CN104867679A - Functional nanoparticle and preparation method and application thereof - Google Patents
Functional nanoparticle and preparation method and application thereof Download PDFInfo
- Publication number
- CN104867679A CN104867679A CN201510279974.2A CN201510279974A CN104867679A CN 104867679 A CN104867679 A CN 104867679A CN 201510279974 A CN201510279974 A CN 201510279974A CN 104867679 A CN104867679 A CN 104867679A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- iodine
- preparation
- methyl
- functional nanoparticle
- 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.)
- Granted
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
-
- 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
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a functional nanoparticle and a preparation method and application thereof. The preparation method comprises the following steps that 1) a siloxane precursor and water react under existence of a catalyst so that a prepolymer is obtained, wherein the siloxane precursor comprises at least one of the following function groups: amino, carboxyl, cyano, nitrogen heterocyclic and mercapto; and 2) the prepolymer and inorganic nanoparticles react in an organic solvent under the inert atmosphere so that functional nanoparticles are obtained. The preparation method is simple, stable in performance, low in price and convenient for industrial production and practical application. The functional nanoparticles are added to an electrolyte so that performance of the electrolyte can be obviously improved, e.g. the electrolyte can be gelatinized, and stability can be greatly enhanced. Besides, conductive capability and ion transmission and diffusion of the electrolyte can also be improved. Therefore, the functional nanoparticles are applied to a dye-sensitized solar cell so that open-circuit voltage, short-circuit current and photoelectric conversion efficiency of the cell can be obviously enhanced.
Description
Technical field
The invention belongs to nanometer particle-modified field, be specifically related to a kind of functional nanoparticle and preparation method thereof and application.
Background technology
At present, liquid electrolyte, quasi-solid electrolyte and all solid state electrolyte three class is generally divided into for the electrolyte in battery.The advantages such as conductivity is high although liquid electrolyte has, ion diffuse speed is fast, its organic solvent used is volatile, toxicity large, thus causes poor stability, the encapsulation difficulty of battery, limits the prolonged application of DSSC.And although all solid state electrolyte does not have above-mentioned shortcoming, its ionic mobility and hole transport speed is lower, with poor to the contact performance of electrode, cause the photoelectric conversion efficiency of battery generally lower.Quasi-solid electrolyte like this between liquid electrolyte and all solid state electrolyte, owing to keeping the high mobility of ion to greatest extent and have long-time stability, has attracted the attention of numerous researchers.
The application of additive agent electrolyte not only can improve the performance of electrolyte itself, can also improve the photoelectric properties of battery.But current used additive major part is contrary on the open circuit voltage of battery and the impact of short circuit current, seldom has additive can improve this two parameters simultaneously.As: the interpolation of tertiary butyl pyridine makes TiO
2conduction band current potential moves toward negative potential direction, can improve open circuit voltage, but also causes excitation state dyestuff and TiO
2between conduction band current potential, electrical potential difference reduces, and is unfavorable for that light induced electron is injected into TiO
2in conduction band, and then short circuit current is declined; Another kind of additive LiI effectively can improve short circuit current, but also reduces open circuit voltage simultaneously; In addition, two kinds of conventional additive agent electrolyte 4-tert .-butylpyridine (TBP) and N-tolimidazole (NMBI), after interpolation, can suppress electron back to compound, and then can significantly improve open circuit voltage and the fill factor, curve factor of battery, but short circuit current slightly declines.
In addition, current used additive mostly cost is very high, and liquid type additive exists the shortcomings such as volatile and unstable; And solid additives is easily separated out, all drastically influence electrolytical performance.
Summary of the invention
The object of the present invention is to provide a kind of functional nanoparticle and preparation method thereof.
The preparation method of functional nanoparticle provided by the present invention, comprises the steps:
1) prepare prepolymer: in the presence of a catalyst, siloxane precursors and water are reacted, obtain prepolymer, wherein, described siloxane precursors is containing, for example at least one in lower functional group: amino, carboxyl, cyano group, nitrogen heterocyclic ring and sulfydryl;
2) prepare functional nanoparticle: under an inert atmosphere, described prepolymer and inorganic nano-particle are reacted in organic solvent, obtains functional nanoparticle.
In above-mentioned preparation method, step 1) in, the mol ratio of described siloxane precursors and water is (0.1-10): 1, specifically can be (0.5-2.5): 1.
The mol ratio of described catalyst and water is 1:(300-10), specifically can be 1:(10-50).
