CN103346026B - A kind of preparation method of nano silicon-carbon composite electrode material of supercapacitor - Google Patents
A kind of preparation method of nano silicon-carbon composite electrode material of supercapacitor Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of nano silicon-carbon composite electrode material of supercapacitor, select deionized water or ethanol or acetone as solvent, in solution, nano-silicon and nano-carbon material solid content in volume are the 1～10% of liquor capacity content, and wherein the solid content in volume of nano-silicon is the 0.5～5% of liquor capacity content；Under 20～60kHz supersonic frequencies, precursor solution is atomized；Transporting of atomized drop: using argon or helium as carrier gas, gas flow is 50～300mL/h, is transported in the conductive substrates that temperature is 100～350 DEG C by atomized drop by carrier gas；Conductive substrates is heated, carries out the deposition of composite, obtain nano silicon-carbon composite electrode material.The advantages such as preparation technology of the present invention is simple, with low cost, it is easy to processing and large-scale production, prepared nano silicon-carbon composite electrode material of supercapacitor, has capacity and efficiency for charge-discharge height, has extended cycle life, good cycling stability.
Description
Technical field
The present invention relates to the preparation method of a kind of nano silicon-carbon composite electrode material of supercapacitor, belong to electrochemical capacitor technology
Field.
Background technology
Ultracapacitor, as novel energy-storing device, has filled up specific energy and the blank of specific power between traditional capacitor and battery,
Have that energy and power density are high, charge/discharge rates is fast, efficiency is high, environmentally safe, have extended cycle life, use temperature model
Enclose width, safety high.
Electrode is as one of important ingredient 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 with carbon element is owing to its specific surface area is big, chemically stable
Property the feature such as good, ultracapacitor is commonly used for electrode in order to form electric double layer capacitance；Metal-oxide and conducting polymer material
Material then can produce pseudo capacitance.But, due in use, conducting polymer (such as polyacetylene, polyaniline, gathers
Pyrroles, coalescence benzene etc.) can degrade, strand caves in, and causes material activity to reduce, the most largely affect
Capacitive property, its cycle life does not the most grow (list of references: [1] Y.Shan, L.Gao.Formation and characterization of
multi-walled carbon nanotubes/Co3O4nanocomposites 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 RuO2、NiOx、IrO2Deng, the most mostly
The efficiency for charge-discharge of number is low or expensive, therefore restricted (list of references: [3] B.J.Lee, S.R. of its application prospect
Sivakkumar,J.M.Ko,J.H.Kim,S.M.Jo,D.Y.Kim.Carbon nanofibre/hydrous RuO2nanocomposite
Electrodes for supercapacitors [J] .Journal of Power Sources, 2007,168 (2): 546-552.) therefore, the most a lot
Researcher is devoted to develop novel nano combination electrode material, and utilize on the cooperative effect between different component and electrochemical properties is excellent
Gesture improves ultracapacitor overall performance.
CNT and Graphene are as novel nano material with carbon element, due to a peacekeeping two-dimensional layer lattice structure of its uniqueness so that it is
There is high-specific surface area and electron mobility, chemistry and mechanical stability are excellent, be expected to as electrode material for super capacitor and obtain
Obtain and extensively apply.Additionally, silicon nano material has good electrical and optical performance, it is electrically integrated in semiconductor light, opto-electronic conversion
Have broad application prospects with fields such as information storages, be one of research topic the most popular in field of nanometer material technology.
It is combined by nano simple substance silicon and nano-carbon material, not only can effectively strengthen and conductive contact between collector, promote and absorb
With store electrolyte ability, and improve the ability that electrode opposing destroys, and its three-dimensional net structure repeatedly adsorbs at ion/is desorbed
In be difficult to avalanche, the energy storage capacity of collaborative bi-material is given full play to, thus preferably improve ultracapacitor specific capacity and
Cyclical stability.
