CN106299130A - Low resistance electrode, preparation method and the application on carbon back perovskite solaode thereof - Google Patents
Low resistance electrode, preparation method and the application on carbon back perovskite solaode thereof Download PDFInfo
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Abstract
The present invention relates to a kind of low resistance electrode, preparation method and the application on carbon back perovskite solaode thereof, this electrode is to be referred to by plane carbon-coating and carbon or two-layer compound carbon-coating structure that carbon web frame layer is constituted, described plane carbon-coating is planar structure, and described carbon refers to or carbon web frame layer is that carbon refers to or carbon web frame；Described carbon refers to or carbon web frame layer is arranged on plane carbon-coating, and its coverage rate is less than 80%.Preparation method includes: prepared by (1) low resistance carbon pastes；(2) working curve between carbon layers having thicknesses and sheet resistance is set up；(3) suitable depth of two-layer compound carbon-coating structure is determined；(4) preparation of plane carbon-coating；(5) low resistance carbon refers to or the preparation of carbon web frame layer.Low resistance electrode is used in without on the carbon back perovskite solaode in hole.Compared with prior art, the present invention has and improves the photoelectric transformation efficiency of battery, improves the advantages such as the stability of battery, low cost, technique are simple.
Description
Technical field
The present invention relates to a kind of low resistance electrode, especially relate to a kind of low resistance carbon and refer to or carbon net electrode, preparation method
And the application on carbon back perovskite solaode.
Background technology
In recent years, the fashionable whole world of research of a new generation's perovskite solaode, its certifying authority is the highest at present
Battery efficiency has broken through 22%, exceedes the efficiency of conventional films solaode.Compared with other type of solaode,
This kind of battery also has unrivaled advantage, and such as material source convenience, processing technology is simple, equipment requirements is the highest and battery
Low cost etc..These features illustrate that perovskite solaode is expected to become the generation of a new generation's solaode most industrialization
Table.
Perovskite solaode is the class all solid state solaode with perovskite as photosensitizer.According to back electrode
Difference, it can be divided into Metal Substrate perovskite solaode and carbon back perovskite solaode, wherein, carbon back perovskite
Solaode, according to the feature with or without hole transmission layer, can be divided into again the carbon back perovskite solar energy without hole transmission layer
Battery and the carbon back perovskite solaode having hole transmission layer.Compared with Metal Substrate perovskite solaode, carbon back calcium
Titanium ore solaode is owing to being not related to noble metal and the processing technology thereof of costliness, and therefore its cost is cheaper with technique more
Simply.It addition, compared with the carbon back perovskite solaode having hole transmission layer, without hole transmission layer carbon back perovskite too
Sun energy battery is not only without hole transmission layer, and Fabrication Technology of Electrode is only with printing technology with low cost, it is to avoid adopt
By the spin coating technique being difficult to industrialized production required for the carbon back perovskite solaode having a hole transmission layer, therefore its work
Industry development prospect is more good.
Carbon electrode is the back electrode of the carbon back perovskite solaode without hole transmission layer, and it is not only the important of battery
Ingredient, but also carry hole transport and constitute the effect of electronic loop.Therefore, the performance of carbon electrode can shadow greatly
Ring the performance of battery.The performance of the carbon electrode investigating the carbon back perovskite solaode without hole transmission layer is the most fine or not main
Showing two aspects, one is the thickness of carbon electrode layer；Two is the surface resistance of carbon electrode layer.Wherein, the thickness of carbon electrode layer
Perfusion with perovskite precursor solution is relevant, and the thickest carbon electrode layer certainly will affect the perfusion effect of perovskite precursor solution
Rate, therefore, the thickness of rational carbon electrode layer is suitable thinner, but can not be the thickest；The surface resistance of carbon electrode layer and the material of carbon electrode layer
Expecting relevant with thickness, for the carbon electrode layer material determined, the surface resistance of carbon electrode layer is as the thickness of carbon electrode layer
Increase and reduce, and variation tendency is first big after small, finally tends towards stability.Visible, thickness and the surface resistance of carbon electrode layer are
Conflict body, wants to obtain excellent carbon electrode performance, is necessary for the thickness to carbon electrode layer and surface resistance carries out the most excellent
Change.It is effectively reduced the thickness of carbon electrode and surface resistance is the prior development direction of this kind of solar cell.But, we send out in investigation
Existing, the research of current most carbon electrode mainly concentrates in little area cells, and focus on optimizing material composition and
On the thickness of carbon electrode, thus obtain rational result.And in area battery, although also having been reported that, but its way and
Little area cells is the same.Compared with little area cells, area battery, along with carbon electrode area increases, the internal resistance of cell increases, empty
In the transmitting procedure of cave, energy loss is big, and the photoelectric transformation efficiency of battery will be substantially reduced.In order to reduce in battery to greatest extent
The increase of resistance, area battery is necessary carbon electrodes is carried out low resistance modification.That merely use little area
The technology of battery is the most infeasible for area battery.Undoubtedly, above-mentioned deficiency will limit the further of this kind of battery
Promote and the process of industrialization development.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of low resistance electrode, system are provided
Method and the application on carbon back perovskite solaode thereof.
The purpose of the present invention can be achieved through the following technical solutions: a kind of low resistance electrode, it is characterised in that this electricity
Pole is to be referred to by plane carbon-coating and carbon or two-layer compound carbon-coating structure that carbon web frame layer is constituted, and described plane carbon-coating is planar junction
Structure, described carbon refers to or carbon web frame layer is that carbon refers to or carbon web frame；Described carbon refers to or carbon web frame layer is arranged on planar carbon
On layer, its coverage rate is less than 80%.Compared with the surface resistance of single plane carbon-coating, two-layer compound carbon-coating structure is due to flat
Introduce carbon on the carbon-coating of face to refer to or carbon web frame layer, thus there is bigger thickness, therefore can have lower surface resistance.Pass through
These low-resistance carbon refer to or the effect of carbon web frame layer, and the surface resistance of planar carbon layer can be made to be effectively reduced, thus
Decrease the energy loss during electronics or hole transport, whole electronic loop plays low-resistance effect.
In inverse ratio between carbon layers having thicknesses and the carbon-coating sheet resistance of described electrode, refer to along with the increase of carbon layers having thicknesses, carbon
The sheet resistance of layer reduces on the contrary, and the trend of minimizing is rear slow, finally trends towards stationary value.The thickness of plane carbon-coating selects
It is positioned at the thickness that carbon-coating sheet resistance reduces rapidly along with the increase of carbon layers having thicknesses, in the range of preferred thickness is a thickness area
Arbitrary value；Carbon refers to or the thickness of carbon web frame layer selects to be positioned at carbon-coating sheet resistance and reduces trend along with the increase of carbon layers having thicknesses and open
Beginning to trend towards the thickness of stationary value, preferred thickness is the arbitrary value of a thickness area scope；The thickness of described plane carbon-coating
Degree is 5-20 micron；Described carbon refers to or the thickness of carbon web frame layer is 30-100 micron.
The thickness of described plane carbon-coating is 10 microns；Described carbon refers to or the thickness of carbon web frame layer is 30-50 micron.
Described carbon refers to or the thickness of carbon web frame layer, if thickness is too small, carbon refers to or the resistance peace of carbon web frame layer
The resistance of face carbon-coating is more or less the same, and low resistance performance is the best；If thickness is excessive, carbon refer to or carbon web frame layer thickness too
Thickness, little to the effect of low resistance performance, but also the adverse influences such as film layer cracking easily occur.
Described carbon refers to or carbon web frame layer refers to that structure sheaf is that carbon refers to layer, or carbon stratum reticulare, and wherein carbon refers to that layer refers to by n bar
Carbon refers to the carbon-coating structure of composition, and n >=2, carbon refers to the carbon-coating structure for similar finger shape, and carbon refers to one end open, and the other end is mutual
Connecting, both sides are straight line or curve；The shape that carbon refers to includes that single carbon refers to or many carbon refers to；
Described carbon stratum reticulare is the carbon-coating structure of similar mesh shape, and quantity n >=1 of grid, as n=1, for single grid
Carbon net, when n >=2, for many grids carbon net, many grids carbon net includes closing structure or hatch frame, and closing structure is that carbon net is complete
Portion is made up of the grid closed, and hatch frame is that to be that the grid that referred to by carbon and close is compound constituted carbon net；The line constituting grid is
Straight line or curve；The shape of carbon net includes single grid carbon net, vertical-shaped many grids carbon net, horizontal shape many grids carbon net, hands over the many grids of shape
Carbon net and many grids list carbon refer to that composite carbon net and the many carbon of many grids refer to any one of composite carbon net or several.
