CN104036973B - A kind of ultracapacitor rich nitrogen Carbon foam electrode material and preparation method thereof - Google Patents

A kind of ultracapacitor rich nitrogen Carbon foam electrode material and preparation method thereof Download PDF

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Publication number
CN104036973B
CN104036973B CN201410285125.3A CN201410285125A CN104036973B CN 104036973 B CN104036973 B CN 104036973B CN 201410285125 A CN201410285125 A CN 201410285125A CN 104036973 B CN104036973 B CN 104036973B
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temperature
follows
resin
technological parameter
ultracapacitor
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CN201410285125.3A
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CN104036973A (en
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林起浪
连琴凤
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福州大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention provides rich nitrogen Carbon foam electrode material of a kind of ultracapacitor and preparation method thereof, using the nickel foam after acid treatment is auxiliary template, with cyanate as raw material, remove technique prepare the rich nitrogen Carbon foam electrode material of ultracapacitor through pre-polymerization, moulding by casting, solidification, carbonization, template.Foam carbon material uniform pore diameter, nitrogen content height, good conductivity, porosity and percent opening that the present invention prepares are high, intensity is high;Its specific capacity is high simultaneously, good cycle;And without foam process, labyrinth molding can be realized.

Description

A kind of ultracapacitor rich nitrogen Carbon foam electrode material and preparation method thereof
Technical field
The invention belongs to high performance carbon cellulosic material field, be specifically related to rich nitrogen Carbon foam electrode material of a kind of ultracapacitor and preparation method thereof.
Background technology
Along with economic rapid development and the sharp increase of population, the energy and resource that the mankind depend on for existence are the most exhausted.In order to solve energy crisis, on the one hand, the novel energies such as solar energy, wind energy, ocean energy and nuclear energy are gradually developed use;On the other hand, exploitation and the utilization of efficient, inexpensive and energy-conservation novel energy-storing device are extremely the most urgent.At present, main energy storage device has secondary cell and traditional physical capacitor.Secondary cell exists that charging interval length, energy storage density be low and the shortcoming such as service life is short.Traditional physical capacitor is limited extensively application equally because of its low energy storage density.Being difficult to meet in the case of growing energy storage requires at traditional energy storage device, novel energy storage device ultracapacitor arises at the historic moment and develops rapidly.Compared with secondary cell and traditional physical capacitor, the advantage such as ultracapacitor has that charge/discharge rates is fast, energy storage density is high, has extended cycle life, the temperature that works limit for width, is a kind of energy-conservation and efficient energy storage device.Super main component includes collector, electrolyte, electrode and barrier film etc..Wherein structure and the characteristic of electrode material is the key determining ultracapacitor performance.Therefore, the research and development of high performance electrode for super capacitor material has great importance.At present, porous carbonaceous electrode material is by one of the most frequently used electrode material of double layer capacitor research.
Carbon foam is a kind of 3 D stereo mesh structural porous property lightweight functional material, in addition to there is the performance of common Carbon Materials, also have that density is little, specific surface area is big, mechanical property is good, thermal shock resistance heat conductivity good, adjustable and a series of mechanics such as dielectric coefficient, good, the structure-controllable of absorbing property, acoustics, optics, electricity, calorifics spy can, be therefore widely studied as newly entering construction material the most always.It is known that, cyanate ester resin has the pyrolysis feature from foaming, can obtain, by being pyrolyzed this resin, the foam carbon material that nitrogen content is high, it is known that nitrogen element can improve the wettability of foam carbon material from document, therefore can improve the utilization rate of Carbon foam electrode material.In addition, the addition of nitrogen element can also produce fake capacitance by faraday's redox reaction.Above 2 chemical properties that can improve Carbon foam electrode material.By the foam carbon material of pyrolysis cyanate ester resin acquisition in addition to there is nitrogen content height, also there is the performances such as porosity height, mechanical strength height, good conductivity, but its percent opening is relatively low.Additionally, Carbon foam is a kind of heat-barrier material, the resin elder generation carbonization on top layer during resin carbonization after solidification is become Carbon foam, heat can not well be conducted to nexine resin, hinder the uniformity of resin carbonization, the hole bubble making Carbon foam is the most uniform, this seriously inhibits the promotion and application as electrode for super capacitor material of this Carbon foam, and use nickel foam can well solve the problem of transmission of heat as the auxiliary template of Carbon foam, nickel foam act as good heat carrier in resin curing process, heat can be well transmitted in the middle of resin by carbonization process, make resin carbonization comprehensive, and then improve the uniformity of Carbon foam abscess.Nickel foam surface after peracid treatment produces rough rough surface and provides reverse template for Carbon foam hole wall, thus increases the specific surface area of Carbon foam.It addition, after being removed by the nickel foam template concentrated hydrochloric acid of prepared Carbon foam, be left with uniform passage in the place of original nickel foam, these passages are conducive to electrolyte turnover in Carbon foam electrode, and then improve its chemical property.
