due to the difference of preparation condition, the pattern of obtained carbon material, specific surface and
Electric conductivity etc. also differs；For example, during the test, it is found that influence of the temperature to product is very big, 600 DEG C and 800 DEG C obtain
Product and 700 DEG C of obtained carbon materials specific surface, pattern and electric conductivity etc. exist very big difference.In addition, by
It needs to be completely dissolved when nitrogen heterocyclic ring class organic ligand is dissolved in organic solvent, the organic solvent or dissolution degree used when it is not
When complete, the performance of final reacting product is influenced also larger.It is tested by electrochemical properties, shows that the carbon material is a kind of excellent
Good double electric layers supercapacitor electrode material, no matter the indexs such as specific capacitance and cycle life, all can be used as practical capacitor
Electrode material, overall target are excellent.
The advantageous effect of the above method：By above-mentioned ligand and activation method, the carbon material of this pattern is obtained, has been had both
Larger specific surface and preferable electric conductivity are used for electrode material for super capacitor, have excellent electrochemical properties (larger
Specific capacitance and longer cycle-index), it is suitable for the exploitation of practical capacitor.
Above-mentioned carbon material has the hole shape pattern that size shape differs, and specific surface area is larger, and electric conductivity is preferable, Er Qieqi
For unformed state, there is porous carbon structure.
Above-mentioned carbon material has the following advantages as the application of electrode of super capacitor：Excellent electrochemical properties, well
Electric conductivity, typical double layer capacitor property, larger specific capacitance, compared with long circulation life.
The invention will be further described below in conjunction with the accompanying drawings.
Description of the drawings
Attached drawing 1 is the X-ray diffraction facies analysis for the carbon material that specific embodiment of the invention treatment of different temperature obtains；
Attached drawing 2 is the scanning electron microscope diagram of specific embodiment of the invention C-700, wherein a schemes for 500nm, and b is
300nm schemes；
Attached drawing 3 is the transmission electron microscope figure of specific embodiment of the invention C-700, wherein a schemes for 100nm, and b is
50nm schemes；
Attached drawing 4 is specific embodiment of the invention C-700 to N2Absorption/desorption isotherm；
Attached drawing 5 is cycle volt of the obtained carbon material of specific embodiment of the invention treatment of different temperature when 50mv/s sweeps speed
Pacify curve；
Attached drawing 6 is charging and discharging curve of the obtained carbon material of specific embodiment of the invention treatment of different temperature in 1A/g；
Attached drawing 7 is specific capacitances of the specific embodiment of the invention C-700 under different current densities；
The Ragone that attached drawing 8 is specific embodiment of the invention C-700 schemes；
Attached drawing 9 is the AC impedance curve for the carbon material that specific embodiment of the invention treatment of different temperature obtains；
Attached drawing 10 is lifetime changes of the specific embodiment of the invention C-700 in current density 3A/g in 1000 cycles；
Specific implementation mode
The present invention is not limited to following specific implementation modes, and persons skilled in the art are according to disclosed by the invention interior
Hold, other a variety of specific implementation modes may be used and implement of the invention or every design structure using the present invention and think of
Road does simple change or change, both falls within protection scope of the present invention.
Specific embodiments of the present invention are that one kind preparing ultracapacitor carbon by alkali activation nitrogen heterocyclic ring metal complexes
It the method for material and carries out thus obtained carbon material to prepare electrode and carries out electrochemical property test content.
Raw material is as shown in following table 1-1：
The main reagents of table 1-1
Instrument is as shown in following table 1-2：
The main laboratory apparatus of table 1-2
Experimental procedure is as follows：
One, the preparation of electrode material：
1. by organic ligand 2,6-bis (2-pyrazinyl) -4- (4- (tetrazol-5-yl) phenyl) pyridine
(0.00052mol, 0.1972g) is dissolved in 10ml DMF, is stirred in constant temperature blender with magnetic force, until ligand is completely dissolved.
