CN103346026A - Preparation method for nano silicon-carbon composite electrode material of supercapacitor - Google Patents
Preparation method for nano silicon-carbon composite electrode material of supercapacitor Download PDFInfo
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Abstract
The invention relates to a preparation method for a nano silicon-carbon composite electrode material of a supercapacitor. Deionized water or ethyl alcohol or acetone is chosen to serve as solvent, the solid volume content of nano silicon and nano carbon materials in a solution is 1-10% of the volume content of the solution, and the solid volume content of nano silicon is 0.5-5% of the volume content of the solution; under the ultrasonic frequency ranging from 20-60 kHz, the precursor solution is atomized; atomized liquid drops are conveyed; argon or helium serves as carrier gas, the gas flow is 50-300ml/h, and the atomized liquid drops are conveyed to a conducting substrate with the temperature of 100-350 DEG C through the carrier gas; the conducting substrate is heated, sedimentation of composite materials is carried out, and the nano silicon-carbon composite electrode material is obtained. The preparation method is simple in preparation process, low in cost, and easy to process and produce in a large scale; the obtained nano silicon-carbon composite electrode material of the supercapacitor has the advantages of being high in capacity and charge-discharge efficiency, long in service life, good in cycling stability and the like.
Description
Technical field
The present invention relates to a kind of preparation method of ultracapacitor nano-silicone wire/carbon combination electrode material, belong to the electrochemical capacitor technical field.
Background technology
Ultracapacitor is as the novel energy-storing device, filled up the blank of specific energy and specific power between traditional capacitor and the battery, have energy and power density height, the speed that discharges and recharges is fast, efficient is high, environmentally safe, have extended cycle life, characteristics such as serviceability temperature wide ranges, fail safe height.
Electrode is as one of important part of ultracapacitor, and the research to electrode material at present can be divided into four aspects: material with carbon element, metal or metal oxide, conducting polymer, composite material.Characteristics such as material with carbon element is big owing to its specific area, chemical stability is good are commonly used for electrode in order to form electric double layer capacitance in ultracapacitor; Metal oxide and conducting polymer materials then can produce pseudo capacitance.Yet, because in use, conducting polymer (as polyacetylene, polyaniline, polypyrrole, poly-acene etc.) can be degraded, strand caves in, cause material activity to reduce, therefore influence capacitive property to a great extent, its cycle life is not grown (list of references: [1] Y.Shan, L.Gao.Formation and characterization of multi-walled carbon nanotubes/Co
3O
4Nanocomposites for supercapacitors[J] .Materials Chemistry and Physics, 2007,103 (2-3): 206-210.[2] G.Arabale, D.Wagh, M.Kulkarni, I.S.Mulla, S.P.Vernekar, K.Vijayamohanan, A.M.Rao.Enhanced supercapacitance of multiwalled carbon nanotubes functionalized with ruthenium oxide[J] .Chemical Physics Letters, 2003,376 (1-2): 207-213.) metal or metal oxide such as RuO
2, NiO
x, IrO
2Deng, wherein most efficiency for charge-discharge is low or expensive, so the restricted (list of references: [3] B.J.Lee, S.R.Sivakkumar, J.M.Ko, J.H.Kim, S.M.Jo, D.Y.Kim.Carbon nanofibre/hydrous RuO of its application prospect
2Nanocomposite electrodes for supercapacitors[J] .Journal of Power Sources, 2007,168 (2): 546-552.) therefore, nowadays Many researchers is devoted to the development of new nanometer combined electrode material, utilizes cooperative effect and the advantage on the electrochemical properties between different component to improve the ultracapacitor overall performance.
Carbon nano-tube and Graphene are as the novel nano material with carbon element, a because peacekeeping two-dimensional layer lattice structure of its uniqueness, make it have high-specific surface area and electron mobility, chemistry and mechanical stability excellence, be expected to as electrode material for super capacitor and obtain extensive use.In addition, silicon nano material has good electricity and optical property, and there is wide application prospect in field such as, opto-electronic conversion integrated at semiconductor optoelectronic and information storage, is one of research topic the most popular in the field of nanometer material technology.