The reaction temperature of described reaction is 60-100 DEG C, and specifically can be 80 DEG C, the reaction time is 1-2h, specifically can be 1h.
Described catalyst is alkali, and described alkali is selected from least one in calcium hydroxide, NaOH and potassium hydroxide.
Described siloxane precursors specifically can be selected from 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-cyanopropyl triethyl silicane, 3-cyano group trimethoxy silane, 3-mercaptopropyltriethoxysilane, 3-methoxyl group hydrosulphonyl silane, side chain contain at least one in nitrogenous heterocyclic polysiloxanes etc.
In above-mentioned preparation method, step 1) in, described reaction is preferably the first stir process 24-36h at 20-30 DEG C by siloxane precursors and water, add catalyst wherein again, and steaming reaction 1-2h in 60-100 DEG C of backspin, suction filtration obtains supernatant, is described prepolymer.
Described nitrogen heterocyclic ring specifically can be at least one in pyrroles, imidazoles and pyridine.
In above-mentioned preparation method, step 2) in, described inert atmosphere is N
2and/or Ar atmosphere.
Described inorganic nano-particle is specifically selected from oxide and/or the oxide containing doped chemical, and described oxide is SiO
2and/or metal oxide, the described oxide containing doped chemical is the SiO of at least one in doping Nb, Ru, Mn, Ta and Si
2and/or metal oxide.
Described metal oxide is selected from TiO
2, ZnO and Al
2o
3in at least one.
The particle diameter of described inorganic nano-particle is 1-300nm.
The mass ratio of described prepolymer and inorganic nano-particle is 1:(0.1-1), specifically can be 1:0.5.
The reaction temperature of described reaction is 20-30 DEG C, and specifically can be 25 DEG C (room temperatures), the reaction time is 36-48h, specifically can be 48h.
Described organic solvent is at least one in toluene, benzene, dimethylbenzene and butyl toluene.
In above-mentioned preparation method, step 2) in, also comprise obtained functional nanoparticle is washed successively, dry step, concrete steps are as follows: use CH
2cl
2wash three times, then steam in 40-60 DEG C of backspin, after being spin-dried for, in the baking oven of 80-100 DEG C, dry 36-48h.
In addition, preparation-obtained functional nanoparticle also obtains other functional nanoparticles by methods such as oxidation, reduction, addition and displacements, as: how cyanomodified Nano particles of silicon dioxide can be obtained how carboxy-modified Nano particles of silicon dioxide further by oxidizing process.
The preparation-obtained functional nanoparticle of the present invention also belongs to protection scope of the present invention.
Another object of the present invention is to provide a kind of based on the electrolyte of functional nanoparticle as additive.
Electrolyte provided by the present invention comprises described functional nanoparticle, electrolyte solvent and oxidation-reduction pair, and wherein, the mass fraction of described functional nanoparticle is 0.1%-60%, and the mass fraction of oxidation-reduction pair is 1%-20%.
In above-mentioned electrolyte, described electrolyte solvent is organic solvent and/or ionic liquid, and wherein, described organic solvent is selected from least one in trimethoxy propionitrile, acetonitrile, ethylene carbonate and propene carbonate; Described ionic liquid is selected from least one in 1-methyl-3-hexyl imidazolium iodine (HMII), 1-methyl-3-propyl imidazole iodine (PMII), 1-methyl-3-ethyl imidazol(e) iodine (EMII), 1-methyl-3-allyl imidazole iodine (AMII), 1-methyl-3-butyl imidazole iodine (BMII) and 1,3-methylimidazole iodine (DMII).
Described oxidation-reduction pair specifically can be iodine and iodide ion oxidation-reduction pair.Described iodine and iodide ion oxidation-reduction pair specifically can be selected from I
2with containing iodine inorganic salts or I
2with containing iodide ion liquid, wherein, the described at least one be specifically selected from containing iodine inorganic salts in LiI, KI and NaI, the described at least one be specifically selected from containing iodide ion liquid in 1,3-methylimidazole iodine, 1-methyl-3-hexyl imidazolium iodine, 1-methyl-3-ethyl imidazol(e) iodine, 1-methyl-3-allyl imidazole iodine and 1-methyl-3-butyl imidazole iodine.
Certainly, can also add other additive that can improve arbitrarily battery performance in described electrolyte, other additive described is preferably at least one in sulphur cyanoguanidine salt, N-tolimidazole, N-butyl benzimidazole and 4-vinylpridine, 4-tert .-butylpyridine etc.
