CN103779091B - A kind of modified Nano SiO2and preparation method and application - Google Patents

A kind of modified Nano SiO2and preparation method and application Download PDF

Info

Publication number
CN103779091B
CN103779091B CN201210407160.9A CN201210407160A CN103779091B CN 103779091 B CN103779091 B CN 103779091B CN 201210407160 A CN201210407160 A CN 201210407160A CN 103779091 B CN103779091 B CN 103779091B
Authority
CN
China
Prior art keywords
modified nano
nano sio
sio
particle
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201210407160.9A
Other languages
Chinese (zh)
Other versions
CN103779091A (en
Inventor
黄宇剑
周晓文
方世璧
林原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN201210407160.9A priority Critical patent/CN103779091B/en
Publication of CN103779091A publication Critical patent/CN103779091A/en
Application granted granted Critical
Publication of CN103779091B publication Critical patent/CN103779091B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention discloses a kind of modified Nano SiO2And preparation method thereof.This modified Nano SiO2It is made up of following method: polyethylene methyl acrylate glycidyl methacrylate and Nano-meter SiO_22Carry out reacting and i.e. obtain described modified Nano SiO2.Modified Nano SiO provided by the present invention2And preparation method and application have the advantage that 1, with cheap polyethylene acrylate glycidyl methacrylate modified Nano SiO2Particle manipulation is simple, low for equipment requirements.2, the modified Nano SiO prepared by the method2Having the high compatibility in the polymer, it is applied and shows high performance when DSSC so that prepared battery has high photoelectric conversion performance.