The line width scope that described carbon refers to is 0.2mm-2mm, and line thickness is more than or equal to 5 microns；Carbon finger widths a is less than
Or the width of the carbon-coating equal to Tan Zhi lower floor, carbon refers to the length that length b is the carbon-coating being less than or equal to or being more than Tan Zhi lower floor；
The line width scope of described carbon net is 0.5mm-5mm, and line thickness is more than or equal to 10 microns, the overall width of carbon net
C less than or equal to the width of carbon-coating of carbon side off the net, Gridding length d less than or equal to or the length of carbon-coating more than carbon side off the net
Degree.
The line width scope that described carbon refers to is 0.5-1mm, and line thickness is 10-50 micron；The line width of described carbon net
Scope is 1-3mm, and line thickness is 15-50 micron.
The preparation method of a kind of low resistance electrode, it is characterised in that comprise the following steps:
(1) prepared by low resistance carbon pastes；
Graphite, white carbon black, inorganic oxide, organic thickening agent and solvent are mixed, uses ball milling or three roller methods to make carbon
Slurry, described graphite and the weight ratio of white carbon black are 1-10:1, and in described carbon slurry, graphite and the solid content shared by white carbon black are 10-
60wt%, the solid content shared by inorganic oxide is 1-10wt%, and the solid content shared by organic thickening agent is 1-10wt%；
(2) working curve between carbon layers having thicknesses and sheet resistance is set up
Step (1) gained carbon pastes is made carbon-coating by method for printing screen, knife coating or spraying process, then in 350-
500 DEG C sinter 10-60 minute, measure the resistance of carbon-coating with four probe instrument or ohmmeter, set up carbon layers having thicknesses and side
Working curve between resistance；The thickness of described carbon-coating is controlled by the number of times of printing or blade coating or spraying；
(3) suitable depth of two-layer compound carbon-coating structure is determined
According to step (2) gained working curve, select to be positioned at carbon-coating sheet resistance and reduce rapidly along with the increase of carbon layers having thicknesses
Thickness as the thickness of plane carbon-coating；Select be positioned at carbon-coating sheet resistance reduce along with the increase of carbon layers having thicknesses trend start tend to
Thickness in stationary value refers to or the thickness of carbon web frame layer as carbon；
(4) preparation of plane carbon-coating
Method for printing screen, knife coating or spraying process is used to make step (3) determined thickness plane carbon-coating, and in 350-
500 DEG C sinter 10-60 minute；
(5) low resistance carbon refers to or the preparation of carbon web frame layer
Design carbon refers to or the shape and size of carbon net as required, on step (4) gained plane carbon-coating, uses screen printing
Brush method, knife coating or spraying process are made the carbon of step (3) determined thickness and are referred to or carbon net, and sinter 10-60 in 350-500 DEG C
Minute, obtain low resistance electrode.
In step (1) described carbon slurry, graphite and the solid content shared by white carbon black are 25-35wt%, shared by its inorganic oxide
Solid content is 2-5wt%, and the solid content shared by its organic thickening agent is 2-5wt%；The nanometer particle size of described white carbon black is less than 50
Nanometer；Described graphite is graphite flake or graphite nodule；Described white carbon black is nano carbon black, and nanometer particle size is less than 100 nanometers, preferably
For less than 50 nanometers；Described graphite and the weight ratio of white carbon black are 1-5:1；Described inorganic oxide be titanium oxide, zirconium oxide,
Aluminium oxide or silicon oxide；Described organic thickening agent is cellulose or hydroxypropyl cellulose；Described solvent is water, ethanol, pine
One or more in oleyl alcohol, isopropanol, glycerol.
Sintering temperature described in step (1) and (4) and (5) is 400-450 DEG C, and sintering time is 15-45 minute；
Step (4) makes the raw material of plane carbon-coating and uses step (1) gained carbon pastes, or ready-made carbon refers to or carbon web material
Material, or ready-made carbon refers to or the mixing material of carbon net materials and step (1) described carbon pastes.
Step (5) gained low resistance electrode use four probe instrument or ohmmeter test plane carbon-coating and carbon refers to or
The sheet resistance of carbon web frame layer, plane carbon-coating and carbon refers to or difference between the resistance of carbon web frame layer, and difference is the biggest, low-resistance
Performance is the best.
The application of a kind of low resistance electrode, it is characterised in that low resistance electrode is used in the carbon back perovskite without hole too
On sun energy battery, the especially carbon electrode of area battery.The low resistance electrode of the present invention is used in the carbon back perovskite without hole
On solaode, can effectively reduce the surface resistance of carbon electrode layer, reduce the energy during hole transport and electronic loop
Loss.Further, since the carbon on plane carbon-coating refers to or carbon net is to use lines or the form of grid, do not interfere with calcium titanium the most yet
The ore deposit precursor solution osmotic efficiency by carbon electrode layer, thus improve the photoelectric transformation efficiency of battery.
In order to realize the purposes of above-mentioned low resistance electrode, have employed following concrete steps:
(1) conductive substrates processes
Employing electro-conductive glass is conductive substrates, carries out substrate etching, substrate washing and drying treatment successively；Described substrate
Etching mainly laser ablation, or chemical etching；Described substrate is cleaned and is mainly solvent clean or ozone clean or ultralow temperature
Carbon dioxide cleans, and drying means is heat drying；
(2) compacted zone makes
Nano-oxide compacted zone is made by spin-coating method or spray pyrolysis in step (1) gained conductive substrates surface；
Described dense layer thickness is less than 100 nanometers, and preferred thickness is 30-50 nanometer.
Described nano-oxide is mainly titanium oxide；
Described spin-coating method is exactly to use nano-oxide spin coating liquid to prepare under certain rotary speed on spin coating instrument
Form ultra-thin oxide membranous layer, and obtain through high temperature sintering；Described rotary speed is 500-8000rpm, preferably turns
Speed is 2000-5000rpm；Described high temperature sintering temperature is 400-600 DEG C, and preferred temperature is 500-550 DEG C；Described burning
The knot time is 15-120 minute, preferably 30-90 minute.
Described spray pyrolysis is the conductive base using aerosol apparatus to be sprayed in the thermal station of high temperature by titanium source precursor solution
, titanium source presoma is decomposed to form rapidly nano-oxide compacted zone under the effect of high temperature at the end.
Described titanium source precursor solution is mainly the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl ester, described
The temperature of high temperature sintering be generally 400-600 DEG C, preferred temperature is 500-550 DEG C.
(3) mesoporous layer makes
Web plate adds appropriate nano-oxide slurry, uses scraper on the surface of step (2) gained compacted zone
Printing and formed and have certain thickness mesoporous layer, this mesoporous layer forms stable mesoporous Rotating fields after high temperature sintering；Institute
The mesoporous layer thickness stated is 1-5 micron, preferably less than 1-3 micron.
Described nano-oxide slurry is mainly nano-titanium oxide slurry, nanometer alumina slurry, preferably nanometer
The 18NR-T slurry of titanium oxide or 30NR-D slurry；The high temperature sintering temperature of described mesoporous layer is generally 400-600 DEG C, preferably
Temperature be 500-550 DEG C.
(4) insulating barrier makes
Web plate adds appropriate nano-oxide slurry, uses scraper on the surface of the mesoporous layer of step (3) gained
Printing and formed and have certain thickness insulating barrier, this insulating barrier forms stable insulated hole Rotating fields after high temperature sintering,
Described thickness of insulating layer is 1-5 micron, preferably less than 1-3 micron.
Described nano-oxide slurry is mainly nano zircite slurry, nanometer alumina slurry, nano silicon oxide slurry
Material, preferably nano zircite slurry；Described nano zircite slurry, its particle diameter is 20-100 nanometer, preferred particle diameter
For 20-50 micron；The high temperature sintering temperature of described insulating barrier is generally 400-600 DEG C, and preferred temperature is 500-550 DEG C.