Summary of the invention
The invention discloses the preparation method of a kind of nano silicon-carbon composite electrode material of supercapacitor, its object is to prior art
Middle carbon, metal or metal-oxide, conducting polymer etc. as electrode also exist capacity and efficiency for charge-discharge is low, cycle life not
The problem such as long and expensive.Therefore, the invention aims to overcome the deficiencies in the prior art, with nano-sized carbon silicon composite wood
Material improves the chemical property of ultracapacitor as electrode.
The technical scheme is that and be achieved in that:
The preparation method of a kind of nano silicon-carbon composite electrode material of supercapacitor, it includes nano-silicon, nano-sized carbon and combination electrode material
Preparation method, it is characterised in that: described nano-silicon is nano simple substance silicon ball or granule；Described nano-sized carbon includes carbon nanometer
Pipe or Graphene；
A) preparation method of nano-silicon, specifically includes ball-milling method or sputtering method or chemical vapour deposition technique, prepares gained nano-silicon
A diameter of 10～100nm；
B) preparation method of CNT is to use chemical vapour deposition technique or arc discharge or laser burn method；
C) preparation method of Graphene is to use improvement Hummers method and hydrazine hydrate reduction method or microwave reduction method system
Standby gained；
D) preparing nano silicon-carbon composite electrode material and use the heat sink area method of ultrasonic atomizatio, its detailed process includes:
A) preparation of nano-silicon and nano-carbon material mixing precursor solution: select deionized water or ethanol or acetone as solvent,
In solution, nano-silicon and nano-carbon material solid content in volume are the 1～10% of liquor capacity content, the wherein solid volume of nano-silicon
Content is the 0.5～5% of liquor capacity content；
B) atomization of precursor solution: under 20～60kHz supersonic frequencies, precursor solution is atomized；
C) the transporting of atomized drop: using argon or helium as carrier gas, gas flow is 50～300mL/h, by carrier gas by mist
Change drop to be transported in the conductive substrates that temperature is 100～350 DEG C；
D) conductive substrates is heated, carry out the deposition of composite, obtain nano silicon-carbon composite electrode material.
Described conductive substrates uses ferrum or aluminum or copper or titanium or rustless steel or graphite flake, or employing is coated with on glass or graphite
Ferrum or aluminum or copper or titanium or rustless steel or the substrate of graphite film.
The atomization of described precursor solution, depositing temperature is 100～350 DEG C, and sedimentation time is 15min～2h.
Preparation technology of the present invention is simple, with low cost, it is easy to processing and large-scale production.It is super that employing the inventive method prepares
Capacitor nano silicon-carbon composite electrode material, has that capacity and efficiency for charge-discharge are high, has extended cycle life, and good cycling stability etc. is excellent
Point.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail, but the present embodiment cannot be used for limiting the present invention, and every employing is originally
The similarity method of invention and similar change thereof, all should list protection scope of the present invention in.