Above-mentioned organic ligand structural formula is as follows：
2. by Zn (NO3)2·6H2O (0.00026mol, 0.0774g) is dissolved completely in 10mL deionized waters, is then used
Dropper slowly instills this solution in 1. solution, continues to stir half an hour in constant temperature blender with magnetic force.Zinc salt may be used also
To use other soluble zinc salts, such as zinc chloride.
3. 1.4g potassium hydroxide is added in 25ml mixed solutions (20ml absolute ethyl alcohol+5ml deionized waters), ultrasonic 5-
10min makes it completely dissolved, and is subsequently poured into above-mentioned solution, continues to stir half an hour, finally in digital display temperature constant magnetic stirring
Solution in beaker is evaporated on device.Wherein, potassium hydroxide can be replaced with the general highly basic such as sodium hydroxide.
4. the solid product obtained after being evaporated is added in quartz boat, in vacuum tube furnace under the protection of nitrogen, with
The heating rate of 5 DEG C/min is warming up to 700 DEG C, after naturally cooling to room temperature, and obtained black product is used to 2mol/L's respectively
Hydrochloric acid solution, deionized water, absolute ethyl alcohol are repeatedly washed, finally by the product of washes clean 80 DEG C in thermostatic drying chamber
Dry ten hours, this obtained black product is named as C-700 by us.
5. same processing method, we have got back other three kinds of black products, are respectively designated as C-600, C-
650, C-750, respectively represent product obtained by the reaction at different temperatures.
Two, the preparation of electrode：
1. the carbon material C-700 that will be obtained, weighs 0.4mg, according to mass ratio 8:1:1 ratio, by C-700, acetylene black,
PTFE is mixed in the agate mortar, and a small amount of ethyl alcohol is added, and being sufficiently stirred makes them be uniformly mixed pulp, will be mixed with small key
Condensation material is applied in processed foamed nickel current collector, in air dry oven dry after under infrared tablet press machine 10MPa
Then tabletting can be tested the electrode slice prepared bubble in the potassium hydroxide solution of 3mol/L after a period of time.Together
Sample, we are prepared for the other three electrode C-600, C- 650, C-750 again.
We use three-electrode system, and using platinum filament as to electrode, as reference electrode, (interior liquid is Hg/HgO electrodes
The potassium hydroxide solution of 1mol/L), working electrode is exactly the foam nickel electrode that we prepare, and electrolyte uses the hydrogen of 3mol/L
Potassium oxide solution carries out electro-chemical test using electrochemical workstation CHI760E to electrode.
Three, the electro-chemical test of electrode：
First, the physical characterization of electrode：
X-ray diffraction facies analysis (XRD)
We have done X-ray diffraction analysis, such as Fig. 1 to four kinds of prepared electrode materials, from figure it may be seen that
All all electrode materials obtained are all amorphous carbon, are only gone out in the position that about 2Theta is 14 °, 30 ° and 44 °
Several wider peaks are showed, and we can also be seen that the peak that Zn elements and K elements are not present in material, it was demonstrated that obtain
Material is purer.
Scanning Electron microscopic analysis (SEM)
It is observed by scanning electron microscope, we have carried out morphology characterization, such as Fig. 2 to electrode material C-700, from figure
It will be seen that there is the holes that various size shapes differ on the surface of material, this is the knot of activation of potassium hydroxide
The presence of fruit, these holes substantially increases the specific surface area of material, so as to optimize the electrochemistry side of the electrode material
The performance in face.
Tem study (TEM)
By transmission electron microscope, we have carried out finer observation, such as Fig. 3 to electrode material C-700 again, from
We can see that coming, after electron beam permeable material, materials exhibit is almost transparent, this illustrates the thickness right and wrong of material in figure
Often thin, such appearance structure is advantageous to electronics and is quickly transmitted, and enhances the electric conductivity of material.
The specific surface area test (BET) of material
By carrying out N to material2Adsorption desorption, we can measure the specific surface area of electrode material, such as Fig. 4, be us
To the specific surface area test that electrode material C-700 is carried out, show that the suction of porous solid is presented in material from the point of view of the shape of curve
Attached feature, is calculated by BET formula, we can also obtain the specific surface area of the material, SBet=1613.3123m2/g.So
Big specific surface area is conducive to more electrolyte ions and is adsorbed on above, stores more capacitances, it is super to greatly strengthen its
Capacitive property.