(5) planar carbon electrode layer makes
In step (4) gained surface of insulating layer, the method using aforesaid plane carbon-coating, make plane carbon-coating；Planar carbon
The thickness of electrode layer is generally 5-20 micron, and preferred thickness is 10 microns.
(6) carbon refers to or carbon web frame layer makes
Refer to aforesaid carbon or the method for carbon web frame layer.Described carbon refers to or the thickness of carbon web frame layer is generally 30-
100 microns, preferred thickness is 30-50 micron.Described carbon refers to or one end of carbon web frame layer is positioned at the outside of plane carbon-coating,
Contacting with conductive substrates, the other end is positioned in planar carbon electrode layer surface, contacts with planar carbon electrode layer.
(7) absorption of perovskite precursor solution
Using two-step method or one-step method to carry out the absorption of perovskite precursor solution, described two-step method is first will be certain
The lead iodide solution of amount refers to from carbon or instills and penetrate in mesoporous layer or insulating barrier carbon web frame layer, heats and make at 70 DEG C
Solvent volatilizees, and then the electrode of absorption lead iodide is immersed in several minutes in methylamine iodine solution, takes out juxtaposition after black is formed
In the thermal station of 50 DEG C, add heat extraction solvent, form perovskite battery；
Described one-step method is for refer to a certain amount of methylamine lead iodine precursor solution from carbon or to instill also carbon web frame layer
Penetrating in mesoporous layer or insulating barrier, then at 100 DEG C, heating makes solvent volatilize, and forms perovskite battery.
Described lead iodide solution, its consumption is generally micro updating or milliliter level, preferably micro updating；Its solvent is main
For dimethylformamide, dimethyl sulfoxide, butyrolactone or their mixed solvent；Its concentration is generally 0.5-1.5 mol/L,
Preferably concentration is 1 mol/L.
The solution of described first ammonia iodine, its consumption is generally submergence electrode；Its solvent be mainly isopropanol, ethanol or
Their mixed solvent；Its concentration is generally 5-15 mg/ml, and preferred concentration is 10 mg/ml.
Described methylamine lead iodine precursor solution, its consumption is generally micro updating or milliliter level, preferably micro updating；Its
Solvent is mainly dimethylformamide, dimethyl sulfoxide, butyrolactone or their mixed solvent；Its concentration is generally 0.5-1.5
Mol/L, preferred concentration is 1 mol/L.
(8) battery performance test
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).
Compared with prior art, the invention have the advantages that
1. what the technology of the present invention related to comprise carbon refers to or the low resistance electrode of carbon web frame layer, can effectively reduce carbon back
The surface resistance of the carbon electrode layer of perovskite solaode, reduces the energy loss during hole transport and electronic loop, from
And improve the photoelectric transformation efficiency of battery；
2. what the technology of the present invention related to comprise carbon refers to or the low resistance electrode of carbon web frame layer, owing to its structure is to use
Lines or the form of grid, do not interfere with the perovskite precursor solution osmotic efficiency by carbon electrode layer the most yet；
3. what the technology of the present invention related to comprise carbon refers to or the low resistance electrode of carbon web frame layer, both may be used for little area
Battery, it is also possible to for area battery；
4. what the technology of the present invention related to comprise carbon refers to or the low resistance electrode of carbon web frame layer, lower cost for material, system
Make technique simple, both can be suitable for laboratory and prepare, it is also possible to produce for bulk industrial；
5. what the technology of the present invention related to comprise carbon refers to or the low resistance electrode of carbon web frame layer, uses stable carbon material
Expect, and other electrode material will not occur any reaction or corrosion, be conducive to improving the stability of battery.
Accompanying drawing explanation
Fig. 1 is the graph of a relation between the carbon layers having thicknesses of certain carbon pastes and carbon-coating sheet resistance；
Fig. 2 is the structural representation that carbon refers to, in figure, a is carbon finger widths；B is that carbon refers to length；E is adjacent finger distance between centers of tracks；
Fig. 3 is two-layer compound carbon-coating structure sheaf；In figure, 6 refer to or carbon web frame layer for carbon, and 5 is plane carbon-coating；
Fig. 4 is carbon web frame schematic diagram, and in figure, c is carbon net width；D is carbon net length；E is adjacent finger distance between centers of tracks；F: phase
Neighbour refers to distance between centers of tracks；
Fig. 5 is that low resistance carbon refers to or the schematic diagram of the carbon back perovskite solaode without hole of carbon net；
Fig. 6 is the top view of Fig. 5；
In figure, 1 is conductive layer；2 is compacted zone；3 is mesoporous layer；4 is insulating barrier；5 is plane carbon-coating；6 refer to or carbon for carbon
Web frame layer；
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
Single carbon refers to the preparation of structure sheaf (n=2)
1. prepared by low resistance carbon pastes
By graphite flake (particle diameter 325 mesh) 2 grams, graphite flake (particle diameter 7-12 micron) 8 grams, white carbon black (mean diameter 30 microns) 2
Gram, zirconium oxide (< 50 microns) 1 gram, 1 gram of mixing of cellulose be placed in the terpineol of 30 grams, then on zirconia ball mill
Ball milling 12 hours, rotating speed 400rpm, prepares low resistance carbon electrode slurry.Wherein, the solid content C% of carbon component is 27.3%.
2. set up the working curve between carbon layers having thicknesses and sheet resistance
Take 5 grams of low resistance carbon electrode slurry, use the silk screen printing web plate of 150 mesh, formed according to different print pass
The carbon-coating of different-thickness, and sinter 30 minutes respectively at 400 DEG C.Carbon layers having thicknesses uses step instrument to measure, and sheet resistance uses four probes
Resistance meter is measured.Relation between the carbon electrode layer thickness and the sheet resistance that obtain.When the thickness of carbon-coating is less than 20 microns, carbon
Layer sheet resistance significantly reduce along with the increase of the thickness of carbon-coating, when carbon-coating thickness more than 30 microns time, the sheet resistance of carbon-coating with
The increase of the thickness of carbon-coating and slowly reduce, finally tend to stable.As shown in Figure 1.
3. determine the suitable depth of two-layer compound carbon-coating structure
Based on the relation between carbon layers having thicknesses and carbon-coating sheet resistance, select suitable depth 10 microns and the list of plane carbon-coating respectively
The thickness that carbon refers to 40 microns.The corresponding sheet resistance that sheet resistance is plane carbon-coating is 25 Europe, and the sheet resistance that single carbon refers to is 7 Europe.
4. the preparation of plane carbon-coating；
Take 5 grams of low resistance carbon pastes (solid content 27.3%), use 250 mesh ground silk screen web plates, at a kind of clean glass
On substrate 50 × 50 (mm) surface, print one layer of carbon electrode layer, electrode area length × a width of 40 × 35 (mm), the carbon electricity after printing
Pole layer was through 400 DEG C of high temperature sinterings 30 minutes.Through measuring, the thickness of the plane carbon-coating after sintering is 9 microns.
5. single carbon refers to that structure sheaf (n=2) makes
Take 5 grams of low resistance carbon pastes (solid content 27.3%), use 150 mesh ground silk screen web plates, on the surface of plane carbon-coating
On, print one layer of single carbon and refer to structure sheaf.Single carbon refers to that the shape of structure sheaf refers to shown in I such as carbon single in Fig. 2, and its length b × width a is
35 × 30 (mm), line width 1mm, adjacent finger distance between centers of tracks 28mm.Single carbon refers to that structure sheaf is positioned at the inside of plane carbon-coating.After printing
Single carbon refer to that structure sheaf was through 400 DEG C of high temperature sinterings 30 minutes.Measuring through step instrument, the single carbon printing 2 times refers to that structure sheaf is through burning
Line thickness after knot is 35 microns.
Gained two-layer compound carbon-coating structure sheaf is as it is shown on figure 3,1 refers to or carbon web frame layer for carbon, and 2 is plane carbon-coating.
6. resistance test and performance evaluation
Use four probe instrument to test the sheet resistance of above-mentioned plane carbon-coating respectively and single carbon refers to the sheet resistance of structure sheaf, knot
Fruit is 21 Europe for the sheet resistance of plane carbon-coating, and the sheet resistance that single carbon refers to structure sheaf is 7 Europe.
Embodiment 2:
Many carbon refer to the making of structure (n=3)
1. prepared by low resistance carbon pastes
With embodiment 1.
2. set up the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determine the suitable depth of two-layer compound carbon-coating structure
With embodiment 1.
