CN104465125B - TiO2Three-dimensional interdigital microelectrodes of/NiO and preparation method thereof - Google Patents

TiO2Three-dimensional interdigital microelectrodes of/NiO and preparation method thereof Download PDF

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CN104465125B
CN104465125B CN201410697924.1A CN201410697924A CN104465125B CN 104465125 B CN104465125 B CN 104465125B CN 201410697924 A CN201410697924 A CN 201410697924A CN 104465125 B CN104465125 B CN 104465125B
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tio
nio
titanium
dimensional
electrode
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CN104465125A (en
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郭丽芳
柴晶
李刚
赵清华
张君慧
张文栋
桑胜波
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Taiyuan University of Technology
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Taiyuan University of Technology
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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

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

The present invention relates to ultracapacitor, specially TiO in button capacitor field2Three-dimensional interdigital microelectrodes of/NiO and preparation method thereof.The preparation method of the electrode is：First in the layer insulating of silicon substrate surface oxidation one, then splash-proofing sputtering metal titanium layer and the three-dimensional interdigital microelectrode of titanium is prepared by micro-processing technology, this electrode is put into HF solution Anodic Oxidations and forms orderly TiO2Nano-tube array, in TiO2NiO is prepared by electro-deposition method in nanotube, KOH electrolyte is finally filled between the three-dimensional interdigital microelectrode with NiO active materials.The present invention utilizes the TiO with high-specific surface area2Reversible redox reaction principle can occur in KOH electrolyte for nano-tube material and NiO, design the three-dimensional interdigital microelectrode structure of fake capacitance mechanism, compared to the specific capacitance that traditional " sandwich " structure substantially increases capacitor.