Of the present invention based on the electrolyte preparation method of functional nanoparticle as additive, above-mentioned functions nano particle, electrolyte solvent and oxidation-reduction pair is comprised the steps: to mix in described ratio, quasi-solid electrolyte can be obtained, namely based on the electrolyte of functional nanoparticle as additive.
In above-mentioned preparation method, during described mixing, impose external force, described external force is grinding, ultrasonic or stirring etc.
In addition, the preparation-obtained functional nanoparticle of the present invention and/or the application of electrolyte in preparation DSSC also belong to protection scope of the present invention.
Functional nanoparticle preparation method of the present invention is simple, stable performance, cheap, be convenient to suitability for industrialized production and practical application.In addition, play the effect making electrolyte gelation as the functional nanoparticle in the electrolyte of additive based on functional nanoparticle, greatly improve electrolytical stability, electrolytical performance can also be improved, as: strengthen electrolytical conductive capability and ionic mobility etc., reason is that functional nanoparticle is rich in electron group or strong electron-withdrawing group group, effectively can act on ion in electrolyte (as: with oxidation electricity to reacting) or work electrode (as: makes TiO by these functional groups
2flat-band potential is moved), even with to electrode (strengthening its catalytic performance) occur to interact.Moreover, be applied in DSSC, open circuit voltage and the short circuit current of battery can be improved simultaneously, thus improve the photoelectric conversion efficiency of battery to a great extent, make the photoelectric conversion efficiency of battery more than 8%.
Accompanying drawing explanation
Fig. 1 is the NH adding different content in embodiment 1
2-SiO
2rear electrolytical conductivity variations;
Fig. 2 is the NH of interpolation 5% in embodiment 1
2-SiO
2electrolytical battery efficiency trend over time;
Fig. 3 is the NH adding different content in embodiment 1
2-SiO
2rear electrolytical gelation.
Fig. 4 surveys by embodiment 1-6 the photoelectricity I-V curve of the peak efficiency of DSSC
Embodiment
Be described method of the present invention below by specific embodiment, but the present invention is not limited thereto, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Nano particles of silicon dioxide particle diameter used in each embodiment following is 7nm, purchased from Alfa.
Embodiment 1, the Nano particles of silicon dioxide additive preparing polyamino modification, electrolyte and DSSC:
One, the Nano particles of silicon dioxide additive of polyamino modification is prepared:
1) prepare APTS (3-aminopropyl triethoxysilane) prepolymer: in 250mL single port bottle, add 0.3mol APTS, in stirring, add 0.2mol water, continue stirring at room temperature 24h; Subsequently, add 0.4g calcium hydroxide, after stirring 30min after 80 DEG C of backspins steam reaction 1h, suction filtration obtains supernatant, obtains APTS prepolymer;
2) APTS prepolymer modification SiO
2inorganic nano-particle: add 2g SiO in 250mL there-necked flask
2with 100mL toluene, N
2under atmosphere, stir 30min, drip 4g APTS prepolymer, be spin-dried for after stirred at ambient temperature 48h; Then CH is used
2cl
2wash three times, then steam in 40 DEG C of backspins, in the baking oven of 85 DEG C, dry 48h after being spin-dried for, obtain polyamino improved silica nano particle, be labeled as NH
2-SiO
2.
Two, nano-composite gel electrolyte is prepared:
1) ionic liquid electrolyte HA is configured: after first 0.224g sulphur cyanoguanidine salt (GuNCS) and 0.25g N-tolimidazole (NMBI) being heated at 90 DEG C 1h dissolving, add 3.178g 1-methyl-3-allyl imidazole iodine (AMII), 3.718g 1-methyl-3-hexyl imidazolium iodine (HMII) and 0.4g I
2, mixing, namely obtains HA.
2) NH is added
2-SiO
2make ionic liquid electrolyte HA gel: weigh 3g HA respectively, then by the method for grinding, ultrasonic or magnetic agitation by NH
2-SiO
2mix with HA, make NH
2-SiO
2mass fraction be 1%-20%, specifically can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 15%, 20%, prepare nano-composite gel electrolyte.
