CN105696115B - A kind of method that electrode material for super capacitor is prepared based on rotor spinning method - Google Patents
A kind of method that electrode material for super capacitor is prepared based on rotor spinning method Download PDFInfo
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- CN105696115B CN105696115B CN201610220070.7A CN201610220070A CN105696115B CN 105696115 B CN105696115 B CN 105696115B CN 201610220070 A CN201610220070 A CN 201610220070A CN 105696115 B CN105696115 B CN 105696115B
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- 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
Abstract
A kind of method that electrode material for super capacitor is prepared based on rotor spinning method, the method include following six step：1) preparation of spinning solution, 2) rotor spinning process, 3) curing process, 4) charing process, 5) pickling processes, 6) half-cell assembling.The present invention not only prepares the nano carbon fiber with high specific surface area, and can be by changing regulation and control of the addition realization of pore creating material to fiber pore structure.Running cost is greatly reduced using rotor spinning method, and ensure that the yield of fiber, is advantageously implemented industrialized production.
Description
Technical field：
The present invention relates to a kind of method that electrode material for super capacitor is prepared based on rotor spinning method.
Background technology
Ultracapacitor, also known as electrochemical capacitor are a kind of performances between traditional capacitor and secondary cell
New type of energy storage device, there is big specific capacity, long circulation life, high power density, thus receive significant attention.Super
In capacitor assembly, electrode material is the key factor for influenceing performance of the supercapacitor.
The unitary electrode material and combination electrode material of Carbon Materials, metal oxide and conducting polymer are conventional at present
Electrode material for super capacitor.It is larger because of its from the preparation technology and chemical property of various electrode materials, nano carbon fiber
Specific surface area and relatively low resistance have obvious advantage.At present, the method for preparing carbon nano-fiber is mainly vapor growth method,
Such as Chinese invention patent CNI172846C, CN1061706C and CNI292984C etc..This method production cost is high, and this side
The Carbon fiber dimension that method obtains is shorter, typically at a few micrometers to nearly hundred microns, it is difficult to play the advantage of nano carbon fiber.Some grind
The person of studying carefully proposes the method that nano carbon fiber is prepared using the method for electrostatic spinning, such as Chinese patent CN103882559A and
CN103014921A with polyacrylonitrile (hereinafter referred to as PAN), phenolic resin, pitch etc. for presoma, be separately added into potassium sulfide and
Terephthalic acid (TPA) obtains as-spun fibre, then obtain Nano carbon by solidification, charing, pickling as pore creating material by electrostatic spinning
Fiber.This method can obtain continuous nano carbon fiber, and fibre diameter is uniform, have certain advantage.But presently relevant research
It is based primarily upon laboratory equipment to study, rare large-scale production equipment, spinning efficiency is low.
Chinese patent CN102936764A provides one kind and prepares PAN based nano-fibers using solution jet spinning method,
The method through pre-oxidizing (i.e. non-fusible), carbon nano-fiber is made in carbonization treatment, the patent relate only to simple Carbon fibe again.This
Invention uses rotor spinning device, pore creating material is added in spinning solution porous carbon fiber is made and is used for electrode of super capacitor
Material, production efficiency is substantially increased, be advantageous to large-scale production.
The content of the invention：
It is this it is an object of the invention to provide a kind of method that electrode material for super capacitor is prepared based on rotor spinning method
Porous nano Carbon fibe prepared by method has higher specific capacitance as the electrode material of ultracapacitor.
The preparation method of the present invention comprises the following steps：
1. the preparation of spinning solution：
The preparation of PAN spinning solutions：(1) weighing a certain amount of PAN makes it be dissolved in DMF (hereinafter referred to as
DMF in), 2-6h is stirred, is made into 8-30wt% PAN solution；(2) 1-9% mass fractions are added in the PAN solution in (1)
Pore creating material, stir 3-6 hours, produce PAN spinning solutions.