4. the preparation of plane carbon-coating；
With embodiment 1.
5. three carbon refer to that structure sheaf (n=3) makes
Take 5 grams of low resistance carbon pastes (solid content 27.3%), use 150 mesh ground silk screen web plates, on the surface of plane carbon-coating
On, printing carbon more than one layer refers to structure sheaf.Three carbon refer to that the shape of structure sheaf refers to shown in II such as carbon many in Fig. 2, its length b × width a
It is 38 × 30 (mm), line width 1mm, adjacent finger distance between centers of tracks 13.5mm.Three carbon refer to that structure sheaf is positioned at the inside of plane carbon-coating.Print
Three carbon after brush refer to that structure sheaf was through 400 DEG C of high temperature sinterings 30 minutes.Measure through step instrument, print three carbon after 2 times and refer to structure
Line thickness after layer sintering is 40 microns.
6. resistance test and performance evaluation.
Use four probe instrument to test the sheet resistance of above-mentioned plane carbon-coating respectively and single carbon refers to the sheet resistance of structure sheaf, knot
Fruit is 21 Europe for the sheet resistance of plane carbon-coating, and many carbon refer to that the sheet resistance of structure sheaf is 5 Europe.
Embodiment 3:
The making of single network layer (n=1)
1. prepared by low resistance carbon pastes
With embodiment 1.
2. set up the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determine the suitable depth of two-layer compound carbon-coating structure
With embodiment 1.
4. the preparation of plane carbon-coating；
With embodiment 1.
5. single network layer (n=1) makes
Take 5 grams of low resistance carbon pastes (solid content 27.3%), use 150 mesh ground silk screen web plates, on the surface of plane carbon-coating
On, print one layer of single network layer.The shape of single network layer as shown in grid III single in Fig. 4, its length c × width d
It is 45 × 30 (mm), line width 1mm, adjacent finger distance between centers of tracks 28mm.The open at one end of single network layer is positioned at plane carbon-coating
Inside, another Guan Bi end is positioned at the outside of plane carbon-coating, exposes length 8mm of outside.Many carbon after printing refer to structure sheaf warp
Cross 400 DEG C of high temperature sinterings 30 minutes.Measure through step instrument, print single carbon of 2 times refer to structure sheaf sinter after line thickness be 38 micro-
Rice.
6. resistance test and performance evaluation
Use four probe instrument to test the sheet resistance of above-mentioned plane carbon-coating respectively and single carbon refers to the sheet resistance of structure sheaf, knot
Fruit is 21 Europe for the sheet resistance of plane carbon-coating, and many carbon refer to that the sheet resistance of structure sheaf is 6 Europe.
Embodiment 4:
The making of vertical-shaped three network layers (n=3)
1. prepared by low resistance carbon pastes
With embodiment 1.
2. set up the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determine the suitable depth of two-layer compound carbon-coating structure
With embodiment 1.
4. the preparation of plane carbon-coating；
With embodiment 1.
The most vertical-shaped three network layers (n=3) make
Take 5 grams of cryogenic carbon slurries (solid content 27.3%), use 150 mesh ground silk screen web plates, on the surface of plane carbon-coating,
Print one layer of vertical-shaped three network layer.The shape of vertical-shaped three network layers as shown in many grids carbon net IV vertical-shaped in Fig. 4, its
Length c × width d is 45 × 30 (mm), line width 1mm, adjacent finger distance between centers of tracks 13.5mm.The one of vertical-shaped three network layers
End is positioned at the inside of plane carbon-coating, and the other end is positioned at the outside of plane carbon-coating, exposes length 8mm of outside.Vertical-shaped after printing
Three network layers were through 400 DEG C of high temperature sinterings 30 minutes.Measuring through step instrument, the vertical-shaped three network layers printing 2 times burn
Line thickness after knot is 37 microns.
6. resistance test and performance evaluation.
Four probe instrument are used to test sheet resistance and the side of vertical-shaped three network layers of above-mentioned plane carbon-coating respectively
Resistance, result be the sheet resistance of plane carbon-coating be 21 Europe, the sheet resistance of vertical-shaped three network layers is 6 Europe.
Embodiment 5:
Shape many grids carbon web frame layer is handed over to make
1. prepared by low resistance carbon pastes
With embodiment 1.
2. set up the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determine the suitable depth of two-layer compound carbon-coating structure
With embodiment 1.
4. the preparation of plane carbon-coating；
With embodiment 1.
5. hand over shape many grids carbon web frame layer to make
Take 5 grams of cryogenic carbon slurries (solid content 27.3%), use 150 mesh ground silk screen web plates, on the surface of plane carbon-coating,
Print one layer and hand over shape many grids carbon web frame layer, hand over the shape of shape many grids carbon web frame layer as shown in grid VI single in Fig. 4, its
Length c × width d is 45 × 30 (mm), line width 1mm.This friendship shape many grids carbon web frame layer include vertical-shaped four grid carbon nets and
The double grid carbon net of horizontal shape.Wherein, the adjacent finger line width of vertical-shaped four grid carbon web frame layers is 8mm, the double grid carbon net of horizontal shape
Adjacent finger line width be 13.5mm.The one end handing over shape many grids carbon web frame layer is positioned at the inside of plane carbon-coating, the other end
It is positioned at the outside of plane carbon-coating, exposes length 10mm of outside.Friendship shape many grids carbon web frame layer after printing is high through 400 DEG C
Temperature sintering 30 minutes.Measuring through step instrument, it is 37 micro-for print the line thickness after friendship shape many grids carbon web frame layer of 2 times sinters
Rice.
6. resistance test and performance evaluation
Four probe instrument are used to test the sheet resistance of above-mentioned plane carbon-coating respectively and hand over shape many grids carbon web frame layer
Sheet resistance, result be the sheet resistance of plane carbon-coating be 21 Europe, hand over shape many grids carbon web frame layer sheet resistance be 6 Europe.
Embodiment 6:
As seen in figs. 5-6, low resistance list carbon refers to the preparation of carbon back perovskite solaode
1) conductive substrates processes
First the FTO electro-conductive glass of 50 × 50 (mm) being carried out laser ablation, the position of etching is at conducting surface 40 × 50
(mm) boundary of and 10 × 50 (mm) has a width to be the etching groove of 3mm, and conducting surface is divided into 38.5 × 50 by this etching groove
(mm) and 8.5 × 50 (mm) two part.Then etching conductive substrate is clear with alkali glass water, water and EtOH Sonicate the most respectively
Wash, until totally, dried for standby, obtain conductive layer 1 (as shown in Figure 5).
2) compacted zone makes
First configure the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl ester of 10wt%, then clean is led
Electric layer 1 (electro-conductive glass) is placed on the warm table of 450 DEG C, and the conducting surface of glass upward, then uses aerosol apparatus by two-(acetyl
Acetone) aqueous isopropanol of-metatitanic acid diisopropyl ester is sprayed on conducting surface one layer of ultra-thin titanium dioxide dense of formation equably
Layer 2.Compacted zone 2 forms thickness about 50 ran after 500 DEG C sinter 30 minutes.
3) mesoporous layer makes
Use screen printing technique, titania slurry (solid content 1.5%, solvent the is terpineol) print that will prepare in advance
Brush, on the surface of above-mentioned compacted zone 2, obtains mesoporous layer, and the electrode area of mesoporous layer is 30 × 40 (mm), two after printing
Medium pore of titania layer was through 500 DEG C of high temperature sinterings 30 minutes.Now, the thickness of mesoporous layer 3 is 2 microns.
4) insulating barrier makes
Use screen printing technique, zirconium dioxide slurry (solid content 1.5%, solvent the is terpineol) print that will prepare in advance
Brush, on the surface of above-mentioned mesoporous layer 3, obtains insulating barrier 4, and the electrode area of this insulating barrier 4 is 32 × 45 (mm), after printing
Insulating barrier through 500 DEG C of high temperature sinterings 30 minutes.Now, the thickness of insulating barrier 4 is 2 microns.
5) plane carbon-coating makes
Use screen printing technique, low resistance carbon pastes (solid content 30%, solvent is terpineol) is printed on above-mentioned
On the surface of insulating barrier 4, obtaining plane carbon-coating 5, the electrode area of plane carbon-coating 5 is 32 × 45 (mm), the planar carbon after printing
Layer 5 was through 400 DEG C of high temperature sinterings 30 minutes.Now, the thickness of plane carbon-coating 5 is 10 microns.
