CN107068407A - DSSC and its manufacture method - Google Patents
DSSC and its manufacture method Download PDFInfo
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- CN107068407A CN107068407A CN201710001827.8A CN201710001827A CN107068407A CN 107068407 A CN107068407 A CN 107068407A CN 201710001827 A CN201710001827 A CN 201710001827A CN 107068407 A CN107068407 A CN 107068407A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2045—Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of DSSC and its manufacture method.The DSSC of the present invention, includes a combined counter electrode, a working electrode and an electrolyte；Wherein, the combined counter electrode is comprising a platinum layer and as many as is arranged on the platinum layer wall carbon nanotube graphene complex layer.Because many wall carbon nanotube graphene complex layers have porous, electric transmission can be improved, the conversion efficiency of DSSC is lifted.
Description
Technical field
The present invention provides a kind of DSSC and its manufacture method, includes the compound electric with high conductance
Pole, it includes the composite layer of many wall carbon nanotube-graphenes, increases electron transmission to provide high response area, lifts light
Photoelectric transformation efficiency.
Background technology
The technology that DSSC actively develops for industry today, it is widely used in various electronics
In product, with environmental protection, low cost, be difficult to be influenceed by temperature in use, a variety of advantages such as pliability and the transparency.
DSSC primary structure is sequentially arranged two saturating comprising working electrode, electrolyte and to electrode
Between bright electrically-conductive backing plate.Wherein, photosensitizer (or photoinitiator dye) can convert light energy into electricity to be attached on working electrode
Energy.And how to be effectively increased photoelectric transformation efficiency and stability, then it is decided by the material and architectural characteristic of electrolyte and electrode.
Carbon nanotube and graphene are brand-new material in recent years, and it is " pure carbon " material, special with special construction and tool
Performance.Carbon nanotube is nm tubular-type, with good electrical, optical and hot etc., frequently as composite, bioid
Sensor and electronic equipment etc. are learned, a variety of different fields are widely used in.Graphene has two-dimensional structure, connects each other between its atom
Knot constitutes structure as honeycomb, conductive rich in having electronics in each interlayer free migration.That is, due to having the performance of conduction,
Carbon nanotube and graphene have been used in the field of solar cell, to aid in strengthening photoelectric transformation efficiency.
Although carbon nanotube and graphene have been used in solar cell, because of the characteristic of itself, photoelectricity is still caused to turn
Change efficiency problem of poor.Carbon nanotube has the situation generation for being difficult often to have in scattered characteristic, practice and easily reuniting, drop
The electron-transporting of the low interbed as electrode；And graphene also has similar situation, when it is with being used as the organic poly- of matrix
After compound mixing coating, easily produce storehouse each other and extrude, the effect that reduction electronics is transmitted by graphene hole.
The content of the invention
It is an object of the invention to provide a kind of many wall carbon nanotube-graphene complexes, it can be coated on dye sensitization
The interlayer of solar cell, forms a film layer；Many wall carbon nanotube-graphene complexes are modification carbon nanotube and modification
The composite of graphene, the film layer of its formation has porous, and then lifts DSSC.
That is, present inventor provides a kind of DSSC, comprising：One combined counter electrode, it includes a platinum
Layer and as many as it is arranged on the platinum layer wall carbon nanotube-graphene complex layer；On one working electrode, the wherein platinum layer
As many as wall carbon nanotube-graphene complex layer be located between the platinum layer and the working electrode；And an electrolyte, positioned at this
Between working electrode and the combined counter electrode.
In preferred embodiment, many wall carbon nanotube-graphene complex series of strata are by many wall carbon nanotubes and graphene
Modified after each acidified with the agent of silane even summation, and heat and formed after mixing.
In preferred embodiment, working electrode system TiO2、SnO2And ZnO.
The present invention provides the method that one kind prepares the combined counter electrode of above-mentioned used by dye sensitization solar battery, and it is wrapped
Contain：(a) platinum layer is provided；(b) by the carbon nanotube of wall more than one and a graphene it is each acidified after modified with the agent of silane even summation,
And mix, obtain a modification carbon nanotube-graphene slurries；And (c) by the modification carbon nanotube-graphene slurries coat to
After on the platinum layer, dry the modification carbon nanotube-graphene slurries obtain a porous modification carbon nanotube-graphene it is multiple
Compound layer is formed on the platinum layer, forms the combined counter electrode.