Embodiment 1
Using ball-milling method to be pulverized under argon atmosphere by a diameter of 3 μm silica flours, rotating speed is 250r/min, and the time is 2h,
Prepare a diameter of 100nm silica flour.After nickel sheet sand papering is carried out pretreatment, each in acetone and deionized water respectively
Ultrasonic 30min, then utilizes low pressure chemical vapor deposition equipment to grow CNT in nickel sheet, and acetylene is with hydrogen flowing quantity respectively
For 50sccm and 250sccm, growth temperature is 550 DEG C, and after growth 1h, the carbon nanotube powder of gained is prepared in collection.Will preparation
The nano silica fume of gained mixes with CNT ball milling, and rotating speed is 100r/min, and the time is 2h, and then preparation solid content is 1%
Composite aqueous solution is as precursor solution for nano-silicon-CNT (wherein nano-silicon solid content is 0.5%), and Copper Foil is as leading
Electricity substrate, the frequency of ultrasound atomizer is 20kHz, and heating platen temperature is 150 DEG C, and sedimentation time controls at 2h.Assemble super
During capacitor, using stacked method make battery core and be assembled in model is CR2032 button cell shell, concrete stacking order is such as
Under, it is injected simultaneously into electrolyte: anode cover, nano-sized carbon silicon electrode, electrolyte, barrier film, electrolyte, nano-sized carbon silicon electrode, pad
Sheet, spring leaf, negative electrode casing, electrolyte uses 6mol/L KOH.Use hydraulic pressure button cell sealing machine to prepared super electricity
Closing containers, pressure is set to 1500N cm-2。
Embodiment 2
Using radio-frequency magnetron sputter method to prepare nano-silicon, target is purity 99.999% high purity single crystal silicon target, and radio-frequency power is 150W,
Underlayer temperature is 200 DEG C, thin film deposition time 2h, and deposition pressure is 8Pa.Improvement Hummers method is used to prepare graphite oxygen
Compound, after i.e. adding graphite powder, mix homogeneously in the nitric acid that volume ratio is 2: 1 and sulfuric acid solution, constant temperature under 80 DEG C of oil baths
Stirring；After filtering, obtained solid residue adds sulphuric acid, be slowly added to potassium permanganate under condition of ice bath and continue
Stirring；Then reactant is diluted and add hydrogen peroxide and obtain jonquilleous graphene oxide suspension, above-mentioned solution is put
Putting in single mold microwave synthesis system, by reacting 10min at the heats of 80W to 150 DEG C, product is black
Color suspension, carries out filtering gained filtering residue and is Graphene.
To prepare gained nano-silicon to mix with Graphene ball milling, rotating speed is 500r/min, and the time is 15min, is then configured to solid
Content is 10% nano-silicon-Graphene (wherein nano-silicon solid content is 5%) composite aqueous solution ultrasonic mixing, and the time is
30min.The mixed solution prepared is as precursor solution, and graphite flake is as conductive substrates, and the frequency of ultrasound atomizer is 60
KHz, heating platen temperature is 200 DEG C, and sedimentation time controls at 15min.According to method as described in example 1 above, by made
Standby electrode assembling becomes ultracapacitor and seals.
Embodiment 3
Chemical vapour deposition technique is used to prepare nano-silicon, first with vacuum mechanical pump to whole system evacuation, then to whole system
System fills high-purity argon gas, evacuation again after being full of, and is so repeated 3 times.Cavity is heated to 600 DEG C, after arriving design temperature, with
Constant flow rate 60sccm is passed through silane gas in system, and keeping inside cavity pressure is 0.1MPa, and the response time is 1h.
After system temperature naturally cools to room temperature, nano silica fume in collection chamber.Prepare according to the method described in embodiment 2
Glassy yellow graphene oxide suspension, is added dropwise over hydrazine hydrate in above-mentioned suspension until product is black suspension, enters
Row filters gained filtering residue and is Graphene.Use laser ablation method to prepare CNT, specifically include and utilize long pulsewidth Nd:YAG
Millisecond laser ablation infiltration white carbon black target in ethanol, wherein pulsewidth is 0.6ms, and frequency is 20Hz, and laser power density is
1.28×107W/cm2, single pulse energy is 2.4J, and laser ablation time is 1h.After reaction terminates, collect in alcoholic solution
Carbon nanotube powder.
Being mixed than ball milling with 0.1: 2: 2 mass with Graphene and CNT by prepared nano-silicon, rotating speed is 250r/min,
Time is 30min, and being then configured to solid content is 2% nano-silicon-graphene-carbon nano tube composite material aqueous solution ultrasonic mixing,
Time is 30min.The mixed solution prepared is as precursor solution, and graphite flake is as conductive substrates, the frequency of ultrasound atomizer
Rate is 60kHz, and heating platen temperature is 200 DEG C, and sedimentation time controls at 1h.According to method as described in example 1 above, will
Prepared electrode assembling becomes ultracapacitor and seals.