6) single carbon refers to that structure sheaf makes
Use screen printing technique, low resistance carbon pastes (solid content 30%, solvent is terpineol) is printed on above-mentioned
On the surface of plane carbon-coating 5, obtaining carbon and refer to structure sheaf 6, what carbon referred to be shaped as, and single carbon refers to, sees Fig. 2.The size that single carbon refers to is single carbon
Referring to a length of 36mm, single carbon finger widths is 40mm, and every line width is 2mm, adjacent finger distance between centers of tracks 38mm, and single carbon refers to structure sheaf
Open at one end is positioned at the inside of plane carbon-coating, and another Guan Bi end is positioned at the outside of plane carbon-coating, exposes length 8mm of outside.Print
Single carbon after brush 2 times refers to that structure sheaf was through 400 DEG C of high temperature sinterings 30 minutes.Single carbon after sintering refers to that the thickness of structure sheaf is 38 micro-
Rice.
7) absorption of perovskite precursor solution
Take the DMF solution (solid content of the pre-prepd perovskite precursor solution CH3NH3PbI3 of about 1 milliliter
40wt%), drop in carbon and refer to the surface of structure sheaf 6, static 5 minutes, allow solution penetrate into lower floor, then electrode is placed in 70 DEG C
Heating 30 minutes in thermal station, remove volatile solvent, perovskite CH3NH3PbI3 crystallization is complete simultaneously, and set of cells installs complete.
8) battery performance test
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).The results are shown in Table 1.
Embodiment 7:
Low resistance hands over the preparation of shape many grids carbon net carbon back perovskite solaode
1) conductive substrates processes, compacted zone makes, mesoporous layer makes, insulating barrier makes, plane carbon-coating makes, same to embodiment
Six.
2) shape many grids carbon web frame layer is handed over to make
Take 5 grams of cryogenic carbon slurries (solid content 27.3%), use 150 mesh ground silk screen web plates, on the surface of plane carbon-coating,
Print one layer and hand over shape many grids carbon web frame layer, hand over the shape of shape many grids carbon web frame layer as shown in grid IV single in Fig. 4, its
Length x width is 36 × 40 (mm), line width 2mm.This friendship shape many grids carbon web frame layer includes vertical-shaped four grid carbon net and horizontal strokes
The double grid carbon net of shape.Wherein, the adjacent finger line width of vertical-shaped four grid carbon web frame layers is 8mm, the double grid carbon net of horizontal shape
Adjacent finger line width is 15mm.The one end handing over shape many grids carbon web frame layer is positioned at the inside of plane carbon-coating, and the other end is positioned at
The outside of plane carbon-coating, exposes length 10mm of outside.Friendship shape many grids carbon web frame layer after printing burns through 400 DEG C of high temperature
Tie 30 minutes.Measuring through step instrument, printing the line thickness after friendship shape many grids carbon web frame layer sintering of 2 times is 37 microns.
3) absorption of perovskite precursor solution, with embodiment six.
4) battery performance test, with embodiment six.
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).The results are shown in Table 1.
Embodiment 8:
Carbon without low resistance refers to or the preparation of carbon back perovskite solaode of carbon net
1) before conductive substrates process, compacted zone making, the making of mesoporous layer, insulating barrier making, the making of plane carbon-coating, perovskite
Drive the absorption of liquid solution, with embodiment six.Difference is, this step does not has carbon to refer to or the making of carbon net.
2) battery performance test, with embodiment six.
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).The results are shown in Table 1.
Table 1
It can be seen that arrange the electrode of two-layer compound carbon-coating structure the most as described herein, its every battery performance is all
Not as being provided with the electrode of two-layer compound carbon-coating structure of the present invention, especially photoelectric transformation efficiency has obtained greatly carrying
High.
Embodiment 9
(1) conductive substrates processes
Employing electro-conductive glass is conductive substrates, carries out substrate etching, substrate washing and drying treatment successively；Described substrate
Etching mainly chemical etching；Predominantly ozone clean is cleaned in described substrate, and drying means is heat drying；
(2) compacted zone makes
Nano-oxide compacted zone is made by spin-coating method in step (1) gained conductive substrates surface；Described compacted zone
Thickness is less than 100 nanometers.
Described nano-oxide is mainly titanium oxide；Described spin-coating method uses nano-oxide spin coating liquid in rotation exactly
It is coated with on instrument preparation under the rotary speed of 500rpm and forms ultra-thin oxide membranous layer, and through 400 DEG C of high temperature sinterings 120 minutes
And obtain.
(3) mesoporous layer makes
Web plate adds appropriate nanometer alumina slurry, uses scraper on the surface of step (2) gained compacted zone
Printing and formed the mesoporous layer of 1 micron, this mesoporous layer forms stable mesoporous Rotating fields after 400 DEG C of high temperature sinterings.
(4) insulating barrier makes
Web plate adds appropriate nanometer alumina slurry, uses scraper on the surface of the mesoporous layer of step (3) gained
Printing and formed the insulating barrier of 1 micron, this insulating barrier forms stable insulated hole Rotating fields, institute after 1 um high temperature sintering
The thickness of insulating layer stated is 1 micron.
(5) planar carbon electrode layer makes
In step (4) gained surface of insulating layer, the method using following plane carbon-coating, make plane carbon-coating；Planar carbon electricity
The thickness of pole layer is 5 microns.
The preparation of plane carbon-coating:
Prepared by (a) low resistance carbon pastes；
Graphite, white carbon black, inorganic oxide, organic thickening agent and solvent are mixed, uses ball milling or three roller methods to make carbon
Slurry, described graphite and the weight ratio of white carbon black are 1:1, and in described carbon slurry, graphite and the solid content shared by white carbon black are 10wt%, nothing
Solid content shared by machine oxide is 10wt%, and the solid content shared by organic thickening agent is 1wt%；
Described graphite is graphite flake；Described white carbon black is nano carbon black；Described inorganic oxide is titanium oxide；Described
Organic thickening agent be cellulose；Described solvent is water.
B () sets up the working curve between carbon layers having thicknesses and sheet resistance
Step (a) gained carbon pastes is made carbon-coating by spraying process, then sinters 60 minutes in 350 DEG C, use four probes
Resistance meter or ohmmeter measure the resistance of carbon-coating, set up the working curve between carbon layers having thicknesses and sheet resistance；Described carbon-coating
Thickness is controlled by the number of times of printing or blade coating or spraying；
C () determines the suitable depth of two-layer compound carbon-coating structure
According to step (b) gained working curve, select to be positioned at carbon-coating sheet resistance and reduce rapidly along with the increase of carbon layers having thicknesses
Thickness as the thickness of plane carbon-coating；Select be positioned at carbon-coating sheet resistance reduce along with the increase of carbon layers having thicknesses trend start tend to
Refer to the thickness of structure sheaf as carbon in the thickness of stationary value；
The preparation of (d) plane carbon-coating
Method for printing screen, knife coating or spraying process is used to make step (c) determined thickness plane carbon-coating, and in 350
DEG C sintering 60 minutes, to plane carbon-coating；
(6) carbon refers to that structure sheaf makes
The shape and size that design carbon refers to as required, on plane carbon-coating, use spraying process to make step (c) and are determined
The carbon of thickness refers to, and sinters 60 minutes in 350 DEG C, and the carbon obtained refers to that the thickness of structure sheaf is generally 30 microns.Described carbon refers to
One end of structure sheaf is positioned at the outside of plane carbon-coating, contacts with conductive substrates, and the other end is positioned in planar carbon electrode layer surface, with
Planar carbon electrode layer contacts.
(7) absorption of perovskite precursor solution
First refer to structure sheaf instill and penetrates in mesoporous layer or insulating barrier from carbon by a certain amount of lead iodide solution,
At 70 DEG C, heating makes solvent volatilize, and then the electrode of absorption lead iodide is immersed in several minutes in methylamine iodine solution, treats black shape
Take out after one-tenth and be placed in the thermal station of 50 DEG C adding heat extraction solvent, form perovskite battery；Described lead iodide solution, its consumption
For micro updating；Its solvent is mainly dimethylformamide；Its concentration is 0.5 mol/L.