Summary of the invention
It is an object of the invention to provide rich nitrogen Carbon foam electrode material of a kind of ultracapacitor and preparation method thereof, the foam carbon material uniform pore diameter, nitrogen content height, good conductivity, porosity and the percent opening that prepare are high, intensity is high;Its specific capacity is high simultaneously, good cycle;And without foam process, labyrinth molding can be realized.
For achieving the above object, the present invention adopts the following technical scheme that
Using the nickel foam after acid treatment is auxiliary template, with cyanate as raw material, removes technique prepare the rich nitrogen Carbon foam electrode material of ultracapacitor through pre-polymerization, moulding by casting, solidification, carbonization, template.
Preparation method comprises the following steps: the pretreatment of raw material, the preparation of auxiliary template, the pre-polymerization of thermosetting resin, moulding by casting, curing process, charring process, template are removed.
Specifically comprise the following steps that
(1) pretreatment of raw material
Base stock: one or both the mixture in bisphenol A cyanate ester, polyfunctional group cyanate;
Catalyst: dibutyl tin laurate or N,N-dimethylformamide;
By base stock and catalyst mix homogeneously;
Technological parameter is as follows:
Bisphenol A cyanate ester and the mass ratio of polyfunctional group cyanate: 1:0-1:1
Catalyst accounts for base stock consumption: 0.01-0.1 wt%;
(2) preparation of auxiliary template
Nickel foam is put in hydrochloric acid solution and soak, be then washed with deionized water to neutrality, be dried;
Technological parameter is as follows:
Nickel foam surface density: 250-600 g/m2
Concentration of hydrochloric acid solution: 0.1-1 mol/L
Soak time: 1-4 h
Soaking temperature: 15-25 DEG C
Baking temperature: 80 DEG C;
(3) pre-polymerization of thermosetting resin
Step (1) and the material mix homogeneously of (2), carry out polyreaction, it is thus achieved that pre-polymerization resin;
Technological parameter is as follows:
Temperature: 120-150 DEG C
Time: 0.5-1 h
Protective atmosphere: N2Or Ar
Gas flow: 50-200 mL/min
Mixing speed: 50-1000 rpm;
(4) moulding by casting
Pre-polymerization resin is poured in mould, de-bubbled;
Technological parameter is as follows:
Temperature: 130-160 DEG C
The de-bubbled time: 0.5-2 h
Vacuum: 1.0 × 10-1-1.0×103Pa;
(5) curing process
Resin after de-bubbled solidifies;
Technological parameter is as follows:
Solidification temperature: 130-250 DEG C, uses staged solidification, and i.e. 130-150 DEG C/1-2h → 160-200 DEG C/1-2h → 210-250 DEG C/2h, heating rate is 5 DEG C/min;
Hardening time: 3-6 h;
(6) charring process
Resin after solidification is put in atmosphere furnace after the demoulding, is incubated after being warming up to predetermined temperature with certain heating rate, then cools to room temperature with the furnace and takes out;
Technological parameter is as follows:
Heating rate: 2-20 DEG C/min
Predetermined temperature: 600-1300 DEG C
Temperature retention time: 0.5-10 h
Protective atmosphere: N2Or Ar
Gas flow: 50-200 mL/min;
(7) template is removed
Carbonizing production is put in hydrochloric acid solution and soak, take out, be washed with deionized water to neutrality, 100 DEG C of dry 5h, obtain the rich nitrogen Carbon foam electrode material of ultracapacitor;
Technological parameter is as follows:
Concentration of hydrochloric acid solution: 1-6 mol/L
Soaking temperature: 25-100 DEG C
Soak time: 0.2-5 h.
