CN102765782A - Method for preparing hierarchical porous carbon capacitive deionization electrode - Google Patents
Method for preparing hierarchical porous carbon capacitive deionization electrode Download PDFInfo
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- CN102765782A CN102765782A CN2012102457296A CN201210245729A CN102765782A CN 102765782 A CN102765782 A CN 102765782A CN 2012102457296 A CN2012102457296 A CN 2012102457296A CN 201210245729 A CN201210245729 A CN 201210245729A CN 102765782 A CN102765782 A CN 102765782A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002242 deionisation method Methods 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 30
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000006230 acetylene black Substances 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 238000010612 desalination reaction Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000003990 capacitor Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 8
- 229920003986 novolac Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000006193 liquid solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011806 microball Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004809 Teflon Substances 0.000 abstract 2
- 229920006362 Teflon® Polymers 0.000 abstract 2
- 238000005530 etching Methods 0.000 abstract 1
- 239000002149 hierarchical pore Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 238000011033 desalting Methods 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000005770 birds nest Nutrition 0.000 description 1
- 230000001914 calming effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 235000005765 wild carrot Nutrition 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing a hierarchical porous carbon capacitive deionization electrode and belongs to the field of preparation of capacitive deionization electrodes. According to the method, a silica template is immersed in a precursor solution of a mesoporous carbon material, the carbon material with a hierarchical pore structure is formed on silica spheres by the processes of low temperature volatilization, high temperature curing, carbonization in inert atmosphere and the like, and the porous carbon material with macropores, meso pores and micropores is obtained by hydrofluoric acid etching. The porous carbon material, acetylene black and teflon emulsion are mixed uniformly to be smeared on graphite paper, and the graphite paper onto which a mixture of the porous carbon material, the acetylene black and the teflon emulsion is smeared is dried after the night to form the hierarchical porous carbon capacitive deionization electrode. The method is easy to operate and has potential application prospect in the aspect of capacitive deionization which is low in energy consumption and cost and high in efficiency; conditions are easy to control; and the obtained electrode is large in specific surface, high in electrical conductivity and high in deionization performance.
Description
Technical field
The present invention relates to a kind of preparation method of multistage hole carbon capacitor type desalination electrode.The desalination electrode of the present invention's preparation has the desalting performance of high-level efficiency, less energy-consumption.Belong to the desalination that the present invention of electric desalting electrode manufacturing process technical field can be applicable to seawater and brackish water, for less energy-consumption, low cost, high-performance desalination provide new way.
Background technology
Water resources crisis is one of maximum resource crisis that this century, the whole world faced, and seawater and brackish water desalting are the important channels that solves this crisis.Existing desalting method mainly contains distillation method (comprising MSF, multistage evaporation and the distillation of calming the anger) and embrane method (comprising r-o-and electrodialysis).But the distillation method service temperature is high, serious, the seriously corroded of bird nest harm; Embrane method is strict to film properties, film spoilage height and expensive.In addition, all there is the shortcoming that energy consumption is high, cost is big in these desalting method.Reduce desalinating cost so employ new technology is the most important developing goal of desalination technology always.Therefore, the research and development desalting technology application prospect that energy consumption is low, cost is low is very bright.Capacitor type desalination (Capacitive Deionization; CDI) be based on the brand-new desalting technology of electric double layer capacitance principle.Compare with traditional desalting method, this method has that cost is low, desalting efficiency is high, processing unit is simple, easy to implement, do not have secondary pollution, environment amenable advantage simultaneously, for high-level efficiency, low energy, low-cost desalting technology provide new approach.
Principle based on CDI can find out that the key that obtains high CDI performance is an electrode materials, requires electrode materials to have characteristics such as specific surface area is big, the space is flourishing, good conductivity.Porous carbon materials has that high specific surface area, favorable conductive ability, unique chemical stability, good formability, relative low price, raw material sources are abundant, production technique also advantage such as comparative maturity aspect electrode materials, have very widely and use.Up to now, the porous carbon materials as the CDI electrode mainly comprises gac, charcoal-aero gel, carbon nanofiber, carbon nanotube, Graphene and mesoporous carbon.Wherein gac is because of specific surface area is big, simple, the cheap electrode materials that becomes present widespread use of preparation; But its desalting efficiency is lower, mainly is because the existence of a large amount of micropores is unfavorable for that ionic permeates and absorption causes lower, the unordered pore structure of specific surface area utilization ratio, reaches higher internal resistance.In order to address the above problem, the meso-porous carbon material that mesoporous carbon has high specific surface area, highly homogeneous pore size distribution, big pore volume and high mechanical stability has caused the great interest of investigator.People such as Zou discover ordered mesopore carbon (Zou L, Li LX, Song HH, the Morris G with high-specific surface area; Water Research, 2008,42,2340-2348) or through meso-porous carbon material (the Li LX of Ni finishing; Zou L, Song HH, Morris G; Carbon 2009,47,775-781) all have higher desalination capacity with respect to traditional activated carbon electrodes.But it is to be noted that the ratio capacitance of meso-porous carbon material when the desalination electrode of current preparation well below the theoretical value of carbon material, mainly is because for example higher relatively internal resistance and the lower surface-area utilization ratio of some shortcomings that material exists.Therefore in order to address the above problem; Prepare novel more high surface area, high conductivity, multistage hole (macropore that the space is flourishing, that the surface by utilizing rate is higher; Mesoporous and micropore) carbon electrode material is for the desalination of high-performance, high-level efficiency, less energy-consumption provides new way.