The preparation of phenolic resin spinning solution：(1) phenol is melted at 50-60 DEG C, and adds catalyst n aOH and glue
Agent polyvinyl alcohol (hereinafter referred to as PVA) is tied, 90-100 DEG C is warming up to, formaldehyde, then constant temperature 80- is added after constant temperature 50-60min
120min, wherein formaldehyde and phenol mol ratio is：3.5: 1-4.5: 1, react and product is cooled to room temperature after terminating；(2) will
Obtained phenolic resin is made into the 15%-20% aqueous solution；(3) on the basis of mixed liquor gross mass, solution adds 1- in (2)
The pore creating material of 9% mass fraction, 3-6 hours are stirred, produce phenolic resin spinning solution.
2nd, rotor spinning process：Its general principle is as shown in Fig. 2 spinning solution is extruded by shower nozzle, the speed of high velocity air
Spend and obtain as-spun fibre for 100-1000m/min, thus progress spinning.
3. curing process：PAN as-spun fibres are subjected to pre-oxidation 2-4h under 150-280 DEG C of air atmosphere；By phenolic aldehyde tree
Fat as-spun fibre, which is placed under 120-160 DEG C of air atmosphere, carries out solidification 1.5-3.5h.
4. charing process：Under nonoxidizing atmosphere, 900 DEG C and constant temperature 100-150min are warming up to certain heating rate,
Obtain nano carbon fiber.
5. pickling processes：Obtained product is placed in 24-72h in 5-30% hydrochloric acid solution, is then washed to neutrality.
6. half-cell assembles：Gained Carbon fibe film is directly cut into disk, this disk is placed in two panels piece after weighing
In nickel foam disk, electrode is pressed into tablet press machine.Using 6M KOH solutions as electrolyte, using Pt electrodes as to electrode, with Hg/
HgO electrodes are reference electrode.Test is carried out at room temperature.
The nonoxidizing atmosphere refers to completely cut off air or under inert gas shielding, such as non-oxide gas of nitrogen, argon gas
Atmosphere.
Advantages of the present invention is as follows：
Prepare the nano carbon fiber with high specific surface area, its specific surface area and pore volume can with using Static Spinning
Nano carbon fiber made from silk method compares favourably.
Can be by changing regulation and control of the addition realization of pore creating material to fiber pore structure.
Running cost is greatly reduced using rotor spinning method, and ensure that the yield of fiber, is advantageously implemented industrialization
Production.
Brief description of the drawings：
Fig. 1 show whole preparation process flow chart
Fig. 2 show rotor spinning principle sketch
Label is as follows in figure：
1- spinning solution 2- high velocity air 3- as-spun fibres
Embodiment：
Embodiment 1：Take 2g PAN to be put into 50ml beakers, 14.67g DMF, stirring 2-4h to dissolving are added into beaker
Uniformly, that is, it is made into 12wt%PAN DMF solution.0.167g zinc chloride are added into above-mentioned solution, 4h is to being uniformly dissolved for stirring,
Obtain spinning solution.As-spun fibre is obtained by rotor spinning.Obtained as-spun fibre is placed in 250 DEG C of Muffle furnaces two
Hour is pre-oxidized.Cured fiber is placed in tube type resistance furnace, under nitrogen protection, with 3 DEG C/min heating rate liter
800 DEG C of constant temperature 30min are raised to 600 DEG C of constant temperature one hour, then with 5 DEG C/min heating rate.Carbon fiber is put in 5wt%
HCl/water solution in soak 24h after, product is washed to neutrality by the way of suction filtration, 24h dries sample at 100 DEG C,
Finally give the porous nano Carbon fibe with high specific surface area.Electro-chemical test shows it under 0.2A/g current density
Specific capacitance be 219F/g, N2 adsorption test shows that the specific surface area of sample is 506m2/g。
Embodiment 2：Take 2g PAN to be put into 50ml beakers, 14.67g DMF, stirring 2-4h to dissolving are added into beaker
Uniformly, that is, it is made into 12wt%PAN DMF solution.0.833gKOH is added into above-mentioned solution, 4h is to being uniformly dissolved for stirring, produces