Three, DSSC is prepared:
1) first carry out preliminary treatment to electro-conductive glass (first to remove the organic substances such as the oil stain of conductive glass surface with organic solvent, and then repeatedly rinse with running water and deionized water, dry; Then be soaked in isopropyl alcohol for subsequent use), be then the self-control TiO of 12% successively by bottom (isopropyl oxygen alcohol titanium), solid content
2(concrete grammar is as follows: in beaker, first add 120mL n-butanol, 20mL acetone, 10mL glacial acetic acid and 20mL butyl titanate, and electromagnetic agitation is even, is labeled as solution A for colloid; Then in another beaker, add the deionized water of 80mL n-butanol, the 2.4mL 30wt%PEG aqueous solution and 6mL, electromagnetic agitation is even, is labeled as solution B; Under constantly stirring, solution B is dropped in solution A by dropping funel uniform speed slow, dropwise rear continuation and stir 1h, then transfer them in autoclave, hydro-thermal reaction 6h at 240 DEG C, naturally cool to after room temperature until it, with cell disruptor ultrasonic disperse 30min; Finally steaming is revolved to reactant liquor, obtain the TiO that solid content is 12%
2colloid) be coated on the electro-conductive glass handled well, after high temperature (450 DEG C) process, immerse attach overnight in N3 dyestuff, form the work electrode of battery, smeared on the working electrode (s by the nano-composite gel electrolyte of above-mentioned preparation, what press platinum plating is prepared into DSSC to electrode.
In order to compare, completely by the above-mentioned method preparing DSSC, only smear ionic liquid electrolyte HA on the working electrode (s, thus prepare the DSSC not containing nano-composite gel electrolyte.
Corresponding test result is as follows: Fig. 1 is the NH adding different content
2-SiO
2rear electrolytical conductivity variations, as can be seen from Figure 1: add a certain amount of modification SiO
2after, electrolytical conductivity significantly improves.Corresponding data are as shown in table 1, learn from table 1: the NH adding different content
2-SiO
2after, electrolytical conductivity significantly improves, and electrolytical resistance R declines.
The modification SiO of table 1, interpolation different content
2rear electrolytical conductivity
| Electrolyte | R | Conductivity (S/m) |
| HA-IL | 145.88 | 0.13972 |
| HA-IL+1％NH 2-SiO 2 | 95.007 | 0.21453 |
| HA-IL+2％NH 2-SiO 2 | 98.722 | 0.20646 |
| HA-IL+3％NH 2-SiO 2 | 81.874 | 0.24894 |
| HA-IL+4％NH 2-SiO 2 | 86.529 | 0.23555 |
| HA-IL+5％NH 2-SiO 2 | 106.05 | 0.19219 |
| HA-IL+6％NH 2-SiO 2 | 84.651 | 0.24078 |
| HA-IL+7％NH 2-SiO 2 | 92.697 | 0.21988 |
| HA-IL+10％NH 2-SiO 2 | 98.567 | 0.20678 |
Fig. 2 is the NH of interpolation 5%
2-SiO
2electrolytical battery efficiency trend over time, as can be seen from Figure 2: along with the prolongation of time, the efficiency of battery remains unchanged substantially, illustrates and adds modification SiO
2the stability of rear battery obtains large increase.
Fig. 3 is the NH adding different content
2-SiO
2rear electrolytical gelation, from left to right, is followed successively by interpolation 0,5%, 8% and 10%, as can be seen from Figure 2: add modification SiO
2after, ionic liquid electrolyte becomes gel state from liquid state, and demonstrate battery efficiency in Fig. 2 further and substantially remain unchanged, stability test is greatly improved.
Embodiment 2, how cyanomodified Nano particles of silicon dioxide additive, electrolyte and the DSSC of preparation:
Prepare the method for how cyanomodified Nano particles of silicon dioxide additive with embodiment 1, only APTS is changed to 3-aminopropyl trimethoxysilane (CPTS), is labeled as CN-SiO
2.Prepare the method for nano-composite gel electrolyte and DSSC all with embodiment 1.
Embodiment 3, the Nano particles of silicon dioxide additive preparing polyamino and the common modification of cyano group, electrolyte and DSSC:
The method preparing the Nano particles of silicon dioxide additive of polyamino and the common modification of cyano group, with embodiment 1, only changes APTS into APTS and CPTS, and both mol ratios are 1:1, and both mole and be 0.3mol, be labeled as NH
2aMP.AMp.Amp CN-SiO
2.Prepare the method for nano-composite gel electrolyte and DSSC all with embodiment 1.