Combination electrode prepared in embodiment 3 can work in coordination with Graphene and peacekeeping two-dimensional structure and a nanometer of CNT uniqueness
The chemical property that silicon is good, forms three-dimensional electronic transmission network, and hole, hole and graphite layers and edge are all that ion is inhaled
Attached/desorption provides adequate space.Additionally, CNT also acts as connects the function served as bridge linked up between graphene film and nano-silicon also
Plug the gap, beneficially electric transmission and the migration of ion in cyclic process.Therefore, nano-silicon-graphene-carbon nano tube composite wood
Material prepared by embodiment 1,2 compared by material has on the chemical property such as specific capacity and cycle life promote ultracapacitor
More advantage.
Claims (3)
1. a preparation method for nano silicon-carbon composite electrode material of supercapacitor, it includes nano-silicon, nano-sized carbon and combination electrode material
The preparation method of material, it is characterised in that: described nano-silicon is nano simple substance silicon ball or granule；Described nano-sized carbon includes that carbon is received
Mitron or Graphene；
A) preparation method of nano-silicon, specifically includes ball-milling method or sputtering method or chemical vapour deposition technique, prepares gained nanometer
Silicon a diameter of 10～100nm；
B) preparation method of CNT is to use chemical vapour deposition technique or arc discharge or laser burn method；
C) preparation method of Graphene is to use improvement Hummers method and hydrazine hydrate reduction method or microwave reduction method
Prepare gained；
D) preparing nano silicon-carbon composite electrode material and use the heat sink area method of ultrasonic atomizatio, its detailed process includes:
A) preparation of nano-silicon and nano-carbon material mixing precursor solution: select deionized water or ethanol or acetone as solvent,
In solution, nano-silicon and nano-carbon material solid content in volume are the 1～10% of liquor capacity content, the wherein solid volume of nano-silicon
Content is the 0.5～5% of liquor capacity content；
B) atomization of precursor solution: under 20～60kHz supersonic frequencies, precursor solution is atomized；
C) the transporting of atomized drop: using argon or helium as carrier gas, gas flow is 50～300mL/h, by carrier gas by mist
Change drop to be transported in the conductive substrates that temperature is 100～350 DEG C；
D) conductive substrates is heated, carry out the deposition of composite, obtain nano silicon-carbon composite electrode material.
The preparation method of nano silicon-carbon composite electrode material of supercapacitor the most according to claim 1, it is characterised in that: described
Conductive substrates use ferrum or aluminum or copper or titanium or rustless steel or graphite flake, or use be coated with on glass or graphite ferrum or aluminum or
Copper or titanium or rustless steel or the substrate of graphite film.
The preparation method of nano silicon-carbon composite electrode material of supercapacitor the most according to claim 1, it is characterised in that: described
The atomization of precursor solution, depositing temperature is 100～350 DEG C, and sedimentation time is 15min～2h.
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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 |
| CN106495161B (en) * | 2016-10-24 | 2018-08-31 | 中南大学 | A method of nano-silicon is prepared based on metal intervention metallothermic reduction |
| 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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| CN103035889A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Graphene/nano silicon combined electrode plate and preparation method of same |
| CN103107315A (en) * | 2011-11-10 | 2013-05-15 | 北京有色金属研究总院 | Nano silicon-carbon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103035889A (en) * | 2011-10-09 | 2013-04-10 | 海洋王照明科技股份有限公司 | Graphene/nano silicon combined electrode plate and preparation method of same |
| CN103107315A (en) * | 2011-11-10 | 2013-05-15 | 北京有色金属研究总院 | Nano silicon-carbon composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Flexible free-standing graphene-silicon composite film for lithium-ion batteries;Jia-Zhao Wang等;《Electrochemistry Communications》;20100814;第12卷(第11期);第1467-1470 * |
| 基于纳米碳及其金属氧化物复合电极的超级电容研究;张燕萍;《中国博士学位论文全文数据库 工程科技Ⅱ辑》;20101215(第12期);第3.1章节 * |
| 对石墨烯氧化物化学还原条件的探索;郑薇;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20120915(第9期);第1.1.3章节 * |
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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 |