Secondly, the electro-chemical test of electrode：
Cyclic voltammetry (CV)
By electrochemical workstation, we have carried out cyclic voltammetry, such as Fig. 5 to these four electrode materials, when sweeping speed
For 50mv/s, when potential range is -1V-0V, we have carried out cyclic voltammetry analysis to these four electrode materials, from figure
It will be seen that the cyclic voltammetry curve of these four materials is all biased into rectangle, it is electric double layer electricity that this, which illustrates material all,
Hold electrode material (ideal electric double layer capacitance electrode material cyclic voltammetry curve is rectangle), is not pseudo-capacitance electrode material.From
The area that each curve is surrounded, we substantially can be seen that the specific capacitance size C-700 ＞ C-650 ＞ C-750 of each electrode material
＞ C-600.
Constant current charge-discharge tests (CP)
For the ease of comparing the specific capacitance size for four kinds of electrode materials that we synthesize, we again distinguish these materials
Constant current charge-discharge test (quality current density is 1A/g) is carried out, as a result such as Fig. 6, it will be seen that four kinds from figure
The constant current charge curve of material is nearly all in up-side down triangle, this more illustrates that these electrode materials are electric double layer capacitance electricity
Pole material (preferably double layer electrodes material be standard up-side down triangle), and it will be seen that material C-from figure
700 discharge time is longest, shows that it possesses maximum specific capacitance, and according to formula, we can calculate four kinds of electricity
The quality specific capacitance of pole material C -600, C-650, C-700, C-750 is respectively 184F/g, 208F/g, 241F/g, 210F/g, institute
Possess maximum specific capacitance with the material handled at 700 DEG C, we study emphatically C-700.
We test the constant current charge-discharge curve of different quality current density lower electrode material C-700 again, as a result such as table
1-3,
The ultracapacitor parameter of table 1-3 C-700
According to table results, we depict the specific capacitance of the electrode material under different current densities, such as Fig. 7, from figure
In I it will be seen that when current density be 0.5A/g when, the specific capacitance of material can reach 250F/g.Quality electric current
When density is up to 10A/g, the specific capacitance of material still has 174F/g, capacity retention still can reach nearly 70%.From figure I
It can also be seen that with current density gradual increase, the specific capacitance of material is gradually reduced, this is because current density is got over
When big, the concentration polarization of solution is bigger, and in the case that the internal resistance of electrode material is certain, voltage drop also becomes much larger, so material
Specific capacitance can reduce with the increase of current density.
According to table, again using energy density as abscissa, power density is ordinate for we, is made that Ragon schemes, such as
Fig. 8, it will be seen that when energy density is 34.7Wh/Kg from figure, power density can reach 250W/Kg；Work as energy
When density is 24.2Wh/Kg, power density can reach 5007W/Kg.As energy density gradually becomes larger, power density is gradual
Reduction.But when power density increases to 5007W/Kg from 250W/Kg, the energy density span Wh/ of 10 units
Kg, that is to say, that when power density gradually increases, energy density but change it is smaller or we can directly say can be with
Using high-power, that is, the method for repid discharge uses the ultracapacitor, this is as electrode material for super capacitor
One important performance and feature.
Ac impedance measurement (EIS)
The resistance problems of system when working for Electrode, we again hand over electrode using electrochemical workstation
Flow impedance test, such as Fig. 9, from figure it will be seen that the AC impedance curve of these four materials high frequency region small semicircle with
The intersection point of real axis is all about 0.6 Ω, this resistance includes the internal resistance of electrolyte, the internal resistance of electrode material itself and electrode and
The contact resistance of material, we can also be called this resistance the resistance of system, and the system resistance of these four materials does not almost have
There is difference.And in low frequency range, it will be seen that the phase angle of four kinds of materials is obviously all greater than 45 °, show be not by
The reaction for spreading control, possesses good electrochemical behavior.