Embodiment 4, how carboxy-modified Nano particles of silicon dioxide additive, electrolyte and the DSSC of preparation:
At 30ml H
2sO
4with 30ml H
2cN-SiO prepared by 0.96g embodiment 2 is added in O
2, after stirred at ambient temperature 30min, reflux at 150 DEG C.And then with intermediate water centrifugal 4 times like this, revolve after steaming dewaters and dry 48h in baking oven (90 DEG C) is inner.How carboxy-modified Nano particles of silicon dioxide, be labeled as COOH-SiO
2.Prepare the method for nano-composite gel electrolyte and DSSC all with embodiment 1.
Embodiment 5, the Nano particles of silicon dioxide additive preparing polyamino and the common modification of carboxyl, electrolyte and DSSC:
At 30ml H
2sO
4with 30ml H
2nH prepared by 1.92g embodiment 3 is added in O
2aMP.AMp.Amp CN-SiO
2, after stirred at ambient temperature 30min, reflux at 150 DEG C.And then with intermediate water centrifugal 4 times like this, revolve after steaming dewaters and dry 48h in baking oven (90 DEG C) is inner.Obtain the Nano particles of silicon dioxide of polyamino and the common modification of carboxyl, be labeled as NH
2aMP.AMp.Amp COOH-SiO
2.Prepare the method for nano-composite gel electrolyte and DSSC all with embodiment 1.
Embodiment 6, the titanium dioxide nano-particle additive doped with Nb and Ru preparing polyamino modification, electrolyte and DSSC
First the titanium dioxide nano-particle doped with Nb and Ru is prepared: in beaker, add 120mL n-butanol, 20mL acetone, 10mL glacial acetic acid, 20mL butyl titanate, 0.7142g niobium chloride and 0.0609g ruthenium trichloride, electromagnetic agitation is even, is labeled as solution A; Then in another beaker, add the deionized water of 80mL n-butanol, the 2.4mL 30wt%PEG aqueous solution and 6mL, electromagnetic agitation is even, is labeled as solution B; Under constantly stirring, solution B is dropped in solution A by dropping funel uniform speed slow, dropwise rear continuation and stir 1h, then transfer them in autoclave, hydro-thermal reaction 6h at 240 DEG C, naturally cool to after room temperature until it, with cell disruptor ultrasonic disperse 30min.Finally steaming is revolved to reactant liquor, after being spin-dried for, namely obtain the titanium dioxide nano-particle doped with Nb and Ru.
Then carried out polyamino modification, method, as embodiment 1, obtains the titanium dioxide nano-particle additive doped with Nb and Ru of polyamino modification, then prepares electrolyte and DSSC by the method in embodiment 1.
Measure the DSSC photoelectric conversion efficiency of the functional nanoparticle based on different proportion prepared in embodiment 1-6, wherein, in each embodiment, the addition of functional nanoparticle is total electrolytical 1-20%.Test shows, modification SiO in embodiment 1-6
2mass fraction when being followed successively by 4%, 5%, 5%, 6%, 5%, 5% the photoelectric conversion efficiency of preparation-obtained DSSC as shown in table 2 below.
Corresponding test result is as follows: the test of battery performance be by from battery work electrode with two wires drawn to electrode receive on battery performance test device.The work area of battery is 0.2cm
-2, intensity of illumination is 100Mw/cm
2.Fill factor, curve factor (FF) refers to the product (I that can to obtain electric current on the point of peak power output and voltage in I-V curve
opt× V
opt) and I
scx V
oc(I
scfor short-circuit photocurrent, V
ocfor open-circuit photovoltage) ratio, it embodies the power output of battery with the variation characteristic of load.Photoelectric conversion efficiency (η) is then I
opt× V
optwith the luminous power P of input
inratio.
Fig. 4 surveys by embodiment 1-6 the photoelectricity I-V curve of the peak efficiency of DSSC, can learn: functional nanoparticle can not only make ionic liquid gel, also can significantly improve cell photoelectric performance simultaneously from Fig. 4.Corresponding data is as shown in table 2, illustrate that the DSSC of the electrolyte HA that with the addition of functional nanoparticle additive is compared with the fuel sensitization solar battery of pure electrolyte HA, except the open circuit voltage of embodiment 4 slightly declines, the short circuit current of other embodiments, open circuit voltage and fill factor, curve factor increase all to some extent, thus cause the photoelectric conversion efficiency of each embodiment all greatly to improve.