To spinning solution.As-spun fibre is obtained by rotor spinning.Obtained as-spun fibre is placed in two hours in 250 DEG C of Muffle furnaces
Pre-oxidized.Cured fiber is placed in tube type resistance furnace, under nitrogen protection, 600 are raised to 3 DEG C/min heating rate
DEG C constant temperature one hour, then 800 DEG C of constant temperature 30min are raised to 5 DEG C/min heating rate.Carbon fiber is put into the HCl in 5wt%
After soaking 24h in the aqueous solution, product is washed to neutrality by the way of suction filtration, 24h dries sample at 100 DEG C, finally
Obtain the porous nano Carbon fibe with high specific surface area.Electro-chemical test shows its ratio under 0.2A/g current density
Electric capacity is 240F/g, and N2 adsorption test shows that the specific surface area of sample is 670m2/g。
Embodiment 3：Take 2g PAN to be put into 50ml beakers, 14.67g DMF, stirring 2-4h to dissolving are added into beaker
Uniformly, that is, it is made into 12wt%PAN DMF solution.1.500g zinc chloride are added into above-mentioned solution, 4h is to being uniformly dissolved for stirring,
Obtain spinning solution.As-spun fibre is obtained by rotor spinning.Obtained as-spun fibre is placed in 250 degree of Muffle furnaces two
Hour is pre-oxidized.Cured fiber is placed in tube type resistance furnace, under nitrogen protection, with 3 DEG C/min heating rate liter
800 DEG C of constant temperature 30min are raised to 600 DEG C of constant temperature one hour, then with 5 DEG C/min heating rate.Carbon fiber is put in 5wt%
HCl/water solution in soak 24h after, product is washed to neutrality by the way of suction filtration, 24h dries sample at 100 DEG C,
Finally give the porous nano Carbon fibe with high specific surface area.Electro-chemical test shows it under 0.2A/g current density
Specific capacitance be 276F/g, N2 adsorption test shows that the specific surface area of sample is 780m2/g。
Embodiment 4：25.6g PVA are taken, 192g water, 5.04gNaOH, 60g phenol, pour into three-necked flask heating stirring to 96
DEG C, constant temperature stirring half an hour after add 60g formaldehyde, then constant temperature stir 1 hour after add 15g formaldehyde.Stop after reaction 100min
Heating and stirring, take out flask and the phenolic resin of synthesis is quickly cooled down and surveys its solid content.Above-mentioned resin is made into 18%
The aqueous solution, stir.15g phenol resin solutions are taken, add 0.15g KOH thereto, 4h is to being uniformly dissolved for stirring, that is, obtains
Spinning solution.As-spun fibre is obtained by rotor spinning.Obtained as-spun fibre is placed in 150 DEG C of baking ovens and solidifies 2h, will be solid
Chemical fibre dimension is placed in tube type resistance furnace, under nitrogen protection, 800 DEG C of constant temperature is raised to one hour with 3 DEG C/min heating rate.Will
Carbon fiber is put after immersion 24h, is washed to neutrality, 100 by the way of suction filtration in 5wt% HCl/water solution by product
24h dries sample at DEG C, finally gives the porous nano Carbon fibe with high specific surface area.Electro-chemical test show its
Specific capacitance under 0.2A/g current density is 211F/g, and N2 adsorption test shows that the specific surface area of sample is 499m2/g。
Embodiment 5：25.6g PVA are taken, 192g water, 5.04g NaOH, 60g phenol, pour into three-necked flask heating stirring extremely
96 DEG C, constant temperature stirring half an hour after add 60g formaldehyde, then constant temperature stir 1 hour after add 15g formaldehyde.Stop after reaction 100min
Only heat and stir, take out flask and the phenolic resin of synthesis is quickly cooled down and surveys its solid content.Above-mentioned resin is made into 18%
The aqueous solution, stir.15g phenol resin solutions are taken, add 1.05g KOH thereto, 4h is to being uniformly dissolved for stirring, produces
To spinning solution.As-spun fibre is obtained by rotor spinning.Obtained as-spun fibre is placed in 150 DEG C of baking ovens and solidifies 2h, will
Cured fiber is placed in tube type resistance furnace, under nitrogen protection, 800 DEG C of constant temperature is raised to one hour with 3 DEG C/min heating rate.