The solution of described first ammonia iodine, its consumption is submergence electrode；Its solvent is mainly isopropanol；Its concentration is general
It is 5 mg/ml.
(8) battery performance test
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).It is shown in Table 2.
Embodiment 10
(1) conductive substrates processes
Employing electro-conductive glass is conductive substrates, carries out substrate etching, substrate washing and drying treatment successively；Described substrate
Etching mainly chemical etching；Predominantly ozone clean is cleaned in described substrate, and drying means is heat drying；
(2) compacted zone makes
Nano-oxide compacted zone is made by spin-coating method in step (1) gained conductive substrates surface；Described compacted zone
Thickness is less than 50 nanometers.
Described nano-oxide is mainly titanium oxide；Described spin-coating method uses nano-oxide spin coating liquid in rotation exactly
It is coated with on instrument preparation under the rotary speed of 8000rpm and forms ultra-thin oxide membranous layer, and through 600 DEG C of high temperature sinterings 15 minutes
And obtain.
(3) mesoporous layer makes
Web plate adds appropriate nanometer alumina slurry, uses scraper on the surface of step (2) gained compacted zone
Printing and formed the mesoporous layer of 5 microns, this mesoporous layer forms stable mesoporous Rotating fields after 600 DEG C of high temperature sinterings.
(4) insulating barrier makes
Web plate adds appropriate nanometer alumina slurry, uses scraper on the surface of the mesoporous layer of step (3) gained
Printing and formed the insulating barrier of 5 microns, this insulating barrier forms stable insulated hole Rotating fields, institute after 5 um high temperature sintering
The thickness of insulating layer stated is 5 microns.
(5) planar carbon electrode layer makes
In step (4) gained surface of insulating layer, the method using following plane carbon-coating, make plane carbon-coating；Planar carbon electricity
The thickness of pole layer is 20 microns.
The preparation of plane carbon-coating:
Prepared by (a) low resistance carbon pastes；
Graphite, white carbon black, inorganic oxide, organic thickening agent and solvent are mixed, uses ball milling or three roller methods to make carbon
Slurry, described graphite and the weight ratio of white carbon black are 10:1, and in described carbon slurry, graphite and the solid content shared by white carbon black are 60wt%, nothing
Solid content shared by machine oxide is 10wt%, and the solid content shared by organic thickening agent is 10wt%；
Described graphite is graphite nodule；Described white carbon black is nano carbon black；Described inorganic oxide is silicon oxide；Described
Organic thickening agent be hydroxypropyl cellulose；Described solvent is ethanol.
B () sets up the working curve between carbon layers having thicknesses and sheet resistance
Step (a) gained carbon pastes is made carbon-coating by knife coating, then sinters 10 minutes in 500 DEG C, use four probes
Resistance meter or ohmmeter measure the resistance of carbon-coating, set up the working curve between carbon layers having thicknesses and sheet resistance；Described carbon-coating
Thickness is controlled by blade coating number of times；
C () determines the suitable depth of two-layer compound carbon-coating structure
According to step (b) gained working curve, select to be positioned at carbon-coating sheet resistance and reduce rapidly along with the increase of carbon layers having thicknesses
Thickness as the thickness of plane carbon-coating；Select be positioned at carbon-coating sheet resistance reduce along with the increase of carbon layers having thicknesses trend start tend to
Refer to the thickness of structure sheaf as carbon in the thickness of stationary value；
The preparation of (d) plane carbon-coating
Use knife coating to make step (c) determined thickness plane carbon-coating, and sinter 10 minutes in 500 DEG C, to planar carbon
Layer；
(6) carbon refers to that structure sheaf makes
The shape and size that design carbon refers to as required, on plane carbon-coating, use knife coating to make step (c) and are determined
The carbon of thickness refers to, and sinters 10 minutes in 500 DEG C, and the carbon obtained refers to that the thickness of structure sheaf is generally 100 microns.Described carbon refers to
One end of structure sheaf is positioned at the outside of plane carbon-coating, contacts with conductive substrates, and the other end is positioned in planar carbon electrode layer surface, with
Planar carbon electrode layer contacts.
(7) absorption of perovskite precursor solution
First refer to structure sheaf instill and penetrates in mesoporous layer or insulating barrier from carbon by a certain amount of lead iodide solution,
At 70 DEG C, heating makes solvent volatilize, and then the electrode of absorption lead iodide is immersed in several minutes in methylamine iodine solution, treats black shape
Take out after one-tenth and be placed in the thermal station of 50 DEG C adding heat extraction solvent, form perovskite battery；Described lead iodide solution, its consumption
Generally micro updating or milliliter level, preferably micro updating；Its solvent is mainly in dimethylformamide, dimethyl sulfoxide, fourth
Ester or their mixed solvent；Its concentration is 1.5 mol/L.
The solution of described first ammonia iodine, its consumption is submergence electrode；Its solvent is mainly ethanol；Its concentration is generally
15 mg/ml.
(8) battery performance test
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).It is shown in Table 2.
Embodiment 11
(1) conductive substrates processes
Employing electro-conductive glass is conductive substrates, carries out substrate etching, substrate washing and drying treatment successively；Described substrate
Etching mainly laser ablation；Described substrate is cleaned and is cleaned for ultralow temperature carbon dioxide, and drying means is heat drying；
(2) compacted zone makes
Nano-oxide compacted zone is made by spray pyrolysis in step (1) gained conductive substrates surface；Described cause
Close layer thickness is 30 nanometers.
Described nano-oxide is mainly titanium oxide；
Described spray pyrolysis is the conductive base using aerosol apparatus to be sprayed in the thermal station of high temperature by titanium source precursor solution
, titanium source presoma is decomposed to form rapidly nano-oxide compacted zone under the effect of 400 DEG C of high temperature at the end.Described titanium source forerunner
Liquid solution is mainly the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl ester.
(3) mesoporous layer makes
Web plate adds appropriate nano-oxide slurry, uses scraper on the surface of step (2) gained compacted zone
Printing and formed the mesoporous layer of 1 micron thickness, this mesoporous layer forms stable mesoporous Rotating fields after 400 DEG C of high temperature sinterings.
(4) insulating barrier makes
Web plate adds appropriate nano-oxide slurry, uses scraper on the surface of the mesoporous layer of step (3) gained
Printing and formed the insulating barrier of 1 micron thickness, this insulating barrier forms stable insulation aperture layer knot after 400 DEG C of high temperature sinterings
Structure.
Described nano-oxide slurry is nano zircite slurry, and its particle diameter is 20 nanometers.
(5) planar carbon electrode layer makes
In step (4) gained surface of insulating layer, the method using following plane carbon-coating, make plane carbon-coating；Planar carbon electricity
The thickness of pole layer is 5 microns.
The preparation of plane carbon-coating:
Prepared by (a) low resistance carbon pastes；
Graphite, white carbon black, inorganic oxide, organic thickening agent and solvent are mixed, uses ball milling or three roller methods to make carbon
Slurry, described graphite and the weight ratio of white carbon black are 5:1, and in described carbon slurry, graphite and the solid content shared by white carbon black are 25wt%, nothing
Solid content shared by machine oxide is 2wt%, and the solid content shared by organic thickening agent is 2wt%；
Described inorganic oxide is silicon oxide；Described organic thickening agent is hydroxypropyl cellulose；Described solvent is
Glycerol.
B () sets up the working curve between carbon layers having thicknesses and sheet resistance
Step (a) gained carbon pastes is made carbon-coating by method for printing screen, knife coating or spraying process, then in 350
DEG C sintering 60 minutes, with four probe instrument or ohmmeter measurement carbon-coating resistance, set up between carbon layers having thicknesses and sheet resistance
Working curve；The thickness of described carbon-coating is controlled by the number of times of printing or blade coating or spraying；
C () determines the suitable depth of two-layer compound carbon-coating structure
According to step (b) gained working curve, select to be positioned at carbon-coating sheet resistance and reduce rapidly along with the increase of carbon layers having thicknesses
Thickness as the thickness of plane carbon-coating；Select be positioned at carbon-coating sheet resistance reduce along with the increase of carbon layers having thicknesses trend start tend to
In the thickness of stationary value as the thickness of carbon web frame layer；
The preparation of (d) plane carbon-coating
Method for printing screen, knife coating or spraying process is used to make step (c) determined thickness plane carbon-coating, and in 350
DEG C sintering 60 minutes；
(6) carbon web frame layer makes
Design the shape and size of carbon net as required, on step (d) gained plane carbon-coating, use method for printing screen
Make the carbon net of the determined thickness of step (c), and sinter 60 minutes in 350 DEG C, obtain low resistance electrode.Described carbon web frame
One end of layer is positioned at the outside of plane carbon-coating, contacts with conductive substrates, and the other end is positioned in planar carbon electrode layer surface, with plane
Carbon electrode layer contacts.