Description

A kind of modified Nano SiO2And preparation method and application
Technical field
The present invention relates to a kind of modified Nano SiO2And preparation method and application.
Background technology
Nanoparticle is widely used at such as filling modification of polymer materials, such as the application in DSSC.In the various methods of the most all conductivity at room temperature being used for improving solid polymer electrolyte, it is a kind of more effective method by add inorganic nano-particle in polymer forming nano combined solid polymer electrolyte.Adding in addition to having the effect that electrolyte strengthens reinforcement of nanoparticle, scattered inorganic powder has affinity interaction to residual moisture content in the electrolyte and organic solvent, it is possible to " is captured " by these impurity thus plays the effect of interface stability agent；On the other hand, the addition of high-dielectric constant inorganic particle can promote dissociating and suppressing polymer crystallization of slaine, forms special ion channel at particle surface, thus improves ionic conductivity.Visible, in solid polymer electrolyte, add nanoparticle there is raising ionic conductivity, strengthen mechanical strength and the function of electrolyte interface stability.
Owing to nanoparticle is easily reunited, and poor with polymer compatibility.Therefore want the nano composition that processability is excellent, it is critical only that solving nanoparticle reunites and the problem of polymer compatibility difference.
Summary of the invention
It is an object of the invention to provide a kind of modified Nano SiO2And preparation method and application, this preparation method is that a kind of technique is simple, the Nano-meter SiO_2 of low cost2Particle modified method；The modified Nano SiO that the present invention provides2Have reproducible, good stability and with the advantage such as polymer compatibility is good.
A kind of modified Nano SiO provided by the present invention2Preparation method, comprise the steps:
Polyethylene-methyl acrylate-glycidyl methacrylate and Nano-meter SiO_22Carry out reacting and i.e. obtain described modified Nano SiO2。
In above-mentioned preparation method, described Nano-meter SiO_22Particle diameter can be 7nm～100nm, concretely 7nm～14nm, 7nm or 14nm.
In above-mentioned preparation method, the solvent of described reaction can be at least one in oxolane, acetonitrile and dichloromethane, such as oxolane.
In above-mentioned preparation method, the temperature of described reaction can be 60 DEG C ~ 100 DEG C, when the time can be 2 ~ 24, as reacted 6 hours or 8 hours at 60 DEG C.
Invention further provides the modified Nano SiO prepared by said method2。
Present invention also offers a kind of modified Nano SiO2Particle doping and blending polymer dielectric, it is by above-mentioned modified Nano SiO2Form with polymer blend, described modified Nano SiO2It is (1 ~ 15) with the mass fraction ratio of polymer blend: (1 ~ 100), concretely (1 ~ 5): 50,1:50,1:30 or 1:10；
Described polymer blend can be polyethylene glycol oxide/polyvinyl acetate or polymethyl methacrylate/polyvinyl acetate, wherein in this polymer blend, the mass fraction of polyethylene glycol oxide or polymethyl methacrylate and polyvinyl acetate can be in 1:(1 ~ 5) in the range of be adjusted, such as 3:7.
Invention further provides above-mentioned modified Nano SiO2The application in preparing DSSC of the particle doping and blending polymer dielectric.
Modified Nano SiO provided by the present invention2And preparation method and application have the advantage that
1, with cheap polyethylene-acrylate-glycidyl methacrylate modified Nano SiO2Particle manipulation is simple, low for equipment requirements.
2, the modified Nano SiO prepared by the method2Having the high compatibility in the polymer, it is applied and shows high performance when DSSC so that prepared battery has high photoelectric conversion performance.
Accompanying drawing explanation
Fig. 1 is polyethylene-acrylate-glycidyl methacrylate, modified SiO2Modified Nano SiO with embodiment 1 preparation2Infrared spectrum.
Fig. 2 is the photoelectric properties curve of all-solid-state dye-sensitized solar cell prepared by the electrolyte of embodiment 1 and embodiment 3.
Detailed description of the invention
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, the most commercially obtain.
In following embodiment, use modified Nano SiO prepared by Infrared Characterization2, use the modified Nano SiO prepared by photoelectric properties curve sign2Polymer performance before and after doping.Photoelectric properties are the highest, and modified Nano SiO is described2Doped polymeric physical performance is the best.
Embodiment 1, prepare modified Nano SiO2And modified Nano SiO2Particle doped polymer electrolyte
(1) modified Nano SiO is prepared2
Add in oxolane by polyethylene-acrylate-glycidyl methacrylate, ultrasonic until being completely dissolved；Nano-meter SiO_2 by dried 7nm2Ultrasonic disperse in oxolane, ultrasonic time 20 minutes；By ultrasonic complete SiO2Tetrahydrofuran solution during agitating heating, be slowly added dropwise polyethylene-acrylate-glycidyl methacrylate tetrahydrofuran solution, be warming up to after dropping 60 DEG C react 6 hours.Solvent in vacuo rotation is steamed, is dried and mills, obtain modified Nano SiO2Particle.
