CN105023760A - Flexible nitrogen-doped activated carbon composite electrode material and preparation method thereof - Google Patents
Flexible nitrogen-doped activated carbon composite electrode material and preparation method thereof Download PDFInfo
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- CN105023760A CN105023760A CN201510445900.1A CN201510445900A CN105023760A CN 105023760 A CN105023760 A CN 105023760A CN 201510445900 A CN201510445900 A CN 201510445900A CN 105023760 A CN105023760 A CN 105023760A
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Abstract
The invention provides a flexible nitrogen-doped activated carbon composite electrode material and a preparation method thereof. The preparation method comprises the following steps that multiple cocoon shell sheets are stripped, then the low molecular weight phenolic resin compounding and high temperature activating treatment are performed, finally, the flexible nitrogen-doped activated carbon composite electrode material can be prepared. The carbon composite electrode material has high wettability, certain strength and flexible deformation ability, and the charge transmission property and the capacitive performance thereof are improved substantially.
Description
Technical field
What the present patent application related to is active carbon composite electrodes material and preparation method thereof, in particular ultracapacitor active carbon composite electrodes material and preparation method thereof.
Background technology
Ultracapacitor is the energy storage device between conventional batteries and capacitor, can provide higher power density and energy density simultaneously.But the further technical development of current ultracapacitor is limited by the realistic problems such as electrode material energy density is low, manufacturing cost is high.Activated carbon cost is low, raw material sources are extensive, preparation technology is simple, and be the first-selection of more multi-electrode material, its performance is decided by the factor such as carbon source and preparation technology.But existing active carbon material ratio capacitance is lower, capacitive property awaits improving.Carbon nano-tube is higher at one-dimensional square electric conductivity upwards, and capacitive property is better, but complicated process of preparation, cost are high, restricts the application of its large-scale commercial.Graphene has excellent specific area and electric conductivity, and be the ideal electrode material of ultracapacitor, but manufacturing cost is higher, especially the preparation cost of high activity Graphene is higher.
In addition, electrode material raw materials is generally Powdered, need to use a large amount of adhesives and conductive additive to fix shaping, the use of adhesive and conductive additive, as Kynoar PVSF, acetylene black etc., cause electrode material film resistance to increase and electrode quality increase, make the ratio capacitance of membrane electrode, specific energy and specific power by actual cut low, and can not plastic deformation.
Summary of the invention
The goal of the invention of the present patent application is that the shaping eliminating adhesive and conductive additive relies on, one is provided to have from Brace ability and flexible bending ability, and flexible N doping active carbon composite electrodes material that charge storage function admirable, preparation technology are simple, cost advantage is large and preparation method thereof.
The flexible N doping active carbon composite electrodes material preparation method technical scheme that the present patent application provides, its main technical content is: a kind of flexible N doping active carbon composite electrodes material preparation method, and its preparation method is: 1., softening, point stripping of silkworm cocoon obtains silkworm network of fibers thin slice; 2., silkworm network of fibers thin slice and pf resin of low molecular weight compound: silkworm network of fibers thin slice is inserted pf resin of low molecular weight and synthesized in liquid, reacts 12 ~ 24 hours, obtain middle combination product in 110 ~ 150 DEG C; 3., combination product in the middle of the 2. step is placed in nitrogen atmosphere 500 ~ 800 DEG C bakes, its nitrogen flow is 2 ~ 20ml/min.
The present patent application additionally provides a kind of flexible N doping active carbon composite electrodes material obtained by above-mentioned flexible N doping active carbon composite electrodes material preparation method.
Flexible N doping active carbon composite electrodes material that patent application of the present invention provides and preparation method thereof, the natural fiber silkworm cocoon adopting protein content higher is the active carbon electrode material that raw material prepares, the wetability of this carbon electrode material improves, there is some strength and plastic deformation ability, and charge-conduction performance and capacitive property increase substantially.The various compositions such as graphite, Graphene, activated carbon are included in this carbon electrode material, and inside is distributed with the aperture of abundant large, medium and small different size, wherein the micropore of 4nm and central hole structure account for leading, its specific area is large, resistance is little in transferring charge film, specific power is large, ratio capacitance is high, and in aqueous electrolyte, its electrochemical window reaches 2V, ratio capacitance reaches 211F/g, reaches 23.8wh/Kg by the ultracapacitor specific power density of its assembling.In addition, in preparation process, use adhesive and conductive agent without the need to adding, its membrane electrode quality is light, and activity and the capacitive property of membrane electrode are greatly improved.
Accompanying drawing explanation
Fig. 1 is the x ray photoelectron diffraction spectrogram of this flexible N doping active carbon composite electrodes material.