Cycle life is tested
The size of specific capacitance is one important performance indicator of ultracapacitor, and the service life of electrode material is also
One critically important performance indicator, so, using constant current charge-discharge technology, we have again carried out up to 1000 circles material
Cycle life is tested, such as Figure 10, it has been found that when quality current density is 3A/g, have passed through the charge and discharge up to 1000 circles
After electricity cycle, the capacity retention of the electrode material remains able to up to 94.4%, and it is long that this illustrates that the material has
Service life.
In the prior art, some precursors of activated carbon, such as wood, shell, egg or polymer macromolecule, ratio
Surface area is relatively small, and pore-size distribution is relatively poor.It can be by some physically or chemically activation methods, to increase its specific surface
Product, adjusts suitable aperture.The present invention successfully increases the specific surface area of carbon material by activation of potassium hydroxide method,
Realize the distribution in some apertures.Such structure can effectively increase the specific capacitance of carbon material, and relatively thin material
Thickness is also beneficial to the transmission of electronics, further increases its service life cycle.
Claims (5)
1. a kind of method preparing ultracapacitor carbon material by alkali activation nitrogen heterocyclic ring metal complexes, which is characterized in that
Include the following steps：
1. nitrogen heterocyclic ring class organic ligand is dissolved in organic solvent, until being completely dissolved, the nitrogen heterocyclic ring class is organic for stirring
Ligand uses 2,6-bis (2-pyrazinyl) -4- (4- (tetrazol-5-yl) phenyl) pyridine, structural formula as follows：
The organic solvent uses DMF,
2. zinc salt is dissolved completely in deionized water, then, which is slowly dropped into the solution of step 1., stirring is mixed
It closes, wherein the molar ratio of nitrogen heterocyclic ring class organic ligand and zinc salt is 2:1,
3. by absolute ethyl alcohol and deionized water by volume 4:1 configuration mixed solution, alkali is added in the mixed solution, ultrasound
The molar ratio of dissolving, alkali and zinc salt is 10-100：1, the solution obtained after ultrasonic dissolution is poured into after 2. step is stirred
In solution, continue to stir and heat to be evaporated solution,
4. the solid product obtained after being evaporated is added in quartz boat, in vacuum tube furnace under the protection of nitrogen, with 5 DEG C/
The heating rate of min is warming up to 650-750 DEG C, and after naturally cooling to room temperature, obtained black product is used to 2mol/L's respectively
Hydrochloric acid solution, deionized water, absolute ethyl alcohol are repeatedly washed, finally by the product of washes clean 80 DEG C in thermostatic drying chamber
Dry ten hours, obtain carbon material.
2. the side according to claim 1 for preparing ultracapacitor carbon material by alkali activation nitrogen heterocyclic ring metal complexes
Method, it is characterised in that：The zinc salt includes Zn (NO3)2·6H2O, zinc chloride.
3. the side according to claim 2 for preparing ultracapacitor carbon material by alkali activation nitrogen heterocyclic ring metal complexes
Method, it is characterised in that：The alkali includes sodium hydroxide, potassium hydroxide.
4. a kind of ultracapacitor carbon material, it is characterised in that：It is prepared into according to the method described in claim 1-3 any one
It arrives.
5. a kind of application of ultracapacitor carbon material, which is characterized in that include the following steps：1. using such as claim 1 institute
Carbon material is made in the method stated, by carbon material, acetylene black, PTFE in mass ratio 8:1:1 mixing in the agate mortar, is added a small amount of
Ethyl alcohol, being sufficiently stirred makes them be uniformly mixed pulps, 2. by uniformly mixed diploma applying material to processed bubble
In foam nickel set fluid, the 10MPa tablettings under infrared tablet press machine after being dried in air dry oven, the electrode pressure that then will be prepared
Piece steeps in the potassium hydroxide solution of 3mol/L, after impregnating 10h, obtains target electrode.
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| CN114068200A (en) * | 2021-11-16 | 2022-02-18 | 温州大学 | Super capacitor electrode material based on metal organic complex and preparation method thereof |
| CN114068201A (en) * | 2021-11-17 | 2022-02-18 | 温州大学 | Supercapacitor electrode material prepared from carbon-doped material and preparation method thereof |
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