In preferred embodiment, the acidifying system is 9 using sulfuric acid and phosphoric acid:1 acidifying solution or nitric acid is carried out.
In preferred embodiment, as many as this is acidified, and wall carbon nanotube system is modified with amino silane.
In preferred embodiment, the amino silane is N- (2- amino-ethyls) -3- TSL 8330s.
In preferred embodiment, the acidified graphene system is modified with epoxy radicals silicone hydride.
In preferred embodiment, the epoxy radicals silicone hydride is (3- glycidoxypropyl groups) trimethoxy silane.
The present invention provides a kind of manufacture method of DSSC, comprising：(a) one is prepared in above-mentioned method
Combined counter electrode；(b) working electrode is provided, wherein the porous graphene layer be located at the platinum layer and the working electrode it
Between；And (c) provides an electrolyte between the working electrode and the combined counter electrode.
Brief description of the drawings
Fig. 1 is the DSSC of the present invention.
Fig. 2 is the combined counter electrode of the present invention.
Fig. 3 is the method for the combined counter electrode for preparing used by dye sensitization solar battery of the present invention.
Label declaration in figure：
1 combined counter electrode
3 modification carbon nanotubes-graphene complex layer
5 platinum layers
The 6 many wall carbon nanotubes of modification
7 modification graphenes
9 holes
11 adhesive agents
13 modification carbon nanotube-graphene slurries
15 electrically-conductive backing plates
17 working electrodes
19 electrolyte
Embodiment
The present invention provides a kind of DSSC, comprising：One combined counter electrode, its comprising a platinum layer and
As many as it is arranged on the platinum layer wall carbon nanotube-graphene complex layer；Wall as many as on one working electrode, the wherein platinum layer
Carbon nanotube-between graphene complex layer and the working electrode；And an electrolyte, positioned at the working electrode and this compound pair
Between electrode.As shown in figure 1, being provided with the DSSC of the present invention between two electrically-conductive backing plates 15, it is comprising compound
To electrode 1, electrolyte 19 and working electrode 17；Wherein, combined counter electrode 1 includes many wall carbon nanotubes-graphene complex layer 3
And platinum layer 5, and many wall carbon nanotubes-graphene complex layer 3 is the high reaction surface area of tool.
As many as above-mentioned wall carbon nanotube-graphene complex layer 3 includes modified many wall carbon nanotubes, modified graphene
Composite layer and adhesive agent are mixed, as shown in Fig. 2 the plural number modified many wall carbon nanotubes 6 and modified graphene 7 are
Overlap each other and attach on the platinum layer 5, its thickness is 1~50 μm, such as 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μ
M, 35 μm, 40 μm, 45 μm or 50 μm, the thickness of many wall carbon nanotube-graphene complexes are less than 1 μm, and how is many walls of the modification
Hole can not be produced to increase response area between rice carbon pipe and modification graphene, that is, can do nothing to help electric transmission.
The many wall carbon nanotubes of above-mentioned modification with silane even summation agent modification by being completed after acidified.Wherein, available for changing
The average grain diameter of many wall carbon nanotubes of matter is 10~40nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 35nm or 40nm.Should
Acidifying system uses acid solution, such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or the mixture it, and preferably uses sulfuric acid and phosphorus
Acidifying solution or the nitric acid progress of acid, sulfuric acid and phosphoric acid are 9 in the ratio of the acidifying solution:1~5:1, such as 9:1、8:1、7:1、6:1 or
5:1, and with 9:1 is optimal.Wherein, the acid solution of the acidifying include alcoholic compound, for example methanol, ethanol, isopropanol or its
Deng mixture, but be not limited to these.Wherein, the silane coupling agent is Ammonia silane coupling agent or epoxy radicals silicone hydride coupling agent etc.
General silane coupling agent, and be preferable using Ammonia silane coupling agent, but it is not limited to these.