The present invention is by controlling structure and the performance of the Carbon foam electrode material that the proportioning of different types of cyanate ester resin, the selection of auxiliary material, the pretreatment of nickel foam template, resin solidification and charring process reach to adjust.Carbon foam electrode material obtained by preparation method of the present invention is used to have good chemical property and a mechanical property: porosity 80-95%, percent opening 89%-100%, specific surface area 150-400m2/ g, mesoporous 45%-70%, electrical conductivity 0.8-100S/m, compressive strength 1-10MPa, it can reach nearly 200F/g when electric current density is 0.1A/g than electric capacity, and the loss rate of electric capacity is the least after 2000 discharge and recharges, has good cyclical stability.Compared with prior art, advantage for present invention and effect are: technique is simple, it is easy to produce, easy and simple to handle;Preparation cost is low, excellent product performance;Without foam process, can once complicated molding.
Detailed description of the invention
The following is several specific embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
Embodiment 1
By bisphenol A cyanate ester with polyfunctional group cyanate by 40:0(mass ratio) weigh, it is subsequently adding the dibutyl tin laurate mix homogeneously of cyanate quality 0.01%.By nickel foam (surface density 250g/m2) it being placed in hydrochloric acid (concentration 0.1mol/L) immersion 4h (15 DEG C), the vacuum drying oven using deionized water to put into 80 DEG C after cleaning to neutrality is dried, and then nickel foam is put in cast iron die.The cyanate mixed and dibutyl tin laurate are loaded polymerization container, heats up by the speed of 5 DEG C/min, and start to be passed through Ar(flow 50mL/min from intensification).When temperature rises to 120 DEG C, rotating speed is adjusted to 500rpm stirring 30min and obtains pre-polymerization resin, is subsequently poured into evacuation de-bubbled 0.5h(vacuum 1.0 × 10 in mould (130 DEG C)-1Pa), then solidifying by following technique: 130 DEG C/1h+160 DEG C/2h+250 DEG C/1h, N put into by the resin after solidification2In special atmosphere oven; then 10h is kept after 2 DEG C/min heating rate is warming up to 600 DEG C of temperature; cool to the furnace room temperature take out be placed in concentration be 3mol/L, temperature be that the hydrochloric acid solution of 70 DEG C keeps 2h, be then washed to neutrality with deionized water and be placed in the baking oven of 100 DEG C and be dried 5h.
Prepared Carbon foam electrode material has a following performance: compressive strength 2.5MPa, porosity 85%, percent opening 91%, specific surface area 250m2/ g, mesoporous 55%, electrical conductivity 0.8S/m, N content 4.5%, be 138F/g when electric current density is 0.1A/g than electric capacity, and the loss rate of electric capacity be 7% after 2000 discharge and recharges.
Embodiment 2
Bisphenol A cyanate ester is weighed by 40:10 mass ratio with polyfunctional group cyanate, is subsequently adding the N of cyanate quality 0.05%, N-dimethylformamide mix homogeneously.By nickel foam (surface density 500g/m2) it being placed in hydrochloric acid (concentration 1mol/L) immersion 1h (25 DEG C), the vacuum drying oven using deionized water to put into 80 DEG C after cleaning to neutrality is dried, and then nickel foam is put in cast iron die.The cyanate mixed and dibutyl tin laurate are loaded polymerization container, heats up by the speed of 5 DEG C/min, and start to be passed through N from intensification2(flow 100mL/min).When temperature rises to 130 DEG C, rotating speed is adjusted to 600rpm stirring 40min and obtains pre-polymerization resin, being subsequently poured into evacuation de-bubbled 1h in mould (140 DEG C), then solidify by following technique: 150 DEG C/2h+200 DEG C/1h+240 DEG C/2h, N put into by the resin after solidification2In special atmosphere oven; 5h is kept after being warming up to 800 DEG C of temperature with 5 DEG C/min heating rate; cool to the furnace room temperature take out be placed in concentration be 4 mol/L, temperature be that the hydrochloric acid solution of 80 DEG C keeps 3h, then use deionized water to be washed to neutrality and be placed in the baking oven of 100 DEG C and be dried 5h.