(7) absorption of perovskite precursor solution
A certain amount of methylamine lead iodine precursor solution is instilled and penetrates into mesoporous layer or insulating barrier from carbon web frame layer
In, then at 100 DEG C, heating makes solvent volatilize, and forms perovskite battery.
Described methylamine lead iodine precursor solution, its consumption is micro updating；Its solvent is dimethylformamide, dimethyl Asia
The mixed solvent of sulfone；Its concentration is 0.5 mol/L.
(8) battery performance test
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).It is shown in Table 2.
Embodiment 12
(1) conductive substrates processes
Employing electro-conductive glass is conductive substrates, carries out substrate etching, substrate washing and drying treatment successively；Described substrate
Etching mainly laser ablation；Described substrate is cleaned and is cleaned for ultralow temperature carbon dioxide, and drying means is heat drying；
(2) compacted zone makes
Nano-oxide compacted zone is made by spray pyrolysis in step (1) gained conductive substrates surface；Described cause
Close layer thickness is 50 nanometers.
Described nano-oxide is mainly titanium oxide；
Described spray pyrolysis is the conductive base using aerosol apparatus to be sprayed in the thermal station of high temperature by titanium source precursor solution
, titanium source presoma is decomposed to form rapidly nano-oxide compacted zone under the effect of 600 DEG C of high temperature at the end.Described titanium source forerunner
Liquid solution is mainly the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl ester.
(3) mesoporous layer makes
Web plate adds appropriate nano-oxide slurry, uses scraper on the surface of step (2) gained compacted zone
Printing and formed the mesoporous layer of 3 micron thickness, this mesoporous layer forms stable mesoporous Rotating fields after 600 DEG C of high temperature sinterings.
(4) insulating barrier makes
Web plate adds appropriate nano-oxide slurry, uses scraper on the surface of the mesoporous layer of step (3) gained
Printing and formed the insulating barrier of 3 micron thickness, this insulating barrier forms stable insulation aperture layer knot after 600 DEG C of high temperature sinterings
Structure.
Described nano-oxide slurry is nano zircite slurry, and its particle diameter is 100 nanometers.
(5) planar carbon electrode layer makes
In step (4) gained surface of insulating layer, the method using following plane carbon-coating, make plane carbon-coating；Planar carbon electricity
The thickness of pole layer is 20 microns.
The preparation of plane carbon-coating:
Prepared by (a) low resistance carbon pastes；
Graphite, white carbon black, inorganic oxide, organic thickening agent and solvent are mixed, uses ball milling or three roller methods to make carbon
Slurry, described graphite and the weight ratio of white carbon black are 5:1, and in described carbon slurry, graphite and the solid content shared by white carbon black are 35wt%, nothing
Solid content shared by machine oxide is 5wt%, and the solid content shared by organic thickening agent is 5wt%；
Described inorganic oxide is zirconium oxide；Described organic thickening agent is cellulose；Described solvent is ethanol.
B () sets up the working curve between carbon layers having thicknesses and sheet resistance
Step (a) gained carbon pastes is made carbon-coating by method for printing screen, then sinters 10 minutes in 500 DEG C, use
Four probe instrument or ohmmeter measure the resistance of carbon-coating, set up the working curve between carbon layers having thicknesses and sheet resistance；Described
The thickness of carbon-coating is controlled by the number of times of printing or blade coating or spraying；
C () determines the suitable depth of two-layer compound carbon-coating structure
According to step (b) gained working curve, select to be positioned at carbon-coating sheet resistance and reduce rapidly along with the increase of carbon layers having thicknesses
Thickness as the thickness of plane carbon-coating；Select be positioned at carbon-coating sheet resistance reduce along with the increase of carbon layers having thicknesses trend start tend to
In the thickness of stationary value as the thickness of carbon web frame layer；
The preparation of (d) plane carbon-coating
Method for printing screen, knife coating or spraying process is used to make step (c) determined thickness plane carbon-coating, and in 500
DEG C sintering 10 minutes；
(6) carbon web frame layer makes
Design the shape and size of carbon net as required, on step (d) gained plane carbon-coating, use method for printing screen
Make the carbon net of the determined thickness of step (c), and sinter 10 minutes in 500 DEG C, obtain low resistance electrode.Described carbon web frame
The thickness of layer is 50 microns.One end of described carbon web frame layer is positioned at the outside of plane carbon-coating, contacts with conductive substrates, another
End is positioned in planar carbon electrode layer surface, contacts with planar carbon electrode layer.
(7) absorption of perovskite precursor solution
A certain amount of methylamine lead iodine precursor solution is instilled and penetrates into mesoporous layer or insulating barrier from carbon web frame layer
In, then at 100 DEG C, heating makes solvent volatilize, and forms perovskite battery.
Described methylamine lead iodine precursor solution, its consumption is milliliter level；Its solvent be dimethyl sulfoxide, butyrolactone mixed
Bonding solvent；Its concentration is 1.5 mol/L.
(8) battery performance test
The battery of above-mentioned assembling is placed under the illumination of AM1.5, test its short circuit current (Jsc), open-circuit voltage (Voc),
Fill factor, curve factor (FF), photoelectric transformation efficiency (η).It is shown in Table 2..
Table 2
Claims (10)
1. a low resistance electrode, it is characterised in that this electrode is to be referred to by plane carbon-coating and carbon or that carbon web frame layer is constituted is double
Layer composite carbon Rotating fields, described plane carbon-coating is planar structure, and described carbon refers to or carbon web frame layer is that carbon refers to or carbon net knot
Structure；Described carbon refers to or carbon web frame layer is arranged on plane carbon-coating, and its coverage rate is less than 80%.
A kind of low resistance electrode the most according to claim 1, it is characterised in that the carbon layers having thicknesses of described electrode and carbon-coating
In inverse ratio between sheet resistance, the thickness of plane carbon-coating selects to be positioned at the thickness that carbon-coating sheet resistance reduces rapidly along with the increase of carbon layers having thicknesses
Degree；Carbon refer to or carbon web frame layer thickness select be positioned at carbon-coating sheet resistance reduce along with the increase of carbon layers having thicknesses trend start tend to
Thickness in stationary value；The thickness of described plane carbon-coating is 5-20 micron；Described carbon refers to or the thickness of carbon web frame layer is
30-100 micron.
A kind of low resistance electrode the most according to claim 2, it is characterised in that the thickness of described plane carbon-coating is 10 micro-
Rice；Described carbon refers to or the thickness of carbon web frame layer is 30-50 micron.
A kind of low resistance electrode the most according to claim 1, it is characterised in that described carbon refers to or carbon web frame layer refers to
Structure sheaf is that carbon refers to layer, or carbon stratum reticulare, and wherein carbon refers to layer to refer to by n bar carbon and refers to the carbon-coating structure that forms, and n >=2, carbon refers to be similar
The carbon-coating structure of finger shape, carbon refers to that one end open, the other end are connected with each other, and both sides are straight line or curve；The shape bag that carbon refers to
Include single carbon to refer to or many carbon refers to；
Described carbon stratum reticulare is the carbon-coating structure of similar mesh shape, quantity n >=1 of grid, as n=1, for single grid carbon
Net, when n >=2, for many grids carbon net, many grids carbon net includes closing structure or hatch frame, and closing structure is that carbon net is whole
Being made up of the grid closed, hatch frame is that to be that the grid that referred to by carbon and close is compound constituted carbon net；The line constituting grid is straight
Line or curve；The shape of carbon net includes single grid carbon net, vertical-shaped many grids carbon net, horizontal shape many grids carbon net, hands over shape many grids carbon
Net and many grids list carbon refer to that composite carbon net and the many carbon of many grids refer to any one of composite carbon net or several.