Carbon fiber is put after soaking 24h in 5wt% HCl/water solution, product is washed to neutrality by the way of suction filtration,
24h dries sample at 100 DEG C, finally gives the porous nano Carbon fibe with high specific surface area.Electro-chemical test shows
Its specific capacitance under 0.2A/g current density is 249F/g, and N2 adsorption test shows that the specific surface area of sample is 682m2/g。
Embodiment 6：25.6g PVA are taken, 192g water, 5.04gNaOH, 60g phenol, pour into three-necked flask heating stirring to 96
DEG C, constant temperature stirring half an hour after add 60g formaldehyde, then constant temperature stir 1 hour after add 15g formaldehyde.Stop after reaction 100min
Heating and stirring, take out flask and the phenolic resin of synthesis is quickly cooled down and surveys its solid content.Above-mentioned resin is made into 18%
The aqueous solution, stir.15g phenol resin solutions are taken, add 1.35g KOH thereto, 4h is to being uniformly dissolved for stirring, that is, obtains
Spinning solution.As-spun fibre is obtained by rotor spinning.Obtained as-spun fibre is placed in 150 DEG C of baking ovens and solidifies 2h, will be solid
Chemical fibre dimension is placed in tube type resistance furnace, under nitrogen protection, 800 DEG C of constant temperature is raised to one hour with 3 DEG C/min heating rate.Will
Carbon fiber is put after immersion 24h, is washed to neutrality, 100 by the way of suction filtration in 5wt% HCl/water solution by product
24h dries sample at DEG C, finally gives the porous nano Carbon fibe with high specific surface area.Electro-chemical test show its
Specific capacitance under 0.2A/g current density is 269F/g, and N2 adsorption test shows that the specific surface area of sample is 797m2/g。
Claims (7)
- A kind of 1. method that electrode material for super capacitor is prepared based on rotor spinning method, it is characterised in that in precursor solution The mixed liquor for adding different proportion pore creating material is spinning solution, and spinning solution is obtained into just spinning fibre by rotor spinning device spinning Dimension, by solidifying, carbonizing, pickling processes obtain porous carbon fiber as electrode material.
- 2. a kind of method that electrode material for super capacitor is prepared based on rotor spinning method as claimed in claim 1, its feature It is zinc chloride or potassium hydroxide to be the pore creating material.
- 3. a kind of method that electrode material for super capacitor is prepared based on rotor spinning method as claimed in claim 2, its feature It is the presoma using polyacrylonitrile or phenolic resin as charcoal.
- 4. a kind of method that electrode material for super capacitor is prepared based on rotor spinning method as claimed in claim 3, its feature The quality for being pore creating material addition is the 1-9% of polyacrylonitrile solution or phenol resin solution quality.
- A kind of 5. side that electrode material for super capacitor is prepared based on rotor spinning method as described in claim any one of 1-4 Method, it is characterised in that obtained porous carbon fiber specific surface area ＞ 490m2/g。
- 6. a kind of electrode material, it is characterised in that rotor spinning legal system is based on using one kind described in claim any one of 1-5 The method of standby electrode material for super capacitor is prepared.
- 7. a kind of half-cell being prepared using electrode material as claimed in claim 6, it is characterised in that molten with 6M KOH Liquid is electrolyte, and using Pt electrodes as to electrode, using Hg/HgO electrodes as reference electrode, it is surveyed in 0.2A/g through electrochemical workstation Specific capacitance ＞ 200F/g under current density.
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| CN110656402A (en) * | 2019-01-21 | 2020-01-07 | 深圳维度新材料有限公司 | Preparation method and equipment of inorganic nano-fiber |
| CN112186141A (en) * | 2019-07-04 | 2021-01-05 | 天津工业大学 | Flexible self-supporting carbon fiber negative electrode material of lithium/sodium ion battery and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071542A (en) * | 2011-02-22 | 2011-05-25 | 天津工业大学 | Method for preparing polymeric nano-micro fiber non-woven fabric |
| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
| CN103882559A (en) * | 2014-03-13 | 2014-06-25 | 中国科学院化学研究所 | High-specific surface porous carbon fiber, preparation method and application of carbon fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071542A (en) * | 2011-02-22 | 2011-05-25 | 天津工业大学 | Method for preparing polymeric nano-micro fiber non-woven fabric |
| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
| CN103882559A (en) * | 2014-03-13 | 2014-06-25 | 中国科学院化学研究所 | High-specific surface porous carbon fiber, preparation method and application of carbon fiber |
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