In table 2, embodiment 1-6 survey the photooptical data of DSSC
Claims (10)
1. a preparation method for functional nanoparticle, comprises the steps:
1) prepare prepolymer: in the presence of a catalyst, siloxane precursors and water are reacted, obtain prepolymer, wherein, described siloxane precursors is containing, for example at least one in lower functional group: amino, carboxyl, cyano group, nitrogen heterocyclic ring and sulfydryl;
2) prepare functional nanoparticle: under an inert atmosphere, described prepolymer and inorganic nano-particle are reacted in organic solvent, obtains functional nanoparticle.
2. preparation method according to claim 1, is characterized in that: step 1) in, the mol ratio of described siloxane precursors and water is (0.1-10): 1;
The mol ratio of described catalyst and water is 1:(300-10);
The reaction temperature of described reaction is 60-100 DEG C, and the reaction time is 1-2h.
3. preparation method according to claim 1 and 2, is characterized in that: step 1) in, described catalyst is alkali, and described alkali is selected from least one in calcium hydroxide, NaOH and potassium hydroxide;
Described siloxane precursors is selected from 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-cyanopropyl triethyl silicane, 3-cyano group trimethoxy silane, 3-mercaptopropyltriethoxysilane, 3-methoxyl group hydrosulphonyl silane, side chain contain at least one in nitrogenous heterocyclic polysiloxanes etc.;
Described reaction is the first stir process 24-36h at 20-30 DEG C by siloxane precursors and water, then adds catalyst wherein, and steams reaction 1-2h in 60-100 DEG C of backspin, and suction filtration obtains supernatant, is described prepolymer;
Described nitrogen heterocyclic ring is at least one in pyrroles, imidazoles and pyridine.
4. the preparation method according to any one of claim 1-3, is characterized in that: step 2) in, described inert atmosphere is N
2and/or Ar atmosphere;
Described inorganic nano-particle is selected from oxide and/or the oxide containing doped chemical, and described oxide is SiO
2and/or metal oxide, the described oxide containing doped chemical is the SiO of at least one in doping Nb, Ru, Mn, Ta and Si
2and/or metal oxide, described metal oxide is selected from TiO
2, ZnO and Al
2o
3in at least one;
The particle diameter of described inorganic nano-particle is 1-300nm;
The mass ratio of described prepolymer and inorganic nano-particle is 1:(0.1-1);
The reaction temperature of described reaction is 20-30 DEG C, and the reaction time is 36-48h;
Described organic solvent is at least one in toluene, benzene, dimethylbenzene and butyl toluene.
5. the preparation method according to any one of claim 1-4, is characterized in that: step 2) in, also comprise obtained functional nanoparticle is washed successively, dry step, step is as follows: use CH
2cl
2wash three times, then steam in 40-60 DEG C of backspin, after being spin-dried for, in the baking oven of 80-100 DEG C, dry 36-48h.
6. the preparation method according to any one of claim 1-5 and the functional nanoparticle obtained.
7. an electrolyte, comprises functional nanoparticle according to claim 6, electrolyte solvent and oxidation-reduction pair, and wherein, the mass fraction of described functional nanoparticle is 0.1%-60%, and the mass fraction of oxidation-reduction pair is 1%-20%.
8. electrolyte according to claim 7, is characterized in that: described electrolyte solvent is organic solvent and/or ionic liquid;
Wherein, described organic solvent is selected from least one in trimethoxy propionitrile, acetonitrile, ethylene carbonate and propene carbonate;
Described ionic liquid is selected from least one in 1-methyl-3-hexyl imidazolium iodine, 1-methyl-3-propyl imidazole iodine, 1-methyl-3-ethyl imidazol(e) iodine, 1-methyl-3-allyl imidazole iodine, 1-methyl-3-butyl imidazole iodine and 1,3-methylimidazole iodine;
Described oxidation-reduction pair is iodine and iodide ion oxidation-reduction pair, and described iodine and iodide ion oxidation-reduction pair are selected from I
2with containing iodine inorganic salts or I
2with containing iodide ion liquid, wherein, the described iodine inorganic salts that contain are selected from least one in LiI, KI and NaI, the described at least one be selected from containing iodide ion liquid in 1,3-methylimidazole iodine, 1-methyl-3-hexyl imidazolium iodine, 1-methyl-3-ethyl imidazol(e) iodine, 1-methyl-3-allyl imidazole iodine and 1-methyl-3-butyl imidazole iodine.