Summary of the invention
The objective of the invention is to the problems referred to above, a kind of preparation method that electric double layer capacitance type desalination process carries out the multistage hole carbon capacitor type desalination electrode of sea water desaltination processing that uses is provided.With macropore; The multistage hole of the effective bonded of mesoporous and micropore carbon material; Can select the advantage of comprehensive various holes material; Owing to its huge specific surface area, flourishing pore texture, the pore passage structure that is interconnected, it has been showed at aspects such as diffusion, mass transfers be superior to single pore structure properties of materials simultaneously.Macropore that wherein is interconnected and the mesoporous hole that helps iontophoretic injection to the depths, the effective rate of utilization of raising specific surface; Shorter ion diffusion path has also reduced the internal resistance of electrode materials simultaneously.Simultaneous in addition micropore and mesoporously give the desalination electrode higher specific surface area helps obtaining higher CDI performance.Macropore, mesoporous and micropore are effectively combined a kind of multistage hole carbon capacitor type desalination electrode for preparing, have higher specific surface area, good electrical conductivity and better desalting performance.
The objective of the invention is to reach through following technique means and measure.
The present invention provides a kind of preparation method of multistage hole carbon capacitor type desalination electrode, it is characterized in that following preparation process and step:
(1) preparation of electrode materials:
With monodisperse silica (SiO
2) ultra-sonic dispersion is in a certain amount of ethanolic soln, 15 ~ 35
oC deposits naturally, and high temperature sintering obtains SiO then
2Template; In phenol, add 20 wt% sodium hydroxide solutions, the back that stirs slowly adds 37 wt% formaldehyde solutions, is warming up to 65 ~ 75
oC reacts 1 ~ 2.5 h, is cooled to after the room temperature and regulates pH to neutral with 0.6 M hydrochloric acid, and the cryogenic vacuum underpressure distillation reduces water-content, add then ethanol stir 10-12 h after the centrifugal inorganic salt of removing obtain 20 wt% novolak resin precursor liquid solutions; The ethanolic soln (4.76 wt%) of structure directing agent is mixed with the novolak resin precursor liquid solution.SiO then
2Template is impregnated in the mixing solutions, and suction filtration is removed excessive solution behind the low temperature volatiling reaction, and further low temperature volatilization hot setting adds 10 wt% hydrofluoric acid solution stirring reactions then and removes SiO after the carbonization in inert atmosphere
2Template can obtain multistage hole carbon material after the thorough washing drying; The preparation of multistage hole carbon capacitor type desalination electrode:
With the multistage hole carbon material of step (1) preparation, acetylene black and ptfe emulsion are to be applied to after 80:10:10 ~ 90:5:5 mixes on the conductive substrates graphite paper, subsequently 100 ~ 120 according to mass ratio
oThe C dried over night; Finally make multistage hole carbon capacitor type desalination electrode.
Above-mentioned single SiO that disperses
2Diameter of micro ball is 100 ~ 400 nm; Above-mentioned SiO
2The solid content of microballoon is 1% ~ 10% in the alcohol dispersion liquid of microballoon.The silicon dioxide microsphere dispersion liquid of certain grain size size and density can form quality formwork structure preferably; Undersized or density is crossed when hanging down, and sedimentation velocity is slow excessively, and then dispersion liquid can exist with the equilibrated dispersion system, can cause very difficult formation template or formation time long; When oversize the or dispersion liquid density of microballoon was too high, sedimentation velocity was too fast, and it is relatively poor that the colloid micro ball that concentrates on container bottom has little time to experience the template quality that causes obtaining from changing mutually of disorder to order.