A kind of low resistance electrode the most according to claim 4, it is characterised in that the line width scope that described carbon refers to is
0.2mm-2mm, line thickness is more than or equal to 5 microns；Carbon finger widths a is less than or equal to the width of the carbon-coating of Tan Zhi lower floor, and carbon refers to
Length b is the length of the carbon-coating being less than or equal to or being more than Tan Zhi lower floor；
The line width scope of described carbon net is 0.5mm-5mm, and line thickness is more than or equal to 10 microns, and the overall width c of carbon net is little
In or equal to the width of carbon-coating of carbon side off the net, Gridding length d less than or equal to or the length of carbon-coating more than carbon side off the net.
A kind of low resistance electrode the most according to claim 5, it is characterised in that the line width scope that described carbon refers to is
0.5-1mm, line thickness is 10-50 micron；The line width scope of described carbon net is 1-3mm, and line thickness is 15-50 micron.
7. the preparation method of a low resistance electrode according to claim 1, it is characterised in that comprise the following steps:
(1) prepared by low resistance carbon pastes；
Graphite, white carbon black, inorganic oxide, organic thickening agent and solvent are mixed, use ball milling or three roller methods to make carbon slurry,
Described graphite and the weight ratio of white carbon black are 1-10:1, and in described carbon slurry, graphite and the solid content shared by white carbon black are 10-60wt%,
Solid content shared by inorganic oxide is 1-10wt%, and the solid content shared by organic thickening agent is 1-10wt%；
(2) working curve between carbon layers having thicknesses and sheet resistance is set up
Step (1) gained carbon pastes is made carbon-coating by method for printing screen, knife coating or spraying process, then in 350-500
DEG C sintering 10-60 minute, with four probe instrument or the resistance of ohmmeter measurement carbon-coating, set up carbon layers having thicknesses and sheet resistance it
Between working curve；The thickness of described carbon-coating is controlled by the number of times of printing or blade coating or spraying；
(3) suitable depth of two-layer compound carbon-coating structure is determined
According to step (2) gained working curve, select to be positioned at the thickness that carbon-coating sheet resistance reduces rapidly along with the increase of carbon layers having thicknesses
Spend the thickness as plane carbon-coating；Select to be positioned at carbon-coating sheet resistance to reduce trend along with the increase of carbon layers having thicknesses and start to trend towards steady
The thickness of definite value refers to as carbon or the thickness of carbon web frame layer；
(4) preparation of plane carbon-coating
Method for printing screen, knife coating or spraying process is used to make step (3) determined thickness plane carbon-coating, and in 350-500
DEG C sintering 10-60 minute；
(5) low resistance carbon refers to or the preparation of carbon web frame layer
Design carbon refers to or the shape and size of carbon net as required, on step (4) gained plane carbon-coating, uses silk screen printing side
Method, knife coating or spraying process are made the carbon of step (3) determined thickness and are referred to or carbon net, and divide in 350-500 DEG C of sintering 10-60
Clock, obtains low resistance electrode.
The preparation method of a kind of low resistance electrode the most according to claim 7, it is characterised in that step (1) described carbon is starched
Solid content shared by middle graphite and white carbon black is 25-35wt%, and the solid content shared by its inorganic oxide is 2-5wt%, and it is organic
Solid content shared by thickening agent is 2-5wt%；The nanometer particle size of described white carbon black is less than 50 nanometers；Described graphite is graphite flake
Or graphite nodule；Described white carbon black is nano carbon black, and nanometer particle size is less than 100 nanometers, preferably less than 50 nanometers；Described graphite
It is 1-5:1 with the weight ratio of white carbon black；Described inorganic oxide is titanium oxide, zirconium oxide, aluminium oxide or silicon oxide；Described has
Machine thickening agent is cellulose or hydroxypropyl cellulose；Described solvent is the one in water, ethanol, terpineol, isopropanol, glycerol
Or it is several.
Sintering temperature described in step (1) and (4) and (5) is 400-450 DEG C, and sintering time is 15-45 minute；
Step (4) makes the raw material of plane carbon-coating and uses step (1) gained carbon pastes, or ready-made carbon refers to or carbon net materials,
Or ready-made carbon refers to or the mixing material of carbon net materials and step (1) described carbon pastes.
The preparation method of a kind of low resistance electrode the most according to claim 7, it is characterised in that the low electricity of step (5) gained
Resistance electrode uses four probe instrument or ohmmeter test plane carbon-coating and carbon refers to or the sheet resistance of carbon web frame layer.
10. the application of a low resistance electrode according to claim 1, it is characterised in that low resistance electrode is used in nothing
On the carbon back perovskite solaode in hole.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107146847A (en) * | 2017-05-16 | 2017-09-08 | 华中科技大学 | It is a kind of new based on all solid state printable perovskite solar cell of carbon electrode |
| CN107910445A (en) * | 2017-11-06 | 2018-04-13 | 西安交通大学 | A kind of perovskite solar cell of two-layer electrode and preparation method thereof |
| CN108365108A (en) * | 2018-01-05 | 2018-08-03 | 南京邮电大学 | A kind of perovskite solar cell and preparation method thereof of p-type nano material embedded in carbon electrode |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007029750A1 (en) * | 2005-09-06 | 2007-03-15 | Kyoto University | Organic thin film photoelectric converter and method for manufacturing same |
| CN102122577A (en) * | 2010-12-28 | 2011-07-13 | 复旦大学 | Titanium dioxide (TiO2) nano-rod single-crystal array thin film as well as preparation method and application thereof |
| CN102365753A (en) * | 2008-10-30 | 2012-02-29 | 纳米太阳能公司 | Hybrid transparent conductive electrodes |
| CN102832348A (en) * | 2012-08-28 | 2012-12-19 | 浙江大学 | Patterned electrode, preparation method and organic solar cell |
| US20130256629A1 (en) * | 2012-04-03 | 2013-10-03 | Samsung Electronics Co., Ltd. | Graphene semiconductor device, manufacturing method thereof, organic light emitting display, and memory including graphene semiconductor device |
| CN104022226A (en) * | 2014-05-14 | 2014-09-03 | 中国科学院物理研究所 | Perovskite-based film solar cell and preparation method |
| CN104134752A (en) * | 2014-07-08 | 2014-11-05 | 中国科学院物理研究所 | Perovskite solar cell and preparation method for thermoplastic carbon counter electrode |
-
2016
- 2016-09-07 CN CN201610807007.3A patent/CN106299130B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007029750A1 (en) * | 2005-09-06 | 2007-03-15 | Kyoto University | Organic thin film photoelectric converter and method for manufacturing same |
| CN102365753A (en) * | 2008-10-30 | 2012-02-29 | 纳米太阳能公司 | Hybrid transparent conductive electrodes |
| CN102122577A (en) * | 2010-12-28 | 2011-07-13 | 复旦大学 | Titanium dioxide (TiO2) nano-rod single-crystal array thin film as well as preparation method and application thereof |
| US20130256629A1 (en) * | 2012-04-03 | 2013-10-03 | Samsung Electronics Co., Ltd. | Graphene semiconductor device, manufacturing method thereof, organic light emitting display, and memory including graphene semiconductor device |
| CN102832348A (en) * | 2012-08-28 | 2012-12-19 | 浙江大学 | Patterned electrode, preparation method and organic solar cell |
| CN104022226A (en) * | 2014-05-14 | 2014-09-03 | 中国科学院物理研究所 | Perovskite-based film solar cell and preparation method |
| CN104134752A (en) * | 2014-07-08 | 2014-11-05 | 中国科学院物理研究所 | Perovskite solar cell and preparation method for thermoplastic carbon counter electrode |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107146847A (en) * | 2017-05-16 | 2017-09-08 | 华中科技大学 | It is a kind of new based on all solid state printable perovskite solar cell of carbon electrode |
| CN107146847B (en) * | 2017-05-16 | 2019-05-21 | 华中科技大学 | It is a kind of novel based on all solid state printable perovskite solar battery of carbon electrode |
| CN107910445A (en) * | 2017-11-06 | 2018-04-13 | 西安交通大学 | A kind of perovskite solar cell of two-layer electrode and preparation method thereof |
| CN107910445B (en) * | 2017-11-06 | 2019-08-23 | 西安交通大学 | A kind of perovskite solar battery of two-layer electrode and preparation method thereof |
| CN108365108A (en) * | 2018-01-05 | 2018-08-03 | 南京邮电大学 | A kind of perovskite solar cell and preparation method thereof of p-type nano material embedded in carbon electrode |
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