Prepared Carbon foam electrode material has a following performance: compressive strength 4.8MPa, porosity 90%, percent opening 95%, specific surface area 320m2/ g, mesoporous 62%, electrical conductivity 60S/m, N content 6%, be 167F/g when electric current density is 0.1A/g than electric capacity, and the loss rate of electric capacity be 5% after 2000 discharge and recharges.
Embodiment 3
Bisphenol A cyanate ester is weighed by 40:20 mass ratio with polyfunctional group cyanate, is subsequently adding the dibutyl tin laurate mix homogeneously of cyanate quality 0.1%.By nickel foam (surface density 600g/m2) it being placed in hydrochloric acid (concentration 0.5mol/L) immersion 2h (25 DEG C), the vacuum drying oven using deionized water to put into 80 DEG C after cleaning to neutrality is dried, and then nickel foam is put in cast iron die.The cyanate mixed and dibutyl tin laurate are loaded polymerization container, heats up by the speed of 5 DEG C/min, and start to be passed through N from intensification2(flow 200mL/min).When temperature rises to 140 DEG C, rotating speed is adjusted to 800rpm stirring 50min and obtains pre-polymerization resin, being subsequently poured into evacuation de-bubbled 0.5h in mould (150 DEG C), then solidify by following technique: 140 DEG C/2h+180 DEG C/2h+250 DEG C/1h, N put into by the resin after solidification2In special atmosphere oven; then 2h is kept after 20 DEG C/min heating rate is warming up to 1000 DEG C of temperature; cool to the furnace room temperature be placed on concentration be 5mol/L, temperature be that the hydrochloric acid solution of 90 DEG C keeps 4h, then use deionized water to be washed to neutrality and be placed in the baking oven of 100 DEG C and be dried 5h.
Prepared Carbon foam electrode material has a following performance: compressive strength 8.2MPa, porosity 95%, percent opening 100%, specific surface area 400m2/ g, mesoporous 70%, electrical conductivity 83S/m, N content 6.4%, be 198F/g when electric current density is 0.1A/g than electric capacity, and the loss rate of electric capacity be 3% after 2000 discharge and recharges.
Embodiment 4
Bisphenol A cyanate ester is weighed by 40:30 mass ratio with polyfunctional group cyanate, is subsequently adding the dibutyl tin laurate mix homogeneously of cyanate quality 0.06%.By nickel foam (surface density 400g/m2) it being placed in hydrochloric acid (concentration 0.5mol/L) immersion 2h (25 DEG C), the vacuum drying oven using deionized water to put into 80 DEG C after cleaning to neutrality is dried, and then nickel foam is put in cast iron die.The cyanate mixed and dibutyl tin laurate are loaded polymerization container, heats up by the speed of 5 DEG C/min, and start to be passed through N from intensification2(flow 100mL/min).When temperature rises to 150 DEG C, rotating speed is adjusted to 1000rpm stirring 60min and obtains pre-polymerization resin, is subsequently poured into evacuation de-bubbled 2h(vacuum 1.0 × 10 in mould (160 DEG C)3Pa), then solidifying by following technique: 130 DEG C/2h+170 DEG C/2h+220 DEG C/2h, N put into by the resin after solidification2In special atmosphere oven; then 1h is kept after 10 DEG C/min heating rate is warming up to 1300 DEG C of temperature; cool to the furnace room temperature take out be placed in concentration be 6 mol/L, temperature be that the hydrochloric acid solution of 100 DEG C keeps 5h, be then washed to neutrality with deionized water and be placed in the baking oven of 100 DEG C and be dried 5h.