Above-mentioned structure directing agent is F127 (PEO
106-PPO
70-PEO
106), P123 (PEO
20-PPO
70-PEO
20) or both mixing.In addition, the mol ratio of phenol, formaldehyde, sodium hydroxide and structure directing agent is 1:2:0.1:0.005 ~ 0.025.The water-wet side at triblock copolymer PEO-PPO-PEO two ends and novolak resin precursor body have stronger hydrogen bond action, have guaranteed good dispersiveness, for further polymerization pyrolytic reaction provides possibility; Secondly the PEO-PPO-PEO template has a large amount of Sauerstoffatoms and lower decomposition temperature, is easy to remove, and is the good template of preparation porous carbon materials.
SiO behind the above-mentioned presoma dipping
2Template need be passed through low temperature volatilization hot setting two-step reaction, and wherein low temperature evaporable temperature is 30 ~ 60
oC; The temperature of hot setting is 100 ~ 140
oC.Low temperature volatilization, hot setting make resol further volatilize and form after the polymerization to have the inflexible macromolecular scaffold.It is slower that temperature is crossed low resol polycondensation, is unfavorable for being completed into the inflexible macromolecular scaffold.Since under aerobic conditions, solidify, when temperature is too high, resol oxidation blackout.
Above-mentioned carbonization process need realize through sectional temperature-controlled calcining in inert atmosphere that the control temperature rise rate is 1
oC/min at first is warming up to 300 ~ 500
oC, insulation is 1-4 hour under this temperature, is warming up to 500 ~ 1100 then
oC, insulation is 1-6 hour under this temperature.Inert protective gas comprises nitrogen and argon gas, and gas flow rate is 80-140 mL/min.Carbonization process carries out under protection of inert gas, helps keeping the carbon skeleton structure, if containing roasting under the oxygen condition, can cause caving in of carbon skeleton.Carbonization process divides two sections to carry out roasting in addition, is to degrade fully because help triblock copolymer in low temperature insulation for some time; High temperature cabonization forms the stable carbon skeleton structure with certain degree of graphitization subsequently.
The novel porous carbon capacitor type desalination electrode with hierarchy of the inventive method preparation has higher specific surface area, good electrical conductivity and better desalting performance, simple, the easy handling of preparation process.Having the potential application prospect aspect the capacitor type desalination.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment 1
With diameter is the monodisperse silica ultra-sonic dispersion (massfraction is 1 wt%) in ethanolic soln of 150 nm, then 20
oC deposition 1-2 is after week 600
oC sintering 1.5 h make SiO
2Template.In 0.61 g fused phenol, add 0.13 g, 20 wt% sodium hydroxide solutions, the back that stirs slowly adds 1.05 g, 37 wt % formaldehyde solutions, is warming up to 65
oC reacts 2 h, is cooled to after the room temperature and regulates PH to neutral with 0.6 M hydrochloric acid, and the cryogenic vacuum decompression dehydration adds ethanolic soln then and stirs 10 h to sticky, and the final centrifugal inorganic salt of removing obtain 20 wt% novolak resin precursor liquid solutions.With 1 g F127 (PEO
106PPO
70PEO
106) join in the 20 g ethanol after the stirring and dissolving, add precursor solution and mix.Wherein the mol ratio of phenol, formaldehyde, sodium hydroxide and structure directing agent is 1:2:0.1:0.012.Then with 0.5 g SiO
2Template adds in the above-mentioned mixing solutions, and 30
oIt is sticky that C evaporates into solution, and suction filtration is removed further back further 30 of excessive solution
oC volatilization self-assembly 8 h, 100
oC solidifies 24 h and is placed in the tube furnace, is under the nitrogen protection of 100 mL/min at gas flow rate, and the control temperature rise rate is 1
oC/min at first is warming up to 350
oC is 350
oC is incubated 2h, is warming up to 800 then
oC is 800
oC is incubated 4 h.The 10 wt% hydrofluoric acid solution stirred overnight that add to the room temperature to be cooled are removed SiO
2Template promptly obtains multistage hole carbon material after the thorough washing drying.With the multistage hole carbon material of gained, acetylene black and ptfe emulsion are to be applied on the graphite paper after 80:10:10 mixes according to mass ratio, subsequently 100
oC ~ 120
oThe C dried over night.Finally make multistage hole carbon desalination electrode.
Test the ratio electric capacity of above-mentioned multistage hole carbon desalination electrode.Use CHI 660D type electrochemistry electrochemical workstation, ionogen is 1 M sodium chloride solution, and scanning speed is 10 mV/s, and voltage range is-0.5 V ~ 0.5 V; Record the ratio electric capacity of this electrode its desalting performance of electrode test greater than the above-mentioned preparation of 120 F/g., in the salt solution of 600 ppm, its desalting efficiency is greater than 90%.
Embodiment 2
With diameter is the monodisperse silica ultra-sonic dispersion (massfraction is 3 wt%) in ethanolic soln of 250 nm, then 25
oC deposition 1-2 is after week 600
oC sintering 1.5 h make SiO
2Template.In 1.22 g fused phenol, add 0.26 g, 20 wt% sodium hydroxide solutions, the back that stirs slowly adds 2.1 g, 37 wt % formaldehyde solutions, is warming up to 70
oC reacts 1.5 h, is cooled to after the room temperature and regulates PH to neutral with 0.6 M hydrochloric acid, and the cryogenic vacuum decompression dehydration adds ethanol then and stirs 12 h to sticky, and the final centrifugal inorganic salt of removing obtain 20 wt% novolak resin precursor liquid solutions.With 1.5 g P123 (PEO
20-PPO
70-PEO
20) join in the 30 g ethanol after the stirring and dissolving, add precursor solution and mix.Wherein the mol ratio of phenol, formaldehyde, sodium hydroxide and structure directing agent is 1:2:0.1:0.02.Then with 2 g SiO
2Template adds in the above-mentioned mixing solutions, and 45
oIt is sticky that C evaporates into solution, and suction filtration removes behind the excessive solution further 45
oC volatilization self-assembly 5 h, 120
oC solidifies 20 h and is placed in the tube furnace, is under the nitrogen protection of 80 mL/min at gas flow rate, and the control temperature rise rate is 1
oC/min at first is warming up to 400
oC is 400
oC is incubated 2 .5h, is warming up to 600 then
oC is 600
oC is incubated 4 h.The 10 wt% hydrofluoric acid solution stirred overnight that add to the room temperature to be cooled are removed SiO
2Template promptly obtains multistage hole carbon material after the thorough washing drying.With the multistage hole carbon material of gained, acetylene black and ptfe emulsion are to be applied on the graphite paper after 85:10:5 mixes according to mass ratio, subsequently 100
oC ~ 120
oThe C dried over night.Finally make multistage hole carbon desalination electrode.
Test the ratio electric capacity of above-mentioned multistage hole carbon desalination electrode.Use CHI 660D type electrochemistry electrochemical workstation, ionogen is 1 M sodium chloride solution, and scanning speed is 10 mV/s, and voltage range is-0.5V ~ 0.5V; Record the ratio electric capacity of this electrode its desalting performance of electrode test greater than the above-mentioned preparation of 95 F/g., in the salt solution of 800 ppm, its desalting efficiency is greater than 85%.
Embodiment 3
With diameter is the monodisperse silica ultra-sonic dispersion (massfraction is 6 wt%) in ethanolic soln of 400 nm, then 28
oC deposition 1-2 is after week 600
oC sintering 1.5 h make SiO
2Template.In 0.61 g fused phenol, add 0.13 g, 20 wt% sodium hydroxide solutions, the back that stirs slowly adds 1.05 g, 37 wt % formaldehyde solutions, is warming up to 75
oC reacts 1.5 h, is cooled to after the room temperature and regulates PH to neutral with 0.6 M hydrochloric acid, and the cryogenic vacuum decompression dehydration adds ethanol then and stirs 10 h to sticky, and the final centrifugal inorganic salt of removing obtain 20 wt% novolak resin precursor liquid solutions.With 0.5 g F127 (PEO
106PPO
70PEO
106) and 0.5 g P123 (PEO
20-PPO
70-PEO
20) join in the 20 g ethanol after the stirring and dissolving, add precursor solution and mix.Wherein the mol ratio of phenol, formaldehyde, sodium hydroxide and structure directing agent is 1:2:0.1:0.017.Then with 4 g SiO
2Template adds in the above-mentioned mixing solutions, and 55
oIt is sticky that C evaporates into solution, and suction filtration removes behind the excessive solution further 55
oC volatilization self-assembly 5 h, 100
oC solidifies 24 h and is placed in the tube furnace, is under the nitrogen protection of 130 mL/min at gas flow rate, and the control temperature rise rate is 1
oC/min at first is warming up to 500
oC is 500
oC is incubated 3 h, is warming up to 1000 then
oC is 1000
oC is incubated 2 h.The 10 wt% hydrofluoric acid solution stirred overnight that add to the room temperature to be cooled are removed SiO
2Template promptly obtains multistage hole carbon material after the thorough washing drying.With the multistage hole carbon material of gained, acetylene black and ptfe emulsion are to be applied on the graphite paper after 90:5:5 mixes according to mass ratio, subsequently 100
oC ~ 120
oThe C dried over night.Finally make multistage hole carbon desalination electrode.
Test the ratio electric capacity of above-mentioned multistage hole carbon desalination electrode.Use CHI 660D type electrochemistry electrochemical workstation, ionogen is 1 M sodium chloride solution, and scanning speed is 10 mV/s, and voltage range is-0.5 V ~ 0.5 V; Record the ratio electric capacity of this electrode its desalting performance of electrode test greater than the above-mentioned preparation of 80 F/g., in the salt solution of 300 ppm, its desalting efficiency is greater than 80%.
Claims (7)
1. the preparation method of multistage hole carbon capacitor type desalination electrode is characterized in that may further comprise the steps:
(1) preparation of electrode materials: with monodisperse silica (SiO
2) ultra-sonic dispersion is in a certain amount of ethanolic soln, 15 ~ 35
oC deposits naturally, and high temperature sintering obtains SiO then
2Template; In phenol, add 20 wt% sodium hydroxide solutions, the back that stirs slowly adds 37 wt% formaldehyde solutions, is warming up to 65 ~ 75
oC reacts 1 ~ 2.5 h, is cooled to after the room temperature and regulates pH to neutral with 0.6 M hydrochloric acid, and the cryogenic vacuum underpressure distillation reduces water-content, add then ethanol stir 10-12 h after the centrifugal inorganic salt of removing obtain 20 wt% novolak resin precursor liquid solutions; The ethanolic soln and the novolak resin precursor liquid solution of 4.76 wt% structure directing agents are mixed; SiO then
2Template is impregnated in the mixing solutions, and suction filtration is removed excessive solution behind the low temperature volatiling reaction, and further low temperature volatilization hot setting adds 10 wt% hydrofluoric acid solution stirring reactions then and removes SiO after the carbonization in inert atmosphere
2Template can obtain multistage hole carbon material after the thorough washing drying;
(2) preparation of capacitor type desalination electrode: with the multistage hole carbon material of step (1) preparation, acetylene black and ptfe emulsion are to be applied to after 80:10:10 ~ 90:5:5 mixes on the conductive substrates graphite paper, subsequently 100 ~ 120 according to mass ratio
oThe C dried over night; Finally make multistage hole carbon capacitor type desalination electrode.
2. the preparation method of multistage hole carbon capacitor type desalination electrode according to claim 1 is characterized in that described single SiO of dispersion
2Diameter of micro ball is 100 ~ 400 nm.
3. the preparation method of multistage hole carbon capacitor type desalination electrode according to claim 1 is characterized in that described SiO
2The massfraction of microballoon is 1 ~ 10% in the ethanolic soln of microballoon.
4. the preparation method of multistage hole carbon capacitor type desalination electrode according to claim 1 is characterized in that described structure directing agent comprises F127 (PEO
106-PPO
70-PEO
106) and P123 (PEO
20-PPO
70-PEO
20) in a kind of or both mixing.
5. the preparation method of multistage hole carbon capacitor type desalination electrode according to claim 1 is characterized in that in the described preparation process, the mol ratio of phenol, formaldehyde, sodium hydroxide and structure directing agent is 1:2:0.1:0.005 ~ 0.025.
6. the preparation method of multistage hole carbon capacitor type desalination electrode according to claim 1 is characterized in that the SiO that described presoma floods
2Template need be passed through low temperature volatilization and hot setting two-step reaction, and wherein low temperature evaporable temperature is 30 ~ 60
oC; The temperature of hot setting is 100 ~ 140
oC.
7. the preparation method of multistage hole carbon capacitor type desalination electrode according to claim 1 is characterized in that the carbonization process in the described inert atmosphere need be realized through sectional temperature-controlled calcining, and the control temperature rise rate is 1
oC/min at first is warming up to 300 ~ 500
oC, insulation 1-4 h is warming up to 500 ~ 1100 then under this temperature
oC, insulation 1-6 h under this temperature; Inert protective gas comprises nitrogen and argon gas, and gas flow rate is 80-140 mL/min.
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| CN111224189A (en) * | 2020-01-16 | 2020-06-02 | 东莞理工学院 | Activated carbon microsphere electrode material based on waste lithium ion battery negative electrode material and preparation and application thereof |
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