Compound by nano simple substance silicon and nano-carbon material, not only can effectively strengthen with collector between conduction contact, promote and absorb and storage electrolyte ability, and improve electrode and resist the ability of destroying, and its three-dimensional net structure adsorb repeatedly at ion/be difficult for avalanche in the desorption, the energy storage capacity of collaborative two kinds of materials is given full play to, thereby improves ultracapacitor specific capacity and cyclical stability better.
Summary of the invention
The invention discloses a kind of preparation method of ultracapacitor nano-silicone wire/carbon combination electrode material, problem such as its purpose is that carbon in the prior art, metal or metal oxide, conducting polymer etc. exist capacity as electrode and efficiency for charge-discharge is low, cycle life is long and expensive.Therefore, the objective of the invention is to improve the chemical property of ultracapacitor as electrode with the nano-sized carbon silicon composite in order to overcome the deficiencies in the prior art.
Technical solution of the present invention is achieved in that
A kind of preparation method of ultracapacitor nano-silicone wire/carbon combination electrode material, the preparation method that it comprises nano-silicon, nano-sized carbon and combination electrode material is characterized in that: described nano-silicon is nano simple substance silicon ball or particle; Described nano-sized carbon comprises carbon nano-tube or Graphene;
A) preparation method of nano-silicon specifically comprises ball-milling method or sputtering method or chemical vapour deposition technique, and preparation gained nano-silicon diameter is 10～100nm;
B) preparation method of carbon nano-tube adopts chemical vapour deposition technique or arc discharge method or laser burn method;
C) preparation method of graphene is to adopt improvement Hummers method and hydrazine hydrate reduction method or microwave heating method of reducing to prepare gained;
D) preparation nano-silicone wire/carbon combination electrode material adopts ultrasonic atomizatio heat deposition method, and its detailed process comprises:
A) preparation of nano-silicon and nano-carbon material mixing precursor solution: select for use deionized water or ethanol or acetone as solvent, nano-silicon and nano-carbon material solid content in volume are 1～10% of liquor capacity content in the solution, and wherein the solid content in volume of nano-silicon is 0.5～5% of liquor capacity content;
B) atomizing of precursor solution: under 20～60kHz supersonic frequency, precursor solution is atomized;
C) transporting of atomized drop: as carrier gas, gas flow is 50～300mL/h with argon gas or helium, and by carrier gas atomized drop being transported to temperature is on 100～350 ℃ the conductive substrates; Carry out the deposition of composite material;
D) to the conductive substrates heating, carry out the deposition of composite material, obtain the nano-silicone wire/carbon combination electrode material.
Described conductive substrates adopts iron or aluminium or copper or titanium or stainless steel or graphite flake, or employing is coated with the substrate of iron or aluminium or copper or titanium or stainless steel or graphite film at glass or graphite.
The atomizing of described precursor solution, depositing temperature are 100～350 ℃, and sedimentation time is 15min～2h.
Preparation technology of the present invention is simple, with low cost, is easy to processing and large-scale production.The ultracapacitor nano-silicone wire/carbon combination electrode material that adopts the inventive method to make has capacity and efficiency for charge-discharge height, has extended cycle life advantages such as good cycling stability.
Embodiment
The present invention is described in detail below in conjunction with embodiment, but present embodiment can not be used for restriction the present invention, and every employing similarity method of the present invention and similar variation thereof all should be listed protection scope of the present invention in.