Description

TiO2Three-dimensional interdigital microelectrodes of/NiO and preparation method thereof
Technical field
The present invention relates to ultracapacitor, specially TiO in button capacitor field2The three-dimensional interdigital microelectrodes of/NiO and its Preparation method.
Background technology
Microelectromechanical systems（Micro Electro Mechanical System）, abbreviation MEMS, it is by microelectronics skill A kind of industrial technology that art is fused together with mechanical engineering, it has low cost, small volume, automatic control is strong, reliability is high etc. Advantage, it is one of most important technological innovation in recent years.MEMS technology opereating specification is generally in micrometer range, a micron order Power-supply system can realize for a long time, high-effect, multicycle powering mode, can not be applied especially suitable for conventional power source Some particular surroundings, such as radio communication and wireless senser, there is far-reaching Research Significance.
Ultracapacitor is a kind of new energy storage device, and micro super capacitor possesses conventional Super capacitor advantage Also show simultaneously storage energy big, volume microminiaturization, have extended cycle life, can the multiple spy such as cycle charge-discharge and batch production Point, reduces device volume and design cost, improves the reliability and stability of device design system, therefore microsuper electricity Container is paid high attention to by domestic and international researcher.But the energy density of micro super capacitor is low, therefore how to improve miniature The energy density of ultracapacitor turns into a Main way of electrochemical capacitance research.Ultracapacitor according to energy storage mechnism not Together, foundation can be divided into the double layer capacitor on the basis of interfacial electric double layer and established counterfeit on the basis of " pseudo capacitance " Capacity capacitor.The capacitive source of double layer capacitor in the electrostatic attraction of physics, and the power source of fake capacitance capacitor in The redox reaction of electroactive material, for the fake capacitance capacitor compared with double layer capacitor, its specific capacitance is electric double layer electricity 10-100 times held, therefore researchers start more energy to have been invested the design of fake capacitance capacitor, fake capacitance electric capacity Device electrode material is mostly metal oxide, high molecular polymer etc., and metal oxide has good electrochemical properties, such as Redox reaction can occur in aqueous slkali for NiO, therefore design the fake capacitance miniature ultracapacitor based on the electrode material Device will have important application as high-energy energy storage device in electronics, automobile, space flight and military field, promote micro- energy The innovation and development of source technology, material impact is produced to human lives.
The content of the invention
The present invention is in order to solve the problems, such as that the energy density of micro super capacitor is low, there is provided TiO2/ NiO three-dimensionals are interdigital Microelectrode and preparation method thereof.
The present invention adopts the following technical scheme that realization：TiO2The three-dimensional interdigital microelectrodes of/NiO, including silicon chip, silicon chip Insulating barrier is provided with, being sputtered on insulating barrier has layer of titanium metal, and the three-dimensional fork of titanium is formed by the method for spin coating in layer of titanium metal Refer to microelectrode, aoxidized on the three-dimensional interdigital microelectrode of titanium and form TiO2Nano-tube array, TiO2Deposition has NiO, three-dimensional fork in nanotube KOH electrolyte is filled between finger microelectrode.
TiO2Its preparation method of the three-dimensional interdigital microelectrodes of/NiO, comprises the following steps：
S1：Choose silicon chip and carry out Wafer Cleaning, get rid of organic oil, inorganic oil on silicon chip, remove oxide film dissolving and gold Belong to ion；
S2：Silicon chip cleaned in step S1 is aoxidized, forms insulating barrier of the oxide-film as microelectrode；
S3：Put the silicon chip that insulating barrier is formed in step S2 into vacuum sputter system, one is sputtered on the insulating barrier of silicon chip Layer layer of titanium metal；
S4:Last layer photoetching is uniformly applied using the method for spin coating in the layer of titanium metal that silicon chip is formed in step s3 Glue is simultaneously exposed by interdigital mask plate, development, then removes exposed layer of titanium metal by the method for corrosion, then removes photoresist to form titanium Three-dimensional interdigital microelectrode；
S5:The three-dimensional interdigital microelectrode of the titanium formed in step S4 is put into anodic oxidation device oxidation, titanium is three-dimensional interdigital micro- TiO is formed on electrode2Nano-tube array；
S6：The TiO formed in step s 52NiO is deposited by electro-deposition, electroxidation, heat-treating methods in nanotube, Form active material electrode；
S7：KOH electrolyte is filled between the three-dimensional interdigital microelectrode of the titanium with NiO active materials formed in step s 6, Form TiO2The three-dimensional interdigital microelectrodes of/NiO.
By TiO produced by the present invention2The three-dimensional interdigital microelectrodes of/NiO can obtain microsuper electricity after encapsulating finished product Container.
The present invention replaces traditional " sandwich overlaying structure " using the three-dimensional interdigital microelectrode of titanium first, has reached raising electrode Surface area and the purpose for reducing ion displacement between electrode, three-dimensional interdigital microelectrode structural manufacturing process program is simple, is easy to big Amount production, secondly, the microelectrode uses the TiO of loose structure2Nano-tube material does substrate, significantly improves the ratio table of microelectrode Area, improve the capacitance characteristic of the ultracapacitor based on this electrode, TiO2Anodizing technology has controllable, stabilization, easily The features such as operation, finally, TiO2The three-dimensional interdigital microelectrodes of/NiO use faraday " pseudo-capacitance " electrochemical energy storage mechanism, that is, utilize Reversible redox reaction can occur in aqueous slkali for NiO, compared with electric double layer energy storage mechnism, faraday " pseudo-capacitance " energy storage electricity Container significantly increases the energy density of capacitor, and the performance of the ultracapacitor based on this electrode is improved well.
The invention provides the TiO applied to micro super capacitor2The three-dimensional interdigital microelectrodes of/NiO, based on this electrode The performance of ultracapacitor is improved well, and energy density is high, solves the energy density of existing micro super capacitor The problem of low.
Brief description of the drawings
Fig. 1 is the flow chart of invention.
Fig. 2 is the structural representation of anodic oxidation device.
Embodiment
TiO2The three-dimensional interdigital microelectrodes of/NiO, including silicon chip, silicon chip are provided with insulating barrier, and being sputtered on insulating barrier has Titanium Layer, the three-dimensional interdigital microelectrode of titanium is formed by the method for spin coating in layer of titanium metal, shape is aoxidized on the three-dimensional interdigital microelectrode of titanium Into TiO2Nano-tube array, TiO2Deposition has NiO in nanotube, and KOH electrolyte is filled between three-dimensional interdigital microelectrode.
TiO2Its preparation method of the three-dimensional interdigital microelectrodes of/NiO, comprises the following steps：
S1：4 cun of silicon chips are chosen as substrate, silicon chip successively dimethylbenzene, acetone, alcohol, sulfuric acid/hydrogen peroxide, ammoniacal liquor/ Cleaned in hydrogen peroxide and hydrochloric acid/hydrogen peroxide solution to remove organic oil, inorganic oil, remove oxide film dissolving and metal ion;
S2：Put silicon chip cleaned in step S1 into oxidation furnace to be aoxidized, be followed successively by dry-oxygen oxidation-wet oxygen oxygen Change-dry-oxygen oxidation, oxidization time are 10 hours, form insulating barrier of the oxide-film as micro super capacitor electrode, oxidation Film thickness is 1.5 microns；
S3：Put silicon chip cleaned in step S2 into vacuum sputter system, a layer thickness is sputtered as 400 in front side of silicon wafer The Titanium of nanometer；
S4：One layer of SU-8 photoetching is uniformly coated with using the method for rotation spin coating in the layer of titanium metal on silicon chip in step s3 Glue, and pass through the exposure of interdigital mask plate, development；The Titanium of exposure is removed with the method for corrosion again, is finally removed photoresist, forms titanium three Tie up interdigital microelectrode；
S5：The three-dimensional interdigital microelectrode of titanium in step S4 is put into anodic oxidation device and carries out anodic oxidation, oxidation is First apply 10 volts of voltage 20 seconds, then apply 0.5 volt of voltage and the TiO that height is 90-270 nanometers is formed after 25 minutes2Nanotube Array；
S6：Three-electrode electro Chemical reaction system is established, the TiO that will be formed in step S52Nanotube is working electrode, platinized platinum For to electrode, saturated calomel electrode is reference electrode, 0.02M Ni (Ac)2The aqueous solution is reaction electrolyte, in -1.0mAcm-2It is permanent Electrodeposit reaction 30 minutes under current condition, in TiO2Metallic nickel sedimentary is generated on nano-tube support, then in 1.0M NaOH In aqueous electrolyte, working electrode potential is in -0.9V to 0.9V vs.SCE（Saturated calomel electrode）In the range of cyclic voltammetric 15min is scanned, electro-oxidation reaction generation nickel hydroxide sedimentary, is generated within 2 hours finally by 300 DEG C of heat treatment dehydrations TiO2/ NiO electrode materials；
S7：KOH electrolyte, shape are filled between the three-dimensional interdigital microelectrode with NiO active materials formed in step s 6 Into TiO2The three-dimensional interdigital microelectrodes of/NiO.

Claims (1)

1.TiO2The three-dimensional interdigital microelectrodes of/NiO, it is characterised in that including silicon chip, silicon chip is provided with insulating barrier, is sputtered on insulating barrier There is layer of titanium metal, pass through mask, the three-dimensional interdigital microelectrode of method formation titanium of corrosion, the three-dimensional interdigital microelectrode of titanium in layer of titanium metal Upper oxidation forms TiO2Nano-tube array, TiO2Deposition has NiO in nanotube, is electrolysed between three-dimensional interdigital microelectrode filled with KOH Matter, TiO2The preparation method of the three-dimensional interdigital microelectrodes of/NiO, comprises the following steps：
S1：Choose silicon chip simultaneously carry out Wafer Cleaning, get rid of organic oil, inorganic oil on silicon chip, go oxide film dissolving and metal from Son；
S2：Put silicon chip cleaned in step S1 into oxidation furnace to be aoxidized, be followed successively by dry-oxygen oxidation-wet-oxygen oxidation-dry Oxygen aoxidizes, and oxidization time is 10 hours, forms insulating barrier of the oxide-film as micro super capacitor electrode, oxide thickness For 1.5 microns；
S3：Put the silicon chip formed in step S2 into vacuum sputter system, a layer thickness is sputtered as 400 nanometers in front side of silicon wafer Titanium；
S4：One layer of SU-8 photoresist is uniformly coated with using the method for rotation spin coating in the layer of titanium metal on silicon chip in step s3, And exposed by interdigital mask plate, development；The Titanium of exposure is removed with the method for corrosion again, is finally removed photoresist, it is three-dimensional to form titanium Interdigital microelectrode；
S5：The three-dimensional interdigital microelectrode of titanium in step S4 is put into anodic oxidation device and carries out anodic oxidation, oxidation is first to apply Add 10 volts of voltage 20 seconds, then apply 0.5 volt of voltage and the TiO that height is 90-270 nanometers is formed after 25 minutes2Nano-tube array；
S6：Three-electrode electro Chemical reaction system is established, the TiO that will be formed in step S52Nanotube is working electrode, and platinized platinum is pair Electrode, saturated calomel electrode are reference electrode, 0.02M Ni (Ac)2The aqueous solution is reaction electrolyte, in -1.0mAcm-2Permanent electricity Electrodeposit reaction 30 minutes under the conditions of stream, in TiO2Metallic nickel sedimentary is generated on nano-tube support, then in 1.0M NaOH In aqueous electrolyte, working electrode potential cyclic voltammetry scan 15min, electric oxygen in the range of -0.9V to 0.9V vs.SCE Change reaction generation nickel hydroxide sedimentary, finally by 300 DEG C of heat treatment dehydrations, 2 hours generation TiO2/ NiO electrode materials Material；
S7：KOH electrolyte is filled between the three-dimensional interdigital microelectrode with NiO active materials formed in step s 6, is formed TiO2The three-dimensional interdigital microelectrodes of/NiO.
CN201410697924.1A 2014-11-28 2014-11-28 TiO2Three-dimensional interdigital microelectrodes of/NiO and preparation method thereof Expired - Fee Related CN104465125B (en)

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CN106158411A (en) * 2016-08-17 2016-11-23 武汉理工大学 A kind of high-performance symmetrical expression metal-oxide base micro super capacitor and preparation method thereof
CN106340445B (en) * 2016-09-13 2019-10-15 复旦大学 Sequential 2 D TiO2The preparation method of nanometer well film and the application in self energizing photoelectric device
CN108793065B (en) * 2018-06-25 2020-09-15 太原理工大学 Preparation method of MEMS (micro-electromechanical systems) supercapacitor with controllable dielectric film thickness
CN112582184B (en) * 2020-12-01 2022-07-08 上海集成电路研发中心有限公司 Nanowire electrode, capacitor electrode and preparation method of nanowire electrode and capacitor electrode
CN113776699B (en) * 2021-09-18 2024-01-30 太原理工大学 Positive pressure insensitive interdigital capacitive strain sensor and preparation method thereof
CN114141544B (en) * 2021-10-13 2023-03-24 四川大学 Electrode material of on-chip integrated super capacitor and preparation method thereof

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Inventor after: Guo Lifang

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Inventor after: Li Gang

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Inventor after: Zhang Junhui

Inventor after: Zhang Wendong

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