Fig. 1 is followed successively by polyethylene-acrylate-glycidyl methacrylate, Nano-meter SiO_2 from top to bottom2With modified SiO2Infrared spectrum.
The SiO of the most modified nanometer23000cm occurs-1To 2700cm-1Methyl and methylene peak, and 910cm-1Epoxy peak, place disappears, and modified success is described.
(2) modified Nano SiO is prepared2Particle doped polymer electrolyte
Add 0.35g polyvinyl acetate, 0.15 polymethyl methacrylate, 0.083LiI and 0.416g I2In tetrahydrofuran solution, stir dissolving.Take modified Nano SiO prepared by 0.01g step (1)2Particle adds solution, ultrasonic 20 minutes, obtains modified Nano SiO after vacuum drying2Particle doped polymer.
Embodiment 2, prepare modified Nano SiO2And modified Nano SiO2Particle doped polymer electrolyte
(1) preparation method is with step (1) in embodiment 1.
(2) modified Nano SiO is prepared2Particle doped polymer electrolyte
Prepare modified Nano SiO2During particle doped polymer electrolyte, except adding 0.03g modified Nano SiO2Particle replaces 0.01g modified Nano SiO2Outside particle, remaining is with embodiment 1.
Embodiment 3, prepare modified Nano SiO2And modified Nano SiO2Particle doped polymer electrolyte
(1) preparation method is with step (1) in embodiment 1.
(2) modified Nano SiO is prepared2Particle doped polymer electrolyte
Prepare modified Nano SiO2During particle doped polymer electrolyte, except adding 0.05g modified Nano SiO2Particle replaces 0.01g modified Nano SiO2Outside particle, remaining is with embodiment 1.
Embodiment 4, prepare modified Nano SiO2And modified Nano SiO2Particle doped polymer electrolyte
(1) modified Nano SiO is prepared2
Polyethylene-acrylate-glycidyl methacrylate is added in oxolane, ultrasonic until being completely dissolved；Nano-meter SiO_2 by dried 14nm2Ultrasonic disperse in oxolane, ultrasonic time 30 minutes；By ultrasonic complete SiO2Tetrahydrofuran solution during agitating heating, be slowly added dropwise the tetrahydrofuran solution of polyethylene-acrylate-glycidyl methacrylate, be warming up to 60 DEG C after dropping and react 8 hours.Solvent in vacuo rotation is steamed, is dried and mills, obtain modified Nano SiO2Particle.
(2) modified Nano SiO is prepared2Particle doped polymer electrolyte
Add 0.35g polyvinyl acetate, 0.15g polymethyl methacrylate, 0.083LiI and 0.416g I2In tetrahydrofuran solution, it is evenly stirred until dissolving.Take modified Nano SiO prepared by 0.01g above-mentioned steps (1)2Particle adds solution, ultrasonic 20 minutes, obtains modified Nano SiO after vacuum drying2Particle doped polymer.
Embodiment 5, prepare modified Nano SiO2And modified Nano SiO2Particle doped polymer electrolyte
(1) preparation method is with step (1) in embodiment 4.
(2) modified Nano SiO is prepared2Particle doped polymer electrolyte
Prepare modified Nano SiO2During particle doped polymer electrolyte, except adding 0.03g modified Nano SiO2Particle replaces 0.01g modified Nano SiO2Outside particle, remaining is with embodiment 4.
The application of polymer dielectric prepared by embodiment 6, embodiment 1-5
By the modified Nano SiO of above-mentioned preparation2Particle doped polymer is applied in DSSC, and surveys the photoelectric properties of assembled battery.
Method particularly includes: colloidal tio 2 is coated in FTO electro-conductive glass substrate (FTO is that fluorine mixes tin ash), then carries out 450 DEG C of sintering and obtain the titanium deoxid film that thickness is 10 microns, after cooling, be immersed in 5 × 10-4mol L-1In the ethanol solution of double (N, N'-2,2'-bipyridyl-4, the 4'-formic acid) ruthenium dye of N3(CIS-bis-thiocyano-, adsorb 12 hours；Afterwards electrode taking-up dehydrated alcohol is rinsed well, as working electrode after drying；By 0.1mol L-1Isopropyl alcohol solution of chloroplatinic acid is coated in FTO electro-conductive glass substrate, then carries out 390 DEG C of sintering and obtain homemade platinum electrode in 15 minutes.By prepared modified Nano SiO2Particle doped polymer is dissolved in acetonitrile, slowly drips on the working electrode (s, presses self-control platinum electrode, and the battery the vacuum drying that are packaged into sandwich structure thoroughly remove solvent.
Test at ambient temperature with electrochemical workstation (Model 273, EG&G).Using xenon lamp to be light source and correct light intensity with standard silion cell, illuminating area is 0.2cm-2.Fill factor, curve factor (ff) refers to that the current/voltage product (Jopt*Vopt) that can obtain on the point of peak power output in J-V curve and Jsc*Voc(Jsc are short-circuit photocurrent, Voc is open-circuit photovoltage) ratio, it embody battery output with load variation characteristic.Photoelectric transformation efficiency (η) is then the ratio of Jopt*Vopt luminous power Pin with input.
It Fig. 2 is the most successively the current-voltage curve of DSSC prepared of the electrolyte of embodiment 1 and embodiment 3 preparation.As shown in Figure 2, the Jsc (circuit photocurrent density) of battery prepared by the electrolyte of embodiment 1 preparation is 4.43mA/cm2, Voc is 664mV, and being calculated fill factor, curve factor (ff) is 0.58, and photoelectric transformation efficiency (η) is 1.71%, and the Jsc (circuit photocurrent density) of battery prepared by the electrolyte of embodiment 3 preparation is 7.84mA/cm2, Voc is 637mV, and being calculated fill factor, curve factor (ff) is 0.61, and photoelectric transformation efficiency (η) is 3.04%.