Fig. 2 is nitrogen adsorption, desorption curve and graph of pore diameter distribution.
Fig. 3 is this flexible N doping active carbon composite electrodes material, and area is 1 cm * 1 cm, at 1M Na
2sO
4cyclic voltammetry curve figure in electrolyte aqueous solution.
Fig. 4 is the charging and discharging curve figure of symmetric form bipolar electrode ultracapacitor under different constant current assembled by this flexible N doping active carbon composite electrodes material.
Embodiment
Flexible N doping active carbon composite electrodes material preparation method disclosed in the present patent application, is after dividing stripping by many for silkworm cocoon thin slices, then carries out pf resin of low molecular weight compound and high-temperature activation process, final obtained flexible N doping active carbon composite electrodes material.Its preparation method is specifically:
1., by aqueous slkali, as sodium hydroxide solution or potassium hydroxide solution soak natural fiber silkworm cocoon, make it softening, swelling, the molar concentration of described aqueous slkali is 0.01 ~ 5M, soak time is 10 ~ 48 hours, best molar concentration is 0.2M, and soak time is 24 hours, is easier to stripping and obtains multi-disc silkworm network of fibers thin slice;
2., described silkworm network of fibers thin slice and pf resin of low molecular weight compound:
Silkworm network of fibers thin slice is inserted in pf resin of low molecular weight synthesis liquid, reacts 12 ~ 24 hours, obtain middle combination product at 110 ~ 150 DEG C of temperature.Wherein said pf resin of low molecular weight synthesis liquid is phenol, formaldehyde and catalyst NaOH, 7 ~ 8 hours obtained synthesis liquid is stirred in 60 ~ 70 DEG C of temperature, wherein the mol ratio of phenol and formaldehyde is 1:2 ~ 4, NaOH molar concentration is 0.01 ~ 0.03M, the thin slice caking property that combination process obtains is strong, and phenolic resin particle is little and be evenly distributed in fiber surface and inside configuration;
3., product in the middle of the 2. step are placed in nitrogen atmosphere 500 ~ 800 DEG C bake, its nitrogen flow is 2 ~ 20ml/min; In this processing step, preferably adopt 350 DEG C and 600 DEG C of two-segment calcinings, respectively roasting 1 hour and 2 hours, the temperature rise rate before sintering temperature is 5 DEG C/min.
By N
2adsorption/desorption test curve Fig. 2 BET is known, and this flexible N doping active carbon composite electrodes material has abundant pore structure, and specific area is comparatively large, and BET surface area is 499 m
2/ g, higher than 200 ~ 400 general m
2the specific area of/g carbon nano-tube.Bore gauge lattice distribution is wherein wider, and by 1.7nm to 300nm, wherein the micropore of 4nm and central hole structure account for leading, and average pore size is 2.0nm.This loose structure is conducive to electric charge to be transmitted therein, reduces electrode material film internal resistance, thus is conducive to the raising of energy density and power density.
This flexible N doping active carbon composite electrodes material is that raw material obtains by the natural fiber silkworm cocoon that protein content is higher.As shown in Figure 1, this carbon electrode material contains higher carbon content and a small amount of oxygen element and nitrogen element.The existence of oxygen element and nitrogen element, improve the wetability of this electrode material, thus the charge-conduction performance that improve between electrolyte aqueous solution and this carbon electrode material, through C1s, the XPS spectrum map analysis of N1s is known, N element peak is divided into N-5(pyridine nitrogen), N-6(pyrroles's nitrogen) and N-Q(graphite nitrogen) three kinds of peaks, account for 40% of N content respectively, 30% and 10%, wherein N-Q is conducive to the electric conductivity improving electrode in this carbon electrode material, and the existence of N-5 and N-6 can improve the capacitive property of material with carbon element greatly.
Fig. 3 is by this flexible N doping active carbon composite electrodes material in three-electrode system, at 1M Na
2sO
4cyclic voltamogram curve in electrolyte aqueous solution.As seen from the figure, this material carbon electrode has higher electro-chemical activity in-1.0 ~ 1.0V potential range, its CV curve symmetry is good, there is typical electric double layer capacitance performance, and there is no obvious liberation of hydrogen oxygen evolution reaction at terminal voltage place, illustrate that this flexible N doping active carbon composite electrodes material has higher capacitive property in very wide potential range, its in aqueous potential range can reach 2V, by constant current charge-discharge curve calculation, its constant current is 1mA/cm
2, calculating ratio capacitance is 211F/g, and area ratio electric capacity is 560 mF/ cm
2.