Embodiment 1
Adopting ball-milling method is that 3 μ m silica flours are pulverized under argon shield atmosphere with diameter, and rotating speed is 250r/min, and the time is 2h, and preparing diameter is the 100nm silica flour.After the nickel sheet carried out preliminary treatment with sand papering, each ultrasonic 30min in acetone and deionized water respectively, utilize low pressure chemical vapor deposition equipment carbon nano-tube on the nickel sheet then, acetylene and hydrogen flowing quantity are respectively 50sccm and 250sccm, growth temperature is 550 ℃, collects the carbon nanotube powder of preparation gained behind the growth 1h.The nano silica fume of preparation gained is mixed with the carbon nano-tube ball milling, rotating speed is 100r/min, time is 2h, preparing solid content then is that 1% nano-silicon-carbon nano-tube (wherein the nano-silicon solid content is 0.5%) composite material aqueous solution is as precursor solution, Copper Foil is as conductive substrates, the frequency of ultrasonic atomizer is 20kHz, and the heating station temperature is 150 ℃, and sedimentation time is controlled at 2h.During the assembling ultracapacitor, adopting stacked method to make electric core and be assembled to model is in the CR2032 button cell shell, concrete stacking order is as follows, inject electrolyte simultaneously: anode cover, nano-sized carbon silicon electrode, electrolyte, barrier film, electrolyte, nano-sized carbon silicon electrode, pad, spring leaf, negative electrode casing, electrolyte adopts 6mol/L KOH.Adopt hydraulic pressure button cell packaging machine that prepared ultracapacitor is sealed, pressure is made as 1500Ncm
-2
Embodiment 2
Adopt radio-frequency magnetron sputter method to prepare nano-silicon, target is purity 99.999% high-purity monocrystalline silicon target, and radio-frequency power is 150W, and underlayer temperature is 200 ℃, thin film deposition time 2h, and deposition pressure is 8Pa.Adopt improvement Hummers method to prepare graphite oxide, namely after volume ratio was to add graphite powder in 2: 1 nitric acid and the sulfuric acid solution, mix, constant temperature stirred under 80 ℃ of oil baths; After filtering, in resulting solid residue, add sulfuric acid, slowly add potassium permanganate under the condition of ice bath and continue to stir; Then reactant dilution and adding hydrogen peroxide are obtained jonquilleous graphene oxide suspension, above-mentioned solution is placed in the single mold microwave synthesis system, heats to 150 ℃ following reaction 10min by 80W, product is black suspension, filters the gained filter residue and is Graphene.
To prepare the gained nano-silicon and mix with the Graphene ball milling, rotating speed is 500r/min, and the time is 15min, and being mixed with solid content then is 10% nano-silicon-Graphene (wherein the nano-silicon solid content is 5%) composite material aqueous solution and ultrasonic mixing, and the time is 30min.The mixed solution of preparing is as precursor solution, and graphite flake is as conductive substrates, and the frequency of ultrasonic atomizer is 60kHz, and the heating station temperature is 200 ℃, and sedimentation time is controlled at 15min.According to method as described in example 1 above, prepared electrode is assembled into ultracapacitor and seals.
Embodiment 3
Adopt chemical vapour deposition technique to prepare nano-silicon, at first with vacuum mechanical pump whole system is vacuumized, then whole system is filled high-purity argon gas, vacuumize again after being full of, so repeat 3 times.Cavity is heated to 600 ℃, behind the arrival design temperature, feeds silane gas with constant flow rate 60sccm in system, keeping the cavity internal pressure is 0.1MPa, and the reaction time is 1h.After treating that system temperature naturally cools to room temperature, nano silica fume in the collection chamber.Prepare glassy yellow graphene oxide suspension according to the method described in the embodiment 2, hydrazine hydrate is dropwise added in the above-mentioned suspension be black suspension until product, filter the gained filter residue and be Graphene.Adopt the Prepared with Laser Ablation carbon nano-tube, specifically comprise and utilize the carbon black target of the wide Nd:YAG millisecond of long pulse laser ablation infiltration in ethanol, wherein pulsewidth is 0.6ms, and frequency is 20Hz, and laser power density is 1.28 * 10
7W/cm
2, single pulse energy is 2.4J, the laser ablation time is 1h.After reaction finishes, collect the carbon nanotube powder in the alcoholic solution.
Prepared nano-silicon is mixed than ball milling with 0.1: 2: 2 quality with Graphene and carbon nano-tube, rotating speed is 250r/min, time is 30min, and being mixed with solid content then is 2% nano-silicon-graphene-carbon nano tube composite material aqueous solution and ultrasonic mixing, and the time is 30min.The mixed solution of preparing is as precursor solution, and graphite flake is as conductive substrates, and the frequency of ultrasonic atomizer is 60kHz, and the heating station temperature is 200 ℃, and sedimentation time is controlled at 1h.According to method as described in example 1 above, prepared electrode is assembled into ultracapacitor and seals.