Claims (3)

1. a modified Nano SiO2Particle doping and blending polymer dielectric, it is by modified Nano SiO2Form with polymer blend, described modified Nano SiO2With the mass fraction of polymer blend than for 1:10 or 1:50；
Described polymer blend is polymethyl methacrylate/polyvinyl acetate, and wherein, the mass fraction of described polymethyl methacrylate and described polyvinyl acetate is than for 3:7；
Described modified Nano SiO2Prepare according to the method comprised the steps:
Polyethylene-methyl acrylate-glycidyl methacrylate and Nano-meter SiO_22Carry out reacting and i.e. obtain described modified Nano SiO2；
Described Nano-meter SiO_22Particle diameter be 7nm～100nm；
The solvent of described reaction is at least one in oxolane, acetonitrile and dichloromethane；
Described reaction is reacted 6 hours or 8 hours at 60 DEG C.
2. modified Nano SiO described in claim 12The application in preparing DSSC of the particle doping and blending polymer dielectric.
3. a DSSC, it includes modified Nano SiO described in claim 12Particle doping and blending polymer dielectric.
CN201210407160.9A 2012-10-23 2012-10-23 A kind of modified Nano SiO2and preparation method and application Expired - Fee Related CN103779091B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210407160.9A CN103779091B (en) 2012-10-23 2012-10-23 A kind of modified Nano SiO2and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210407160.9A CN103779091B (en) 2012-10-23 2012-10-23 A kind of modified Nano SiO2and preparation method and application

Publications (2)

Publication Number Publication Date
CN103779091A CN103779091A (en) 2014-05-07
CN103779091B true CN103779091B (en) 2016-10-26

Family

ID=50571229

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210407160.9A Expired - Fee Related CN103779091B (en) 2012-10-23 2012-10-23 A kind of modified Nano SiO2and preparation method and application

Country Status (1)

Country Link
CN (1) CN103779091B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109326447A (en) * 2018-11-07 2019-02-12 广州金立电子有限公司 A kind of electrolytic capacitor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050094560A (en) * 2004-03-23 2005-09-28 대한유화 주식회사 Coating agent of material and its manufacturing method
CN101423735A (en) * 2008-12-05 2009-05-06 武汉科技学院 Method for preparing environment-friendly type organosilicon modified acrylic ester binding agent
CN102504611A (en) * 2011-10-17 2012-06-20 中科院广州化学有限公司 Improved silicon dioxide, high-performance lithium ion battery separator membrane and application thereof
CN102605621A (en) * 2012-03-08 2012-07-25 陕西科技大学 Method for preparing waterproof moisture-permeability fabric coating agent with nano SiO2 modified polyacrylate
CN102703009A (en) * 2012-07-05 2012-10-03 黑龙江省科学院石油化学研究院 Preparation method of nano silicon dioxide/polyacrylate modified epoxy resin adhesive
CN102738275A (en) * 2011-04-12 2012-10-17 苏州尚善新材料科技有限公司 Solar cell assembly backplane and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070293603A1 (en) * 2006-06-19 2007-12-20 Ashland Licensing And Intellectual Property Llc Epoxy adhesive composition and use thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050094560A (en) * 2004-03-23 2005-09-28 대한유화 주식회사 Coating agent of material and its manufacturing method
CN101423735A (en) * 2008-12-05 2009-05-06 武汉科技学院 Method for preparing environment-friendly type organosilicon modified acrylic ester binding agent
CN102738275A (en) * 2011-04-12 2012-10-17 苏州尚善新材料科技有限公司 Solar cell assembly backplane and preparation method thereof
CN102504611A (en) * 2011-10-17 2012-06-20 中科院广州化学有限公司 Improved silicon dioxide, high-performance lithium ion battery separator membrane and application thereof
CN102605621A (en) * 2012-03-08 2012-07-25 陕西科技大学 Method for preparing waterproof moisture-permeability fabric coating agent with nano SiO2 modified polyacrylate
CN102703009A (en) * 2012-07-05 2012-10-03 黑龙江省科学院石油化学研究院 Preparation method of nano silicon dioxide/polyacrylate modified epoxy resin adhesive