This flexible N doping active carbon composite electrodes material is assembled into symmetrical expression capacitor, and wherein the quality of each flexible N doping active carbon composite electrodes material is 3.5mg, adopts PVAC polyvinylalcohol gel to be barrier film, with sodium sulphate Na
2sO
4for electrolyte, test its constant current charge-discharge performance, the charging and discharging curve obtained as shown in Figure 4.This ultracapacitor operating voltage is 2V, does not have obvious Pressure Drop, illustrates that the interior resistance of membrane electrode is less, and the curve symmetry of discharge and recharge within the scope of 0 ~ 2V is good, illustrates that this ultracapacitor has higher charge storage performance thus.According to formula E=1/2CV
2p=E/t, wherein E is energy density, C is the ratio capacitance of capacitor, and P is power density, and t is discharge time, the energy density calculated under different current density is respectively 23.8 Wh/kg, 19.9 Wh/kg, 14.6 and 10.5 Wh/kg, corresponding power density is respectively 0.14 kW/ kg, 0.36 kW/ kg, 0.75 kW/ kg and 1.26 kW/ kg, shows that this ultracapacitor can keep higher power density under higher energy density thus, possesses high current charge-discharge service behaviour.
Claims (6)
1. a flexible N doping active carbon composite electrodes material preparation method, is characterized in that this its preparation method is:
1., silkworm cocoon softens, divides a stripping to obtain silkworm network of fibers thin slice;
2., silkworm network of fibers thin slice and pf resin of low molecular weight compound: silkworm network of fibers thin slice is inserted pf resin of low molecular weight and synthesized in liquid, reacts 12 ~ 24 hours, obtain middle combination product in 110 ~ 150 DEG C;
3., combination product in the middle of the 2. step is placed in nitrogen atmosphere 500 ~ 800 DEG C bakes, its nitrogen flow is 2 ~ 20ml/min.
2. flexible N doping active carbon composite electrodes material preparation method according to claim 1, it is characterized in that: soak natural fiber silkworm cocoon by sodium hydroxide solution, make it softening, swelling, the molar concentration of described sodium hydroxide solution is 0.01 ~ 5M, and soak time is 10 ~ 48 hours.
3. flexible N doping active carbon composite electrodes material preparation method according to claim 2, it is characterized in that NaOH molar concentration is 0.2M, soak time is 24 hours.
4. flexible N doping active carbon composite electrodes material preparation method according to claim 1, it is characterized in that pf resin of low molecular weight synthesis liquid is phenol, formaldehyde and catalyst NaOH, 7 ~ 8 hours obtained synthesis liquid is stirred in 60 ~ 70 DEG C of temperature, wherein the mol ratio of phenol and formaldehyde is 1:2 ~ 4, and NaOH molar concentration is 0.01 ~ 0.03M.
5. flexible N doping active carbon composite electrodes material preparation method according to claim 1, it is characterized in that 3. step employing 350 DEG C and 600 DEG C of two-stage roastings, respectively roasting 1 hour and 2 hours, the temperature rise rate wherein before sintering temperature is 5 DEG C/min.
6. one kind by the obtained flexible N doping active carbon composite electrodes material of flexible N doping active carbon composite electrodes material preparation method one of any in the claims 1 to 5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020225733A1 (en) * | 2019-05-06 | 2020-11-12 | The American University In Cairo | Electrical circuit components made from silkworm silk with silkworm-digested structured materials and methods for manufacturing same |
| CN112537766A (en) * | 2020-11-17 | 2021-03-23 | 浙江大学自贡创新中心 | Preparation method of carbon-nitrogen composite negative electrode material for lithium ion battery |
Citations (2)
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|---|---|---|---|---|
| CN101884932A (en) * | 2010-06-11 | 2010-11-17 | 哈尔滨工业大学深圳研究生院 | Nitrogen-doped carbon nano-fiber oxygen reduction catalyst, and preparation method and application thereof |
| CN103996545A (en) * | 2014-05-19 | 2014-08-20 | 上海大学 | Preparation method for nitrogen-doped ordered mesoporous carbon/carbon fiber composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101884932A (en) * | 2010-06-11 | 2010-11-17 | 哈尔滨工业大学深圳研究生院 | Nitrogen-doped carbon nano-fiber oxygen reduction catalyst, and preparation method and application thereof |
| CN103996545A (en) * | 2014-05-19 | 2014-08-20 | 上海大学 | Preparation method for nitrogen-doped ordered mesoporous carbon/carbon fiber composite material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020225733A1 (en) * | 2019-05-06 | 2020-11-12 | The American University In Cairo | Electrical circuit components made from silkworm silk with silkworm-digested structured materials and methods for manufacturing same |
| CN112537766A (en) * | 2020-11-17 | 2021-03-23 | 浙江大学自贡创新中心 | Preparation method of carbon-nitrogen composite negative electrode material for lithium ion battery |
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