Prepared combination electrode can be worked in coordination with a peacekeeping two-dimensional structure and the nano-silicon good electrochemical of Graphene and carbon nano-tube uniqueness among the embodiment 3, form the three-dimensional electronic transmission network, hole, hole and graphite layers and edge all provide adequate space for ionic adsorption/desorption.In addition, carbon nano-tube also plays connect to be linked up the function served as bridge between graphene film and nano-silicon and plugs the gap, and is conducive to the migration of electric transmission and ion in the cyclic process.Therefore, nano-silicon-graphene-carbon nano tube composite material is compared embodiment 1,2 prepared materials have more superiority at chemical properties such as the specific capacity that promotes ultracapacitor and cycle lives.
Claims (3)
1. the preparation method of a ultracapacitor nano-silicone wire/carbon combination electrode material, the preparation method that it comprises nano-silicon, nano-sized carbon and combination electrode material is characterized in that: described nano-silicon is nano simple substance silicon ball or particle; Described nano-sized carbon comprises carbon nano-tube or Graphene;
A) preparation method of nano-silicon specifically comprises ball-milling method or sputtering method or chemical vapour deposition technique, and preparation gained nano-silicon diameter is 10～100nm;
B) preparation method of carbon nano-tube adopts chemical vapour deposition technique or arc discharge method or laser burn method;
C) preparation method of graphene is to adopt improvement Hummers method and hydrazine hydrate reduction method or microwave heating method of reducing to prepare gained;
D) preparation nano-silicone wire/carbon combination electrode material adopts ultrasonic atomizatio heat deposition method, and its detailed process comprises:
A) preparation of nano-silicon and nano-carbon material mixing precursor solution: select for use deionized water or ethanol or acetone as solvent, nano-silicon and nano-carbon material solid content in volume are 1～10% of liquor capacity content in the solution, and wherein the solid content in volume of nano-silicon is 0.5～5% of liquor capacity content;
B) atomizing of precursor solution: under 20～60kHz supersonic frequency, precursor solution is atomized;
C) transporting of atomized drop: as carrier gas, gas flow is 50～300mL/h with argon gas or helium, and by carrier gas atomized drop being transported to temperature is on 100～350 ℃ the conductive substrates; Carry out the deposition of composite material;
D) to the conductive substrates heating, carry out the deposition of composite material, obtain the nano-silicone wire/carbon combination electrode material.
2. the preparation method of ultracapacitor nano-silicone wire/carbon combination electrode material according to claim 1, it is characterized in that: described conductive substrates adopts iron or aluminium or copper or titanium or stainless steel or graphite flake, or employing is coated with the substrate of iron or aluminium or copper or titanium or stainless steel or graphite film at glass or graphite.
3. the preparation method of ultracapacitor nano-silicone wire/carbon combination electrode material according to claim 1, it is characterized in that: the atomizing of described precursor solution, depositing temperature are 100～350 ℃, sedimentation time is 15min～2h.
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Cited By (3)
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| CN103531761A (en) * | 2013-10-28 | 2014-01-22 | 上海利物盛企业集团有限公司 | Preparation method for nanometer silicon |
| CN106495161A (en) * | 2016-10-24 | 2017-03-15 | 中南大学 | A kind of method that nano-silicon is prepared based on metal intervention metallothermic reduction |
| CN108054341A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of preparation method of graphene/silicon carbon composite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103531761A (en) * | 2013-10-28 | 2014-01-22 | 上海利物盛企业集团有限公司 | Preparation method for nanometer silicon |
| CN106495161A (en) * | 2016-10-24 | 2017-03-15 | 中南大学 | A kind of method that nano-silicon is prepared based on metal intervention metallothermic reduction |
| CN108054341A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of preparation method of graphene/silicon carbon composite |
| CN108054341B (en) * | 2017-12-22 | 2020-09-15 | 湖南工业大学 | Preparation method of graphene/silicon-carbon composite material |
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Application publication date: 20131009 Assignee: Shanghai Li Sheng Nano Technology Co., Ltd. Assignor: Shanghai Co., Ltd of Li Wusheng enterprise group Contract record no.: X2019310000015 Denomination of invention: Preparation method for nano silicon-carbon composite electrode material of supercapacitor Granted publication date: 20160810 License type: Common License Record date: 20191014 |
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