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
凝胶聚合物电解质的制备、改性及其在DSSC中的应用;陈小花;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》;20111215(第12期);第22-23，27页 *
弹性体修饰纳米SiO2 粒子改性PBT;洪月蓉,张玲,牛建华,张天水,李春忠;《复合材料学报》;20090630;第26卷(第3期);摘要，第56页第3段，第57页第2-3段 *

Also Published As

Publication number Publication date
CN103779091A (en) 2014-05-07

Similar Documents

Publication Publication Date Title
Venkatesan et al. Highly efficient quasi-solid-state dye-sensitized solar cells prepared by printable electrolytes for room light applications
Yang et al. The polymer gel electrolyte based on poly (methyl methacrylate) and its application in quasi-solid-state dye-sensitized solar cells
Bella et al. Performance and stability improvements for dye-sensitized solar cells in the presence of luminescent coatings
Huo et al. Nanocomposite gel electrolyte with large enhanced charge transport properties of an I3−/I− redox couple for quasi-solid-state dye-sensitized solar cells
Ren et al. Application of PEO based gel network polymer electrolytes in dye-sensitized photoelectrochemical cells
Yang et al. Improved stability of quasi-solid-state dye-sensitized solar cell based on poly (ethylene oxide)–poly (vinylidene fluoride) polymer-blend electrolytes
Wu et al. A polyblend electrolyte (PVP/PEG+ KI+ I2) for dye-sensitized nanocrystalline TiO2 solar cells
KR101146667B1 (en) Metal oxide paste composition and preparaton method of a semiconductor electrode using the same
Juang et al. Energy harvesting under dim-light condition with dye-sensitized and perovskite solar cells
Lim et al. Dye-sensitized solar cells with quasi-solid-state cross-linked polymer electrolytes containing aluminum oxide
Lan et al. Influence of molecular weight of PEG on the property of polymer gel electrolyte and performance of quasi-solid-state dye-sensitized solar cells
Saikia et al. Influence of polymer concentration and dyes on photovoltaic performance of dye-sensitized solar cell with P (VdF-HFP)-based gel polymer electrolyte
Wu et al. Quasi-solid state dye-sensitized solar cells-based gel polymer electrolytes with poly (acrylamide)–poly (ethylene glycol) composite
Wang et al. Gel polymer electrolytes based on polyacrylonitrile and a novel quaternary ammonium salt for dye-sensitized solar cells
Wang et al. Solidification of liquid electrolyte with imidazole polymers for quasi-solid-state dye-sensitized solar cells
Scully et al. Dye-sensitized solar cells employing a highly conductive and mechanically robust nanocomposite gel electrolyte
Zhang et al. Performance enhancement for quasi-solid-state dye-sensitized solar cells by using acid-oxidized carbon nanotube-based gel electrolytes
EP1724871B1 (en) Composition for Preparing Polymer Electrolyte for use in Dye-Sensitized Solar Cell
JP2008004550A (en) Surface modification method for counter electrode, and counter electrode with modified surface
Gong et al. Polymer electrolyte based on polyethylene glycol for quasi-solid state dye sensitized solar cells
Shah et al. A stable gel electrolyte based on poly butyl acrylate (PBA)-co-poly acrylonitrile (PAN) for solid-state dye-sensitized solar cells
Lu et al. Quasi-solid-state dye-sensitized solar cells with cyanoacrylate as electrolyte matrix
Chang et al. Preparation of nano-composite gel electrolytes with metal oxide additives for dye-sensitized solar cells
Mohan et al. A highly stable and efficient quasi solid state dye sensitized solar cell based on Polymethyl methacrylate (PMMA)/Polyaniline Nanotube (PANI-NT) gel electrolyte
Lan et al. Quasi-solid-state dye-sensitized solar cells with a novel efficient absorbent for liquid electrolyte based on PAA–PEG hybrid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20161026

Termination date: 20191023