9. the electrolyte preparation method described in claim 7 or 8, comprise the steps: described functional nanoparticle, described electrolyte solvent and described oxidation-reduction pair to mix in described ratio, obtain based on the electrolyte of functional nanoparticle as additive.
10. functional nanoparticle according to claim 6 and/or the application of the electrolyte described in claim 7 or 8 in preparation DSSC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510279974.2A CN104867679B (en) | 2015-05-27 | 2015-05-27 | A kind of functional nanoparticle and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510279974.2A CN104867679B (en) | 2015-05-27 | 2015-05-27 | A kind of functional nanoparticle and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104867679A true CN104867679A (en) | 2015-08-26 |
| CN104867679B CN104867679B (en) | 2017-12-26 |
Family
ID=53913452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510279974.2A Active CN104867679B (en) | 2015-05-27 | 2015-05-27 | A kind of functional nanoparticle and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104867679B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105296459A (en) * | 2015-11-10 | 2016-02-03 | 河南工业大学 | Magnetic core-shell type ionic liquid immobilized lipase preparation method and application to edible oil processing |
| CN107163946A (en) * | 2017-07-18 | 2017-09-15 | 厦门世纳芯科技有限公司 | A kind of high temperature resistant hydrophobicity quantum dot fluorescence powder material preparation method |
| CN108097306A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of silica catalysis material of difunctionalization and its preparation and application |
| CN109232987A (en) * | 2017-07-11 | 2019-01-18 | 上海曦灵化工科技有限公司 | A kind of preparation method of silicon dioxide carried nanocomposite and plastic master batch |
| CN110010356A (en) * | 2018-02-15 | 2019-07-12 | 湖南辰砾新材料有限公司 | A kind of preparation method of high conductivity solid electrolyte |
| CN111224154A (en) * | 2020-02-17 | 2020-06-02 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN111653430A (en) * | 2020-04-28 | 2020-09-11 | 安徽诚越电子科技有限公司 | Electrolyte for high-sparking voltage high-conductivity aluminum electrolytic capacitor and aluminum electrolytic capacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791806A (en) * | 2010-01-28 | 2012-11-21 | 新加坡科技研究局 | A nano-composite |
| CN103013182A (en) * | 2012-12-06 | 2013-04-03 | 常州大学 | Surface modification method of nanosilicon dioxide |
| CN104312215A (en) * | 2014-09-22 | 2015-01-28 | 太原理工大学 | Silicon dioxide surface grafting modification method |
-
2015
- 2015-05-27 CN CN201510279974.2A patent/CN104867679B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102791806A (en) * | 2010-01-28 | 2012-11-21 | 新加坡科技研究局 | A nano-composite |
| CN103013182A (en) * | 2012-12-06 | 2013-04-03 | 常州大学 | Surface modification method of nanosilicon dioxide |
| CN104312215A (en) * | 2014-09-22 | 2015-01-28 | 太原理工大学 | Silicon dioxide surface grafting modification method |
Non-Patent Citations (1)
| Title |
|---|
| LIOZ ETGAR等: "Enhancing the open circuit voltage of dye sensitized solar cells by surface engineering of silica particles in a gel electrolyte", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105296459A (en) * | 2015-11-10 | 2016-02-03 | 河南工业大学 | Magnetic core-shell type ionic liquid immobilized lipase preparation method and application to edible oil processing |
| CN105296459B (en) * | 2015-11-10 | 2018-07-06 | 河南工业大学 | The preparation method of magnetic core-shell type ionic liquid immobilized lipase and the application in edible oil and fat processing |
| CN108097306A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of silica catalysis material of difunctionalization and its preparation and application |
| CN108097306B (en) * | 2016-11-24 | 2020-07-21 | 中国科学院大连化学物理研究所 | Dual-functionalized silicon oxide catalytic material and preparation and application thereof |
| CN109232987B (en) * | 2017-07-11 | 2021-02-05 | 上海曦灵化工科技有限公司 | Preparation method of silicon dioxide loaded nano composite material and plastic master batch |
| CN109232987A (en) * | 2017-07-11 | 2019-01-18 | 上海曦灵化工科技有限公司 | A kind of preparation method of silicon dioxide carried nanocomposite and plastic master batch |
| CN107163946B (en) * | 2017-07-18 | 2019-12-17 | 厦门世纳芯科技有限公司 | Preparation method of high-temperature-resistant hydrophobic quantum dot fluorescent powder material |