Prepared Carbon foam electrode material has a following performance: compressive strength 10MPa, porosity 80%, percent opening 89%, specific surface area 178m2/ g, mesoporous 45%, electrical conductivity 100S/m, N content 7%, be 152F/g when electric current density is 0.1A/g than electric capacity, and the loss rate of electric capacity be 6% after 2000 discharge and recharges.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent and modification, all should belong to the covering scope of the present invention.

Claims (1)

1. a ultracapacitor richness nitrogen Carbon foam electrode material, it is characterized in that: using the nickel foam after acid treatment is auxiliary template, with cyanate as raw material, remove technique prepare the rich nitrogen Carbon foam electrode material of ultracapacitor through pre-polymerization, moulding by casting, solidification, carbonization, template, comprise the following steps: the pretreatment of raw material, the preparation of auxiliary template, the pre-polymerization of thermosetting resin, moulding by casting, curing process, charring process, template are removed, and specifically comprise the following steps that
(1) pretreatment of raw material
Base stock: one or both the mixture in bisphenol A cyanate ester, polyfunctional group cyanate;
Catalyst: dibutyl tin laurate or N,N-dimethylformamide;
By base stock and catalyst mix homogeneously;
Technological parameter is as follows:
Bisphenol A cyanate ester and the mass ratio of polyfunctional group cyanate: 1:0-1:1
Catalyst accounts for base stock consumption: 0.01-0.1 wt%;
(2) preparation of auxiliary template
Nickel foam is put in hydrochloric acid solution and soak, be then washed with deionized water to neutrality, be dried;
Technological parameter is as follows:
Nickel foam surface density: 250-600 g/m2
Concentration of hydrochloric acid solution: 0.1-1 mol/L
Soak time: 1-4 h
Soaking temperature: 15-25 DEG C
Baking temperature: 80 DEG C;
(3) pre-polymerization of thermosetting resin
Step (1) and the material mix homogeneously of (2), carry out polyreaction, it is thus achieved that pre-polymerization resin;
Technological parameter is as follows:
Temperature: 120-150 DEG C
Time: 0.5-1 h
Protective atmosphere: N2Or Ar
Gas flow: 50-200 mL/min
Mixing speed: 50-1000 rpm;
(4) moulding by casting
Pre-polymerization resin is poured in mould, de-bubbled;
Technological parameter is as follows:
Temperature: 130-160 DEG C
The de-bubbled time: 0.5-2 h
Vacuum: 1.0 × 10-1-1.0×103Pa;
(5) curing process
Resin after de-bubbled solidifies;
Technological parameter is as follows:
Solidification temperature: 130-250 DEG C, uses staged solidification, and i.e. 130-150 DEG C/1-2h → 160-200 DEG C/1-2h → 210-250 DEG C/2h, heating rate is 5 DEG C/min;
Hardening time: 3-6 h;
(6) charring process
Resin after solidification is put in atmosphere furnace after the demoulding, is incubated after being warming up to predetermined temperature with certain heating rate, then cools to room temperature with the furnace and takes out;
Technological parameter is as follows:
Heating rate: 2-20 DEG C/min
Predetermined temperature: 600-1300 DEG C
Temperature retention time: 0.5-10 h
Protective atmosphere: N2Or Ar
Gas flow: 50-200 mL/min;
(7) template is removed
Carbonizing production is put in hydrochloric acid solution and soak, take out, be washed with deionized water to neutrality, 100 DEG C of dry 5h, obtain the rich nitrogen Carbon foam electrode material of ultracapacitor;
Technological parameter is as follows:
Concentration of hydrochloric acid solution: 1-6 mol/L
Soaking temperature: 25-100 DEG C
Soak time: 0.2-5 h.
CN201410285125.3A 2014-06-24 2014-06-24 A kind of ultracapacitor rich nitrogen Carbon foam electrode material and preparation method thereof CN104036973B (en)

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CN107601500A (en) * 2017-11-02 2018-01-19 福州大学 A kind of preparation method of high-specific surface area active foam Carbon Materials

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