Above-mentioned modification graphene with silane even summation agent modification by being completed after acidified.Wherein, available for modification graphite
0.02~10 μm of the length and width of alkene, thickness about 2~10nm, hole 1nm~10 μm and specific surface area 10m2/ g~1000m2/
g；Its length and width can be such as 0.02 μm, 1 μm, 3 μm, 5 μm, 7 μm or 10 μm；Its thickness can such as 2nm, 3nm, 4nm,
5nm, 6nm, 7nm, 8nm, 9nm or 10nm；Its hole can such as 1nm, 5nm, 10nm, 50nm, 100nm, 200nm, 300nm,
400nm、500nm、600nm、700nm、800nm、900nm、1000nm、1.5μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、
9 μm or 10 μm；Its specific surface area can such as 10m2/g、20m2/g、50m2/g、70m2/g、100m2/g、150m2/g、200m2/g、
250m2/g、300m2/g、350m2/g、400m2/g、450m2/g、500m2/g、550m2/g、600m2/g、650m2/g、700m2/g、
750m2/g、800m2/g、850m2/g、900m2/g、950m2/ g or 1000m2/g.Wherein, the acidifying system uses acid solution, example
Such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or its mixture, and preferably carried out using the acidifying solution or nitric acid of sulfuric acid and phosphoric acid,
Sulfuric acid and phosphoric acid are 9 in the ratio of the acidifying solution:1~5:1, such as 9:1、8:1、7:1、6:1 or 5:1, and with 9:1 is optimal.Its
In, the acid solution of the acidifying includes alcoholic compound, such as methanol, ethanol, isopropanol or the mixture it, but not limited to this
Deng.Wherein, the silane coupling agent is the general silane coupling agent such as Ammonia silane coupling agent or epoxy radicals silicone hydride coupling agent, and with ring
TMOS coupling agent is preferable, but is not limited to these.
Above-mentioned Ammonia silane coupling agent or epoxy radicals silicone hydride coupling agent include N-2 (amino-ethyl) 3- amino propyl methyls
Dimethoxysilane, N-2 (amino-ethyl) -3- TSL 8330s, N-2 (amino-ethyl) -3- aminopropyls three
Ethoxysilane, 3- TSL 8330s, APTES, the ethoxy silicon substrate-N- (1,3- of 3- tri-
Dimethyl-butylidene) propylamine, N- phenyl -3- TSL 8330s, N- (ethenybenzyl) -2- amino-ethyls -3-
The methoxy silane salt of aminopropyl three acid salt, 3- ureidopropyltriethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- sulfydryls
Hydroxypropyl methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane, tetra-sulfurized pair (three ethoxy silicon substrate propyl group), 3- isocyanic acids
Propyl ester triethoxysilane, imidizole silane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, (3- glycidyl epoxides
Propyl group) trimethoxy silane, glycidyl epoxide hydroxypropyl methyl diethoxy silane, glycidyl epoxide propyl-triethoxysilicane
Alkane, vinyltrimethoxy silane or VTES etc., and with N-2 (amino-ethyl) 3- amino propyl methyls two
Trimethoxy silane is preferable for methoxy silane or (3- glycidyl epoxides propyl group), but is not limited to these.
Above-mentioned adhesive agent be polyvinylidene fluoride (PVDF), cellulose or its etc. mixture.Due to gathering inclined difluoro second
Alkene (PVDF) and cellulose are the material for preparing perforated membrane, beneficial to forming mushy material.Sent out in addition, being tested through inventor
It is existing, compared to other compounds are used, using polyvinylidene fluoride (PVDF) or cellulose with modifying many wall carbon nanotubes and changing
When matter graphene is mixed, it can prepare with as many as multiple hole wall carbon nanotube-graphene complex layer, increase response area, with
Beneficial to electron transmission.Polyvinylidene fluoride (PVDF) and cellulose as during adhesive agent can mix and match other solvents use, example
Such as water, N- methyl -2- Pyrrolizidines ketone (NMP), dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide (DMAc), N, N- dimethyl formyls
Amine (DMF), methyl ethyl ketone, acetone, tetrahydrofuran, tetramethylurea, trimethyl phosphate, hexane, pentane, benzene, toluene, methanol,
The aliphatic hydrocarbons such as ethanol, carbon tetrachloride, o-dichlorobenzene, trichloro ethylene, the polyethylene glycol of low molecule amount, aromatic series carbonization
Hydrogen, chlorination hydrocarbon or other chlorination organic liquids etc..
Above-mentioned working electrode can be TiO2、ZnO、SnO2、Nb2O5、In2O3、CdS、ZnS、CdSe、GaP、CdTe、
MoSe2、WO3、KTaO3、ZrO2、SrTiO3、WSe2、SiO2, CdS or its combination, and with TiO2、SnO2And ZnO is preferred.In addition,
The working electrode is added with photosensitizer, and it includes organic metal misfit thing, such as organic ruthenium metal series or sclererythrin series, or
Indoles series, cumarin are serial, cyanine is serial or rhodamine organic dyestuff.
Above-mentioned electrolyte can be general electrolyte, and it includes liquid electrolyte, colloidal electrolyte or solid electrolyte.
Wherein, electrolyte system uses redox electrolyte, and redox ion is to Huo Qi etc. such as iodine, iron, tin, bromine, chromium, anthraquinone
Combination, preferably iodine system and bromine system electrolyte, such as KI, iodate dimethyl propyl imidazoles, lithium iodide or iodine it
Mixture.The electrolyte of the present invention comprising nitrile, amide-type, ethers, carbonic ester lactone or its etc. combination, such as acetonitrile, first
Epoxide acetonitrile, propionitrile, 3- methoxypropionitriles, benzonitrile, diethyl ether, 1,2- dimethoxy-ethanes, tetrahydrofuran, N, N- dimethyl
Formamide, DMAC N,N' dimethyl acetamide, ethylene carbonate, propylene carbonate, gamma-butyrolacton or gamma-valerolactone.In addition, gel
Shape electrolyte system, which utilizes, can add gelating agent, polymer etc. in electrolyte, gel-like electrolyte is presented；And solid electrolyte system
The polymer such as the electrolyte collocation polyethylene oxide derivant using oxidation-reduction quality.
The present invention provides the method that one kind prepares the combined counter electrode of above-mentioned used by dye sensitization solar battery, and it is wrapped
Contain：(a) platinum layer is provided；(b) by the carbon nanotube of wall more than one and a graphene it is each acidified after modified with the agent of silane even summation,
And mix, obtain a modification carbon nanotube-graphene slurries；And (c) by the modification carbon nanotube-graphene slurries coat to
After on the platinum layer, dry the modification carbon nanotube-graphene slurries obtain a porous modification carbon nanotube-graphene it is multiple
Compound layer is formed on the platinum layer, forms the combined counter electrode.As shown in figure 3, a plurality of modify many wall carbon nanotubes 6 and change
Matter graphene 7 is placed in adhesive agent 11 and is mixed to form modification carbon nanotube-graphene slurries 13, the modification carbon nanotube-graphite
Alkene slurries 13 are coated to platinum layer 5, and drying forms modification carbon nanotube-graphene complex layer 3 of porous.
In above-mentioned step (b), many wall carbon nanotubes and the graphene are as many as modification use same as above wall nm
Carbon pipe and graphene, and in before acidifying and modification can first purified processing, to remove impurity, general purifying side can be used in it
Method, such as acidic treatment or chromatography；Wherein, it is preferable, this side to carry out acidic treatment using the mixed liquor using sulfuric acid and nitric acid
Method can obtain more as many as clean wall carbon nanotube and graphene, and its surface can be made to have hydroxyl and carboxyl, beneficial to being changed
Matter.The temperature and time of the acidifying and modification be 60~120 DEG C and 30~80 points, such as 60 DEG C of the temperature, 70 DEG C, 80 DEG C, 90
DEG C, 100 DEG C, 110 DEG C or 120 DEG C, such as 30 points, 40 points, 50 points, 60 points, 70 points or 80 points of the time.The hybrid mode can make
It is preferable with ultrasonic mixing with ultrasonic mixing or mixer, but not limited to this.In the modification carbon nanotube-graphene slurries,
The ratio of many wall carbon nanotubes of the modification and the modification graphene is 6:1~1:6, such as 6:1、4:1、2:1、1:1、1:2、1:4
Or 1:6；It is relative to the modification carbon nanotube-graphene slurries overall, many wall carbon nanotubes of the modification and the modification graphene
Concentration be 0.01~10wt%, 0.01wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%,
8wt%, 9wt% or 10wt%, if it is less than 0.01wt%；If concentration is less than 0.01wt%, density can be made too low, it is difficult to raw
Into hole, if concentration is higher than 10wt%, the density that many wall carbon nanotubes of modification and modification graphene are overlapped each other can be too high, graphite
Alkene may produce storehouse phenomenon, also be difficult to produce hole, therefore density is too high or too low can reduce electric transmission, and then influence
Photoelectric transformation efficiency.
In above-mentioned step (c), the coating is applied comprising rotary coating, slot coated, curtain coating coating, roll-type coating, bar type
Cover or ink-jet coating, but be not limited to these, and coating machine can be used to include roller knife coating machine, rotogravure application machine, pressing mold coating machine,
But it is not limited to these；The drying temperature and time are respectively 100~500 DEG C and 10~60 minutes, such as 100 DEG C of temperature, 150
DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, such as 10 points, 20 points, 30 points, 40 points, 50 points of time
Or 60 points.
The present invention provides a kind of manufacture method of DSSC, comprising：(a) one is prepared in above-mentioned method
Combined counter electrode；(b) working electrode is provided, wherein the porous graphene layer be located at the platinum layer and the working electrode it
Between；And (c) provides an electrolyte between the working electrode and the combined counter electrode.
The dye-sensitized cell of the present invention is due to the combined counter electrode with high J response areas, therefore lifting electron transmission,
And then increase photoelectric transformation efficiency.
[specific embodiment]
Hereinafter, disclosed content will especially be described using specific embodiment.However, disclosed
Content be not restricted to following example.
(acidifying solution is sulfuric acid and phosphoric acid ratio 9 for the preparation example 1- many wall carbon nanotubes of preparation modification and modification graphene:1)
1. many wall carbon nanotubes of modification：The many wall carbon nanotubes of 8g (10~50nm of average grain diameter, 1~25um of length) are inserted
In mixed acid (20% nitric acid and 20% sulfuric acid volume ratio 1:3) heating stirring 60 minutes under 100 degree, are filtered and with deionized water
100 degree of lower drying after cleaning is neutrality to pH, to complete the purifying of many wall carbon nanotubes.Then, by many wall nms after purification
Carbon pipe is placed in containing _ 400__mL acidifying solutions (sulfuric acid and phosphoric acid ratio 9:1), in mistake after 50 degree of lower heating stirrings 120 minutes
Filter, is cleaned to pH to be neutral after 105 degree of lower drying using deionized water.Further take above-mentioned 5g be acidified many wall carbon nanotubes in
It is scattered with ultrasonic vibrating during 200ml tetrahydrochysene fluorine is muttered, it is slowly added to0.3gN-2 (amino-ethyl) -3- aminopropyl trimethoxies
Base silane, filters after 60 minutes in 60 degree of lower heating stirrings, reuses deionized water and clean to pH to be neutral after 105 degree lower bakings
It is dry.
2. modify graphene：By 3g graphenes (about 5 μm of length and width；Thickness about 2~10nm；Specific surface area 20~
40m2/ g) it is placed in acidifying solution (20% nitric acid and 20% sulfuric acid volume ratio 1:3) heating stirring 60 minutes under 100 degree, filtering
And 105 degree of lower drying after being cleaned using deionized water to pH to be neutral, to complete the purifying of graphene.Then, it is many by after purification
Wall carbon nanotube is placed in containing _ 400__mL acidifying solutions (sulfuric acid and phosphoric acid ratio 9:1), in heating stirring 120 minutes under 50 degree
After filter, cleaned using deionized water to pH to be neutral after 105 degree lower drying.Further take above-mentioned 3g acidifying graphites alkene in
It is scattered with ultrasonic vibrating during 200ml tetrahydrochysene fluorine is muttered, it is slowly added to0.3g(3- glycidoxypropyl groups) trimethoxy silane,
Filtered in 60 degree of lower heating stirrings after 60 minutes, reuse deionized water and clean to pH to be neutral after 105 degree lower drying.
(acidifying solution is sulfuric acid and phosphoric acid ratio 7 for the preparation example 2- many wall carbon nanotubes of preparation modification and modification graphene:1)
Manufacture method be the same as Example 1, it using sulfuric acid and phosphoric acid ratio is 7 that difference, which is that acidifying solution is,:1.
(acidifying solution is sulfuric acid and phosphoric acid ratio 5 for the preparation example 3- many wall carbon nanotubes of preparation modification and modification graphene:1)
Manufacture method be the same as Example 1, it using sulfuric acid and phosphoric acid ratio is 5 that difference, which is that acidifying solution is,:1.
Preparation example 4- prepares many wall carbon nanotubes of modification and modification graphene (acidifying solution is nitric acid)
Manufacture method be the same as Example 1, difference is that acidifying solution is nitric acid.
Compare preparation example 1- to prepare many wall carbon nanotubes of modification and modification graphene (acidifying solution is sulfuric acid and nitric acid ratio 3:
1)
Manufacture method be the same as Example 1, it using sulfuric acid and nitric acid ratio is 3 that difference, which is that acidifying solution is,:1.
Preparation example 5 is to 8- combined counter electrodes 1 to 4
By many wall carbon nanotubes of the modification of embodiment 1 to 4 and modification graphene respectively with quality point 1:1 is placed in poly- inclined two
In PVF (PVDF), formed modification carbon nanotube-graphene slurries make many wall carbon nanotubes of modification and modified graphene
Concentration be 10wt%, and ultrasonic vibrating is uniformly after mixing 60 minutes, using spin coater by the modification carbon nanotube-stone
Black alkene slurries are coated to about 100 μm of platinum layers of thickness, form about 10 μm of many wall carbon nanotubes of modification of thickness and modification graphite
Olefinic substance layer, in being dried at temperature 100 DEG C 60 minutes, forms combined counter electrode 1 to 4 respectively.
Compare preparation example 2- and compare combined counter electrode 1
Prepared using the preparation method of be the same as Example 5 and compare combined counter electrode 1, difference is to modify carbon nanotube-graphite
Alkene slurries system uses many wall carbon nanotubes of the modification for comparing preparation example 1 and modification graphene.
Embodiment 1 to the 4- present invention DSSC 1 to 4
Encapsulated respectively using preparation example 5 to 8 to being set between electrode and working electrode (strong ancient cooking vessel science and technology Tripod tech)
Film, after packaging by hot pressing, electrolyte (photochemistry, colloidal state electrolyte EL-300 forever) is injected, dye sensitization of solar is formed
Battery 1 to 4, the effect test result difference of its grade is as shown in table 1.
Comparative example 1- comparative example DSSCs
To compare respectively preparation example 2 between electrode, platinum layer and a working electrode (strong ancient cooking vessel science and technology Tripod tech)
Encapsulating film is set, after packaging by hot pressing, electrolyte (photochemistry, colloidal state electrolyte EL-300 forever) is injected, comparative example is formed
DSSC, its effect test result difference is as shown in table 1.
Table 1
Claims (10)
1. a kind of DSSC, it is characterised in that include：
One combined counter electrode, comprising a platinum layer and as many as is arranged on the platinum layer wall carbon nanotube-graphene complex
Layer；
One working electrode, wherein many wall carbon nanotubes-graphene complex layer are located between the platinum layer and the working electrode；
And
One electrolyte, between the working electrode and the combined counter electrode.
2. DSSC according to claim 1, it is characterised in that：Many wall carbon nanotube-graphenes
Compound series of strata by many wall carbon nanotubes and graphene it is each acidified after modified with the agent of silane even summation, and heating institute shape after mixing
Into.
3. DSSC according to claim 1, it is characterised in that：Working electrode system TiO2、SnO2And
ZnO。
4. a kind of method for the combined counter electrode for preparing used by dye sensitization solar battery as claimed in claim 1, its feature exists
In comprising：
(a) platinum layer is provided；
(b) by the carbon nanotube of wall more than one and a graphene it is each acidified after modified with the agent of silane even summation, and mix, changed
Matter carbon nanotube-graphene slurries；And
(c) after the modification carbon nanotube-graphene slurries are coated to the platinum layer, the modification carbon nanotube-graphite is dried
Modification carbon nanotube-graphene complex layer that alkene slurries obtain a porous is formed on the platinum layer, forms this compound pair
Electrode.
5. method according to claim 4, it is characterised in that：The acidifying system is 9 using sulfuric acid and phosphoric acid:1 acidifying solution
Or nitric acid is carried out.
6. the method according to claim 4 or 5, it is characterised in that：As many as the acidified wall carbon nanotube system is with amino silicone
Alkane is modified.
7. method according to claim 6, it is characterised in that：The amino silane is N- (2- amino-ethyls) -3- amino
Propyl trimethoxy silicane.
8. the method according to claim 4 or 5, it is characterised in that：The acidified graphene system is changed with epoxy radicals silicone hydride
Matter.
9. method according to claim 8, it is characterised in that：The epoxy radicals silicone hydride is (3- glycidoxypropyl groups) front three
TMOS.
10. a kind of manufacture method of DSSC, comprising：
(a) combined counter electrode is prepared in the method for any one of claim 4 to 9；
(b) working electrode is provided, wherein many wall carbon nanotubes-graphene complex layer is located at the platinum layer and work electricity
Between pole；And
(c) electrolyte is provided between the working electrode and the combined counter electrode.
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