| CN107163946A (en) * | 2017-07-18 | 2017-09-15 | 厦门世纳芯科技有限公司 | A kind of high temperature resistant hydrophobicity quantum dot fluorescence powder material preparation method |
| CN110010356A (en) * | 2018-02-15 | 2019-07-12 | 湖南辰砾新材料有限公司 | A kind of preparation method of high conductivity solid electrolyte |
| CN110010356B (en) * | 2018-02-15 | 2021-06-29 | 湖南辰砾新材料有限公司 | Preparation method of high-conductivity solid electrolyte |
| CN111224154A (en) * | 2020-02-17 | 2020-06-02 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN111224154B (en) * | 2020-02-17 | 2021-09-10 | 中国科学院化学研究所 | Mesoporous nanoparticle gel composite electrolyte with lithium ion conduction and preparation method and application thereof |
| CN111653430A (en) * | 2020-04-28 | 2020-09-11 | 安徽诚越电子科技有限公司 | Electrolyte for high-sparking voltage high-conductivity aluminum electrolytic capacitor and aluminum electrolytic capacitor |
| CN111653430B (en) * | 2020-04-28 | 2021-10-08 | 安徽诚越电子科技有限公司 | Electrolyte for high-sparking voltage high-conductivity aluminum electrolytic capacitor and aluminum electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104867679B (en) | 2017-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104867679A (en) | Functional nanoparticle and preparation method and application thereof | |
| US7497975B2 (en) | Method for producing conductive polyaniline | |
| CN104332560B (en) | Preparation method of chlorine-bromine-iodine-mixing perovskite light absorption layer material | |
| Wang et al. | Study of H2SO4 concentration on properties of H2SO4 doped polyaniline counter electrodes for dye-sensitized solar cells | |
| CN104733716B (en) | Molybdenum oxide/nitrogen-doped carbon composite electrode material and preparation method thereof | |
| CN101669249B (en) | Photoelectrical cell, and coating agent for forming porous semiconductor film for the photoelectrical cell | |
| Wang et al. | Polymer-dispersed MWCNT gel electrolytes for high performance of dye-sensitized solar cells | |
| Shih et al. | Electropolymerized polyaniline/graphene nanoplatelet/multi-walled carbon nanotube composites as counter electrodes for high performance dye-sensitized solar cells | |
| Li et al. | Iodide‐free ionic liquid with dual redox couples for dye‐sensitized solar cells with high open‐circuit voltage | |
| Shah et al. | A stable gel electrolyte based on poly butyl acrylate (PBA)-co-poly acrylonitrile (PAN) for solid-state dye-sensitized solar cells | |
| TWI499062B (en) | Photoelectric conversion element | |
| Yuan et al. | Electropolymerization polyoxometalate (POM)-doped PEDOT film electrodes with mastoid microstructure and its application in dye-sensitized solar cells (DSSCs) | |
| Jin et al. | Enhancement in photovoltaic performance of phthalocyanine-sensitized solar cells by attapulgite nanoparticles | |
| CN110311039B (en) | Nb-tin dioxide nano precursor and method for preparing perovskite solar cell by using Nb-tin dioxide nano precursor as electron transport layer | |
| CN105830243A (en) | Dye-sensitized solar cell | |
| CN106058051A (en) | Preparation method of perovskite type solar cell modified by organic/inorganic hybrid hole transport layer | |
| CN107130256A (en) | Boron doping carbonitride modified titanic oxide complex light electrode and preparation method thereof, application | |
| US20130186465A1 (en) | Counter electrode for dye-sensitized solar cell and manufacturing method thereof | |
| Arof et al. | Utilization of saffron (Crocus sativus L.) as sensitizer in dye-sensitized solar cells (DSSCs) | |
| Anantharaj et al. | Interfacial modification of photoanode| electrolyte interface using oleic acid enhancing the efficiency of dye-sensitized solar cells | |
| CN110311043B (en) | Sb-tin dioxide nano precursor and method for preparing perovskite solar cell by using Sb-tin dioxide nano precursor as electron transport layer | |
| CN103069645B (en) | Electrolyte composition additive and employ electrolyte composition and the DSSC of this additive | |
| JP2007073346A (en) | Dye-sensitized solar cell | |
| Shit et al. | An insight into the hybrid dye-sensitized solar cell from polyaniline–CdS nanotubes through impedance spectroscopy | |
| CN104952625B (en) | The solid-state dye sensitized solar cell with long-time stability containing pyridined additives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |