CN106299130B - Low resistance electrode, preparation method and its application on carbon-based perovskite solar battery - Google Patents
Low resistance electrode, preparation method and its application on carbon-based perovskite solar battery Download PDFInfo
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Abstract
The present invention relates to a kind of low resistance electrode, preparation method and its applications on carbon-based perovskite solar battery, the 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, the plane carbon-coating is planar structure, and the carbon refers to or carbon web frame layer refers to for carbon or carbon web frame；The carbon refers to or carbon web frame layer is arranged on plane carbon-coating, and coverage rate is no more than 80%.Preparation method includes: the preparation of (1) low resistance carbon pastes；(2) working curve between carbon layers having thicknesses and sheet resistance is established；(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.By low resistance electrode on the carbon-based perovskite solar battery in no hole.Compared with prior art, the present invention has many advantages, such as the photoelectric conversion efficiency for improving battery, stability, the at low cost, simple process for improving battery.
Description
Technical field
The present invention relates to a kind of low resistance electrode, refer to more particularly, to a kind of low resistance carbon or carbon net electrode, preparation method
And its application on carbon-based perovskite solar battery.
Background technique
In recent years, the fashionable whole world of research of perovskite solar battery of new generation, the at present highest of its certifying authority
Battery efficiency has broken through 22%, more than the efficiency of conventional films solar battery.Compared with other types of solar battery,
This kind of battery also have the advantages that it is incomparable, such as material source is convenient, manufacture craft is simple, equipment requirement is not high and battery
It is at low cost etc..These features illustrate that perovskite solar battery is expected to become the generation of solar battery of new generation most industrialization
Table.
Perovskite solar battery is one kind using perovskite as all solid state solar battery of photosensitizer.According to back electrode
Difference, it can be divided into metal based perovskite solar battery and carbon-based perovskite solar battery, wherein carbon-based perovskite
Solar battery according to the characteristics of whether there is or not hole transmission layers, and can be divided into the carbon-based perovskite solar energy of no hole transmission layer
Battery and the carbon-based perovskite solar battery for having hole transmission layer.Compared with metal based perovskite solar battery, carbon-based calcium
Titanium ore solar battery due to not being related to expensive noble metal and its manufacture craft, cost is cheaper and technique more
Simply.In addition, the carbon-based perovskite of no hole transmission layer is too compared with the carbon-based perovskite solar battery for having hole transmission layer
Positive energy battery is not only not necessarily to hole transmission layer, but also Fabrication Technology of Electrode avoids adopting only with low-cost printing technology
The spin coating technique of industrialized production, therefore its work are difficult to required for the carbon-based perovskite solar battery for having hole transmission layer
Industry development prospect is more good.
Carbon electrode is the back electrode of the carbon-based perovskite solar battery of no hole transmission layer, it is not only the important of battery
Component part, and also carry hole transport and constitute the effect of electronic loop.Therefore, the performance of carbon electrode can greatly shadow
Ring the performance of battery.Whether the performance for investigating the carbon electrode of the carbon-based perovskite solar battery without hole transmission layer is fine or not main
Two aspects are shown, first is that the thickness of carbon electrode layer；Second is that the surface resistance of carbon electrode layer.Wherein, the thickness of carbon electrode layer
Related with the perfusion of perovskite precursor solution, too thick carbon electrode layer certainly will affect the perfusion effect of perovskite precursor solution
Rate, therefore, the thickness of reasonable carbon electrode layer are preferably thinner, but cannot be too thick；The surface resistance of carbon electrode layer and the material of carbon electrode layer
Material is related with thickness, and for determining carbon electrode layer material, the surface resistance of carbon electrode layer is the thickness with carbon electrode layer
Increase and reduce, and variation tendency be it is first big after small, finally tend towards stability.As it can be seen that the thickness and surface resistance of carbon electrode layer are
A pair of contradictory body, to obtain excellent carbon electrode performance, just must thickness to carbon electrode layer and surface resistance carry out it is rationally excellent
Change.The thickness and surface resistance that are effectively reduced carbon electrode are the prior development directions of this kind of solar cell.However, we investigate hair
Existing, most carbon electrode research mainly concentrates on small area battery at present, and focus on optimizing material composition and
On the thickness of carbon electrode, to obtain reasonable result.And in area battery, although also having been reported that, way and
Small area battery is the same.Compared with small area battery, area battery, as carbon electrode area increases, the internal resistance of cell increases, empty
Energy loss is big in the transmission process of cave, and the photoelectric conversion efficiency of battery will substantially reduce.In order to reduce in battery to the maximum extent
The increase of resistance, it is necessary to carry out low resistance modification to carbon electrodes for area battery.That merely uses small area
The technology of battery is clearly infeasible for area battery.Undoubtedly, above-mentioned deficiency will limit the further of this kind of battery
Promote the process with industrialization development.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of low resistance electrodes, system
Method and its application on carbon-based perovskite solar battery.
The purpose of the present invention can be achieved through the following technical solutions: a kind of low resistance electrode, which is characterized in that the 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, the plane carbon-coating are planar junction
Structure, the carbon refers to or carbon web frame layer refers to for carbon or carbon web frame；The carbon refers to or carbon web frame layer is arranged in planar carbon
On layer, coverage rate is no more than 80%.Compared with the surface resistance of individual plane carbon-coating, two-layer compound carbon-coating structure is due to flat
Carbon has been introduced on the carbon-coating of face to refer to or carbon web frame layer, to have bigger thickness, therefore there can be 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
Reduce the energy loss during electronics or hole transport, plays the role of in entire electronic loop low-resistance.
Between the carbon layers having thicknesses and carbon-coating sheet resistance of the electrode be in inverse ratio, refer to carbon layers having thicknesses increase, carbon
Layer sheet resistance reduce instead, the trend of reduction be first rapidly after slowly, be finally intended to stationary value.The thickness of plane carbon-coating selects
The thickness reduced rapidly positioned at carbon-coating sheet resistance with the increase of carbon layers having thicknesses, preferred thickness is within the scope of a thickness area
Arbitrary value；Carbon refer to or the thickness of carbon web frame layer selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend is opened
Begin the thickness for being intended to stationary value, and preferred thickness is the arbitrary value of a thickness area range；The thickness of the plane carbon-coating
Degree is 5-20 microns；The carbon refer to or carbon web frame layer with a thickness of 30-100 microns.
The plane carbon-coating with a thickness of 10 microns；The carbon refer to or carbon web frame layer with a thickness of 30-50 microns.
The carbon refers to or the thickness of carbon web frame layer, if thickness is too small, carbon refers to or the resistance of carbon web frame layer peace
The resistance of face carbon-coating is not much different, and low resistive can be not good enough；If thickness is excessive, carbon refer to or the thickness of carbon web frame layer too
Thickness, it is little to the effect of low resistive energy, but also it is easy to appear the detrimental effects such as film layer cracking.
The 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 item
Carbon refers to the carbon-coating structure of composition, n >=2, and carbon refers to as the carbon-coating structure of similar finger shape, and carbon refers to that one end open, the other end are mutual
Connection, two sides are straight line or curve；The shape that carbon refers to includes that single carbon refers to or more carbon refer to；
The 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 is more grid carbon nets as n >=2, and more grid carbon nets include closing structure or hatch frame, and closing structure is that carbon net is complete
Portion is made of the grid being closed, and hatch frame is that be that the grid that is referred to and be closed by carbon is compound constituted carbon net；Constitute grid line be
Straight line or curve；The shape of carbon net includes single grid carbon net, vertical-shaped more grid carbon nets, the more grid carbon nets of horizontal shape, hands over the more grids of shape
Carbon net and more grid single carbons refer to that composite carbon net and the more carbon of more grids refer to any one of composite carbon net or several.
The line width range that the carbon refers to is 0.2mm-2mm, and line thickness is greater 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 layer, carbon refer to that length b is to be less than or equal to or the length of the carbon-coating greater than Tan Zhi lower layer；
The line width range of the carbon net is 0.5mm-5mm, and line thickness is greater than or equal to 10 microns, the overall width of carbon net
C is less than or equal to the width of the carbon-coating of carbon side off the net, and Gridding length d is less than or equal to or the length of the carbon-coating greater than carbon side off the net
Degree.
The line width range that the carbon refers to is 0.5-1mm, and line is with a thickness of 10-50 microns；The line width of the carbon net
Range is 1-3mm, and line is with a thickness of 15-50 microns.
A kind of preparation method of low resistance electrode, which comprises the following steps:
(1) prepared by low resistance carbon pastes；
Graphite, carbon black, inorganic oxide, organic thickening agent and solvent are mixed, carbon is made using ball milling or three roller methods
Slurry, the weight ratio of the graphite and carbon black are 1-10:1, and solid content shared by graphite and carbon black is 10- in the carbon slurry
60wt%, solid content shared by inorganic oxide are 1-10wt%, and solid content shared by organic thickening agent is 1-10wt%；
(2) working curve between carbon layers having thicknesses and sheet resistance is established
Carbon-coating is made by method for printing screen, knife coating or spray coating method in carbon pastes obtained by step (1), then in 350-
500 DEG C sintering 10-60 minutes, with four probe instruments or ohmmeter measurement carbon-coating resistance, establish carbon layers having thicknesses and side
Working curve between resistance；The thickness of the carbon-coating is controlled by the number for printing or scratching or spray；
(3) suitable depth of two-layer compound carbon-coating structure is determined
According to working curve obtained by step (2), selection is located at carbon-coating sheet resistance and reduces rapidly with the increase of carbon layers having thicknesses
Thickness of the thickness as plane carbon-coating；Selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend starts to tend to
Refer to as carbon or the thickness of carbon web frame layer in the thickness of stationary value；
(4) preparation of plane carbon-coating
The determined thickness plane carbon-coating of step (3) is made using method for printing screen, knife coating or spray coating method, and in 350-
500 DEG C sintering 10-60 minutes；
(5) low resistance carbon refers to or the preparation of carbon web frame layer
Design carbon as needed refers to or the shape and size of carbon net, on the plane carbon-coating obtained by step (4), using screen printing
The carbon that step (3) determined thickness is made in brush method, knife coating or spray coating method refers to or carbon net, and in 350-500 DEG C of sintering 10-60
Minute is to get low resistance electrode.
Solid content shared by graphite and carbon black is 25-35wt% in step (1) carbon slurry, shared by inorganic oxide
Solid content is 2-5wt%, and solid content shared by organic thickening agent is 2-5wt%；The nanometer particle size of the carbon black is less than 50
Nanometer；The graphite is graphite flake or graphite nodule；The carbon black is nano carbon black, and nanometer particle size is less than 100 nanometers, preferably
For less than 50 nanometers；The weight ratio of the graphite and carbon black is 1-5:1；The inorganic oxide be titanium oxide, zirconium oxide,
Aluminium oxide or silica；The organic thickening agent is cellulose or hydroxypropyl cellulose；The solvent is water, ethyl alcohol, pine
One or more of 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 minutes；
The raw material that step (4) makes plane carbon-coating uses carbon pastes obtained by step (1) or ready-made carbon refers to or carbon web material
Expect or ready-made carbon refers to or the mixing material of carbon net materials and step (1) described carbon pastes.
Low resistance electrode obtained by step (5) referred to using four probe instruments or ohmmeter test plane carbon-coating and carbon or
The sheet resistance of carbon web frame layer, plane carbon-coating and carbon refer to or the resistance of carbon web frame layer between difference, difference is bigger, low-resistance
Performance is better.
A kind of application of low resistance electrode, which is characterized in that low resistance electrode is used in the carbon-based perovskite without hole too
It is positive can be on battery, the especially carbon electrode of area battery.Low resistance electrode of the invention is used in the carbon-based perovskite without hole
On solar battery, the surface resistance of carbon electrode layer can be effectively reduced, reduce the energy during hole transport and electronic loop
Loss.In addition, calcium titanium will not be influenced since the carbon on plane carbon-coating refers to or carbon net is the form using lines or grid
Mine precursor solution passes through the osmotic efficiency of carbon electrode layer, to improve the photoelectric conversion efficiency of battery.
In order to realize the purposes of above-mentioned low resistance electrode, using following specific steps:
(1) conductive substrates are handled
It uses electro-conductive glass for conductive substrates, successively carries out substrate etching, substrate washing and drying treatment；The substrate
Etching is mainly laser ablation or chemical etching；The substrate cleaning is mainly solvent cleaning or ozone clean or ultralow temperature
Carbon dioxide cleaning, drying means is heat drying；
(2) compacted zone makes
The conductive substrates surface obtained by step (1) makes nano-oxide compacted zone by spin-coating method or spray pyrolysis；
The dense layer thickness is less than 100 nanometers, preferably with a thickness of 30-50 nanometers.
The nano-oxide is mainly titanium oxide；
The spin-coating method is exactly to be prepared under certain rotation speed on spin coating instrument using nano-oxide spin coating liquid
Ultra-thin oxide membranous layer is formed, and is obtained by high temperature sintering；The rotation speed is 500-8000rpm, preferred to turn
Speed is 2000-5000rpm；The high temperature sintering temperature is 400-600 DEG C, and preferred temperature is 500-550 DEG C；The burning
Tying the time is 15-120 minutes, preferably 30-90 minutes.
The spray pyrolysis is the conductive base being sprayed on titanium source precursor solution using sprayer in the thermal station of high temperature
On bottom, titanium source presoma is decomposed to form rapidly nano-oxide compacted zone under the action of high temperature.
The titanium source precursor solution is mainly the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl esters, described
The temperature of high temperature sintering be generally 400-600 DEG C, preferred temperature is 500-550 DEG C.
(3) mesoporous layer production
Suitable nano-oxide slurry is added on web plate, on the surface using scraper compacted zone obtained by step (2)
It prints and is formed with certain thickness mesoporous layer, which forms stable mesoporous layer structure after high temperature sintering；Institute
The mesoporous layer stated is with a thickness of 1-5 microns, preferably less than 1-3 microns.
The nano-oxide slurry is mainly nano-titanium oxide slurry, nanometer alumina slurry, preferably nanometer
The 18NR-T slurry or 30NR-D slurry of titanium oxide；The high temperature sintering temperature of the mesoporous layer is generally 400-600 DEG C, preferably
Temperature be 500-550 DEG C.
(4) insulating layer makes
Suitable nano-oxide slurry is added on web plate, on the surface using scraper mesoporous layer obtained by step (3)
It prints and is formed with certain thickness insulating layer, which forms stable insulation aperture layer structure after high temperature sintering,
The thickness of insulating layer is 1-5 microns, preferably less than 1-3 microns.
The nano-oxide slurry is mainly nano zircite slurry, nanometer alumina slurry, nano silicon oxide slurry
Material, preferably nano zircite slurry；The nano zircite slurry, partial size are 20-100 nanometers, preferred partial size
It is 20-50 microns；The high temperature sintering temperature of the insulating layer is generally 400-600 DEG C, and preferred temperature is 500-550 DEG C.
(5) planar carbon electrode layer makes
The surface of insulating layer obtained by step (4) makes plane carbon-coating using the method for plane carbon-coating above-mentioned；Planar carbon
The thickness of electrode layer is generally 5-20 microns, preferably with a thickness of 10 microns.
(6) carbon refers to or carbon web frame layer makes
Refer to carbon above-mentioned or the method for carbon web frame layer.The carbon refers to or the thickness of carbon web frame layer is generally 30-
100 microns, preferably with a thickness of 30-50 microns.The carbon refers to or one end of carbon web frame layer is located at the outside of plane carbon-coating,
It is contacted with conductive substrates, the other end is located in planar carbon electrode layer surface, contacts with planar carbon electrode layer.
(7) absorption of perovskite precursor solution
The absorption of perovskite precursor solution is carried out using two-step method or one-step method, the two-step method is first will be certain
The iodate lead solution of amount from carbon refer to or carbon web frame layer in instill and penetrate into mesoporous layer or insulating layer, heating at 70 DEG C makes
The electrode for adsorbing lead iodide, is then immersed in methylamine iodine solution several minutes, takes out juxtaposition after black is formed by solvent volatilization
Solvent is removed in heating in 50 DEG C of thermal station, forms perovskite battery；
The one-step method be by a certain amount of methylamine lead iodine precursor solution from carbon refer to or carbon web frame layer in instill simultaneously
It penetrates into mesoporous layer or insulating layer, then heating makes solvent volatilize at 100 DEG C, and forms perovskite battery.
The iodate lead solution, dosage are generally micro updating or milliliter grade, 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,
Preferred concentration is 1 mol/L.
The solution of the first ammonia iodine, dosage generally submerge electrode；Its solvent be mainly isopropanol, ethyl alcohol or
Their mixed solvent；Its concentration is generally 5-15 mg/ml, and preferred concentration is 10 mg/mls.
The methylamine lead iodine precursor solution, dosage are generally micro updating or milliliter grade, 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 are 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 (FF), photoelectric conversion efficiency (η).
Compared with prior art, the invention has the following advantages that
1. what technology of the invention was related to refers to or the low resistance electrode of carbon web frame layer comprising carbon, can be effectively reduced carbon-based
The surface resistance of the carbon electrode layer of perovskite solar battery reduces the energy loss during hole transport and electronic loop, from
And improve the photoelectric conversion efficiency of battery；
2. what technology of the invention was related to refers to or the low resistance electrode of carbon web frame layer comprising carbon, since its structure is to use
The form of lines or grid, therefore the osmotic efficiency that perovskite precursor solution passes through carbon electrode layer will not be influenced；
3. what technology of the invention was related to refers to or the low resistance electrode of carbon web frame layer comprising carbon, it both can be used for small area
Battery can be used for area battery；
4. what technology of the invention was related to refers to or the low resistance electrode of carbon web frame layer comprising carbon, lower cost for material, system
Make simple process, can both laboratory was suitble to prepare, can be used for bulk industrial production；
5. what technology of the invention was related to refers to or the low resistance electrode of carbon web frame layer comprising carbon, using stable carbon materials
Any reaction or corrosion will not occur for material and other electrode materials, be conducive to the stability for improving battery.
Detailed description of the invention
Fig. 1 is the relational graph between the carbon layers having thicknesses and carbon-coating sheet resistance of certain carbon pastes；
Fig. 2 is the structural schematic diagram that carbon refers to, a is carbon finger widths in figure；B is that carbon refers to length；E is adjacent finger line spacing；
Fig. 3 is two-layer compound carbon-coating structure sheaf；6 refer to or carbon web frame layer in figure for carbon, and 5 be plane carbon-coating；
Fig. 4 is carbon web frame schematic diagram, and c is carbon net width in figure；D is carbon net length；E is adjacent finger line spacing；F: phase
Neighbour refers to line spacing；
Fig. 5 refers to for low resistance carbon or the schematic diagram of the carbon-based perovskite solar battery without hole of carbon net；
Fig. 6 is the top view of Fig. 5；
In figure, 1 is conductive layer；2 be compacted zone；3 be mesoporous layer；4 be insulating layer；5 be plane carbon-coating；6 refer to or carbon for carbon
Web frame layer；
Specific embodiment
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 2 grams of graphite flake (325 mesh of partial size), 8 grams of graphite flake (7-12 microns of partial size), carbon black (30 microns of average grain diameter) 2
Gram, 1 gram of zirconium oxide (< 50 microns), 1 gram of cellulose mixing be placed in 30 grams of terpinol, then on zirconia ball mill
Ball milling 12 hours, revolving speed 400rpm prepared low resistance carbon electrode slurry.Wherein, the solid content C% of carbon component is 27.3%.
2. establishing the working curve between carbon layers having thicknesses and sheet resistance
5 grams of low resistance carbon electrode slurry is taken, using the silk-screen printing web plate of 150 mesh, is formed according to different print pass
The carbon-coating of different-thickness, and be sintered 30 minutes respectively at 400 DEG C.Carbon layers having thicknesses are measured using step instrument, and sheet resistance uses four probes
Resistance meter measurement.Relationship between obtained carbon electrode thickness degree and sheet resistance.When the thickness of carbon-coating is less than 20 microns, carbon
The sheet resistance of layer is significantly reduced with the increase of the thickness of carbon-coating, when the thickness of carbon-coating is greater than 30 microns, the sheet resistance of carbon-coating with
The increase of the thickness of carbon-coating and slowly reduce, finally tend to stablize.As shown in Figure 1.
3. determining the suitable depth of two-layer compound carbon-coating structure
Based on the relationship between carbon layers having thicknesses and carbon-coating sheet resistance, 10 microns of the suitable depth and list of plane carbon-coating are selected respectively
Refer to 40 microns of thickness of carbon.Corresponding sheet resistance is that the sheet resistance of 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；
5 grams of low resistance carbon pastes (solid content 27.3%) are taken, using 250 mesh silk screen web plate, in a kind of clean glass
On the surface substrate 50 × 50 (mm), one layer of carbon electrode layer is printed, electrode area length × width is 40 × 35 (mm), the carbon electricity after printing
Pole layer passes through 400 DEG C high temperature sintering 30 minutes.Through measuring, sintered plane carbon-coating with a thickness of 9 microns.
5. single carbon refers to that structure sheaf (n=2) makes
5 grams of low resistance carbon pastes (solid content 27.3%) are taken, using 150 mesh silk screen web plate, on the surface of plane carbon-coating
On, it prints one layer of single carbon and refers to structure sheaf.Single carbon refer to the shape of structure sheaf as in Fig. 2 single carbon refer to shown in I that length b × width a is
35 × 30 (mm), line width 1mm, adjacent finger line spacing 28mm.Single carbon refers to that structure sheaf is located at the inside of plane carbon-coating.After printing
Single carbon refer to structure sheaf by 400 DEG C high temperature sintering 30 minutes.It is measured through step instrument, the single carbon that printing is 2 times refers to structure sheaf through burning
Line after knot is with a thickness of 35 microns.
For gained two-layer compound carbon-coating structure sheaf as shown in figure 3,1 refers to or carbon web frame layer for carbon, 2 be plane carbon-coating.
6. resistance test and performance evaluation
The sheet resistance of above-mentioned plane carbon-coating is tested respectively using four probe instruments and single carbon refers to the sheet resistance of structure sheaf, knot
Fruit is that the sheet resistance of plane carbon-coating is 21 Europe, and single carbon refers to that the sheet resistance of structure sheaf is 7 Europe.
Embodiment 2:
More carbon refer to the production of structure (n=3)
1. prepared by low resistance carbon pastes
With embodiment 1.
2. establishing the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determining 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
5 grams of low resistance carbon pastes (solid content 27.3%) are taken, using 150 mesh silk screen web plate, 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 such as carbon more in Fig. 2 of structure sheaf refer to shown in II, length b × width a
For 38 × 30 (mm), line width 1mm, adjacent finger line spacing 13.5mm.Three carbon refer to that structure sheaf is located at the inside of plane carbon-coating.Print
Three carbon after brush refer to that structure sheaf passes through 400 DEG C high temperature sintering 30 minutes.It is measured through step instrument, three carbon after printing 2 times refer to structure
The sintered line of layer is with a thickness of 40 microns.
6. resistance test and performance evaluation.
The sheet resistance of above-mentioned plane carbon-coating is tested respectively using four probe instruments and single carbon refers to the sheet resistance of structure sheaf, knot
Fruit is that the sheet resistance of plane carbon-coating is 21 Europe, and more carbon refer to that the sheet resistance of structure sheaf is 5 Europe.
Embodiment 3:
The production of single network layer (n=1)
1. prepared by low resistance carbon pastes
With embodiment 1.
2. establishing the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determining 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
5 grams of low resistance carbon pastes (solid content 27.3%) are taken, using 150 mesh silk screen web plate, on the surface of plane carbon-coating
On, print one layer of single network layer.The shape of single network layer is as shown in grid III single in Fig. 4, length c × width d
For 45 × 30 (mm), line width 1mm, adjacent finger line spacing 28mm.The open at one end of single network layer is located at plane carbon-coating
Inside, another closed end is located at the outside of plane carbon-coating, exposes external length 8mm.More carbon after printing refer to that structure sheaf passes through
Cross 400 DEG C of high temperature sinterings 30 minutes.It is measured through step instrument, the single carbon that printing is 2 times refers to that the sintered line of structure sheaf is micro- with a thickness of 38
Rice.
6. resistance test and performance evaluation
The sheet resistance of above-mentioned plane carbon-coating is tested respectively using four probe instruments and single carbon refers to the sheet resistance of structure sheaf, knot
Fruit is that the sheet resistance of plane carbon-coating is 21 Europe, and more carbon refer to that the sheet resistance of structure sheaf is 6 Europe.
Embodiment 4:
The production of vertical-shaped three networks layer (n=3)
1. prepared by low resistance carbon pastes
With embodiment 1.
2. establishing the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determining the suitable depth of two-layer compound carbon-coating structure
With embodiment 1.
4. the preparation of plane carbon-coating；
With embodiment 1.
5. vertical-shaped three networks layer (n=3) production
5 grams of low temperature carbon pastes (solid content 27.3%) are taken, using 150 mesh silk screen web plate, on the surface of plane carbon-coating,
Print one layer of vertical-shaped three networks layer.The shape of vertical-shaped three networks layer as shown in more grid carbon net IV vertical-shaped in Fig. 4,
Length c × width d is 45 × 30 (mm), line width 1mm, adjacent finger line spacing 13.5mm.The one of vertical-shaped three networks layer
End is located at the inside of plane carbon-coating, and the other end is located at the outside of plane carbon-coating, exposes external length 8mm.It is vertical-shaped after printing
Three network layers pass through 400 DEG C high temperature sintering 30 minutes.It is measured through step instrument, the vertical-shaped three networks layer that printing is 2 times is burnt
Line after knot is with a thickness of 37 microns.
6. resistance test and performance evaluation.
Test the sheet resistance of above-mentioned plane carbon-coating and the side of vertical-shaped three networks layer respectively using four probe instruments
Resistance, result is that the sheet resistance of plane carbon-coating is 21 Europe, and the sheet resistance of vertical-shaped three networks layer is 6 Europe.
Embodiment 5:
Hand over the more grid carbon web frame layer production of shape
1. prepared by low resistance carbon pastes
With embodiment 1.
2. establishing the working curve between carbon layers having thicknesses and sheet resistance
With embodiment 1.
3. determining the suitable depth of two-layer compound carbon-coating structure
With embodiment 1.
4. the preparation of plane carbon-coating；
With embodiment 1.
5. handing over the more grid carbon web frame layer production of shape
5 grams of low temperature carbon pastes (solid content 27.3%) are taken, using 150 mesh silk screen web plate, on the surface of plane carbon-coating,
One layer of more grid carbon web frame layer of friendship shape is printed, hands over the shape of the more grid carbon web frame layers of shape as shown in grid VI single in Fig. 4,
Length c × width d is 45 × 30 (mm), line width 1mm.The more grid carbon web frame layers of the friendship shape include vertical-shaped four grids carbon net and
The double grid carbon nets of horizontal shape.Wherein, the adjacent finger line width of vertical-shaped four grids carbon web frame layer is 8mm, the double grid carbon nets of horizontal shape
Adjacent finger line width be 13.5mm.One end of the more grid carbon web frame layers of shape is handed over to be located at the inside of plane carbon-coating, the other end
Positioned at the outside of plane carbon-coating, expose external length 10mm.The more grid carbon web frame layers of friendship shape after printing pass through 400 DEG C of height
Temperature sintering 30 minutes.It is measured through step instrument, the sintered line of the more grid carbon web frame layers of friendship shape that printing is 2 times is micro- with a thickness of 37
Rice.
6. resistance test and performance evaluation
The sheet resistance of above-mentioned plane carbon-coating is tested respectively using four probe instruments and hands over the more grid carbon web frame layers of shape
Sheet resistance, result is that the sheet resistance of plane carbon-coating is 21 Europe, hand over the more grid carbon web frame layers of shape sheet resistance be 6 Europe.
Embodiment 6:
As seen in figs. 5-6, low resistance single carbon refers to the preparation of carbon-based perovskite solar battery
1) conductive substrates are handled
Laser ablation is carried out to the FTO electro-conductive glass of 50 × 50 (mm) first, the position of etching is in conducting surface 40 × 50
(mm) and the boundary of 10 × 50 (mm) has a width for the etching groove of 3mm, which is divided into 38.5 × 50 for conducting surface
(mm) and two parts 8.5 × 50 (mm).Then etching conductive substrate is successively clear with alkali glass water, water and EtOH Sonicate respectively
It washes, until clean, dried for standby obtains conductive layer 1 (as shown in Figure 5).
2) compacted zone makes
The aqueous isopropanol for configuring two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl esters of 10wt% first, then leads clean
Electric layer 1 (electro-conductive glass) is placed on 450 DEG C of warm table, and the conduction of glass up, then uses sprayer by two-(acetyl
Acetone) aqueous isopropanol of-metatitanic acid diisopropyl ester is equably sprayed on conducting surface one layer of ultra-thin titanium dioxide dense of formation
Layer 2.Compacted zone 2 forms about 50 ran of thickness after 500 DEG C are sintered 30 minutes.
3) mesoporous layer production
Using screen printing technique, the titania slurry prepared in advance (solid content 1.5%, solvent are terpinol) is printed
Brush obtains mesoporous layer on the surface of above-mentioned compacted zone 2, and the electrode area of mesoporous layer is 30 × 40 (mm), and two after printing
Medium pore of titania layer passes through 500 DEG C high temperature sintering 30 minutes.At this point, mesoporous layer 3 with a thickness of 2 microns.
4) insulating layer makes
Using screen printing technique, the zirconium dioxide slurry prepared in advance (solid content 1.5%, solvent are terpinol) is printed
Brush obtains insulating layer 4 on the surface of above-mentioned mesoporous layer 3, and the electrode area of the insulating layer 4 is 32 × 45 (mm), after printing
Insulating layer by 500 DEG C high temperature sintering 30 minutes.At this point, insulating layer 4 with a thickness of 2 microns.
5) plane carbon-coating makes
Using screen printing technique, low resistance carbon pastes (solid content 30%, solvent are terpinol) are printed on above-mentioned
On the surface of insulating layer 4, plane carbon-coating 5 is obtained, the electrode area of plane carbon-coating 5 is 32 × 45 (mm), the planar carbon after printing
Layer 5 passes through 400 DEG C high temperature sintering 30 minutes.At this point, plane carbon-coating 5 with a thickness of 10 microns.
6) single carbon refers to that structure sheaf makes
Using screen printing technique, low resistance carbon pastes (solid content 30%, solvent are terpinol) are printed on above-mentioned
On the surface of plane carbon-coating 5, obtains carbon and refer to structure sheaf 6, the shape that carbon refers to refers to for single carbon, sees Fig. 2.The size that single carbon refers to is single carbon
Finger length is 36mm, and single carbon finger widths are 40mm, and every line width is 2mm, adjacent finger line spacing 38mm, and single carbon refers to structure sheaf
Open at one end is located at the inside of plane carbon-coating, and another closed end is located at the outside of plane carbon-coating, exposes external length 8mm.Print
Single carbon after brush 2 times refers to that structure sheaf passes through 400 DEG C high temperature sintering 30 minutes.Sintered single carbon refers to the micro- with a thickness of 38 of structure sheaf
Rice.
7) absorption of perovskite precursor solution
Take the DMF solution (solid content of about 1 milliliter of pre-prepd perovskite precursor solution CH3NH3PbI3
40wt%), drop refers to the surface of structure sheaf 6 in carbon, static 5 minutes, solution is allowed to penetrate into lower layer, electrode is then placed in 70 DEG C
It is heated 30 minutes in thermal station, removes volatile solvent, while perovskite CH3NH3PbI3 crystallization is complete, battery assembly finishes.
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 (FF), photoelectric conversion efficiency (η).It the results are shown in Table 1.
Embodiment 7:
The preparation of the low resistance friendship carbon-based perovskite solar battery of the more grid carbon nets of shape
1) conductive substrates processing, compacted zone production, the production of mesoporous layer, insulating layer production, the production of plane carbon-coating, same to embodiment
Six.
2) the more grid carbon web frame layer production of shape are handed over
5 grams of low temperature carbon pastes (solid content 27.3%) are taken, using 150 mesh silk screen web plate, on the surface of plane carbon-coating,
One layer of more grid carbon web frame layer of friendship shape is printed, hands over the shape of the more grid carbon web frame layers of shape as shown in grid IV single in Fig. 4,
Length x width is 36 × 40 (mm), line width 2mm.The more grid carbon web frame layers of the friendship shape include vertical-shaped four grids carbon net and cross
The double grid carbon nets of shape.Wherein, the adjacent finger line width of vertical-shaped four grids carbon web frame layer is 8mm, the double grid carbon nets of horizontal shape
Adjacent finger line width is 15mm.One end of the more grid carbon web frame layers of shape is handed over to be located at the inside of plane carbon-coating, the other end is located at
External length 10mm is exposed in the outside of plane carbon-coating.The more grid carbon web frame layers of friendship shape after printing are burnt by 400 DEG C of high temperature
Knot 30 minutes.It is measured through step instrument, the sintered line of the more grid carbon web frame layers of friendship shape that printing is 2 times is with a thickness of 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 (FF), photoelectric conversion efficiency (η).It the results are shown in Table 1.
Embodiment 8:
No low resistance carbon refers to or the preparation of the carbon-based perovskite solar battery of carbon net
1) before conductive substrates processing, compacted zone production, the production of mesoporous layer, insulating layer production, the production of plane carbon-coating, perovskite
The absorption for driving liquid solution, with embodiment six.The difference lies in that this step does not have carbon to refer to or the production 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 (FF), photoelectric conversion efficiency (η).It the results are shown in Table 1.
Table 1
As can be seen that every battery performance is all without the electrode that two-layer compound carbon-coating structure is arranged as described herein
Not as good as the electrode for being provided with two-layer compound carbon-coating structure of the present invention, especially photoelectric conversion efficiency has obtained greatly mentioning
It is high.
Embodiment 9
(1) conductive substrates are handled
It uses electro-conductive glass for conductive substrates, successively carries out substrate etching, substrate washing and drying treatment；The substrate
Etching is mainly chemical etching；The substrate cleaning is mainly ozone clean, and drying means is heat drying；
(2) compacted zone makes
The conductive substrates surface obtained by step (1) makes nano-oxide compacted zone by spin-coating method；The compacted zone
Thickness is less than 100 nanometers.
The nano-oxide is mainly titanium oxide；The spin-coating method is exactly that nano-oxide spin coating liquid is used to revolve
It applies to prepare under the rotation speed of 500rpm on instrument and forms ultra-thin oxide membranous layer, and pass through 400 DEG C high temperature sintering 120 minutes
And it obtains.
(3) mesoporous layer production
Suitable nanometer alumina slurry is added on web plate, on the surface using scraper compacted zone obtained by step (2)
1 micron of mesoporous layer is printed and is formed, which forms stable mesoporous layer structure after 400 DEG C of high temperature sinterings.
(4) insulating layer makes
Suitable nanometer alumina slurry is added on web plate, on the surface using scraper mesoporous layer obtained by step (3)
1 micron of insulating layer is printed and is formed, which forms stable insulation aperture layer structure, institute after the sintering of 1 um high temperature
The thickness of insulating layer stated is 1 micron.
(5) planar carbon electrode layer makes
The surface of insulating layer obtained by step (4) makes plane carbon-coating using the method for following plane carbon-coating；Planar carbon electricity
Pole layer with a thickness of 5 microns.
The preparation of plane carbon-coating:
(a) prepared by low resistance carbon pastes；
Graphite, carbon black, inorganic oxide, organic thickening agent and solvent are mixed, carbon is made using ball milling or three roller methods
Slurry, the weight ratio of the graphite and carbon black are 1:1, and solid content shared by graphite and carbon black is 10wt%, nothing in the carbon slurry
Solid content shared by machine oxide is 10wt%, and solid content shared by organic thickening agent is 1wt%；
The graphite is graphite flake；The carbon black is nano carbon black；The inorganic oxide is titanium oxide；It is described
Organic thickening agent be cellulose；The solvent is water.
(b) working curve between carbon layers having thicknesses and sheet resistance is established
Carbon-coating is made by spray coating method in carbon pastes obtained by step (a), is then sintered 60 minutes in 350 DEG C, with four probes
The resistance of resistance meter or ohmmeter measurement carbon-coating, establishes the working curve between carbon layers having thicknesses and sheet resistance；The carbon-coating
Thickness is controlled by the number for printing or scratching or spray；
(c) suitable depth of two-layer compound carbon-coating structure is determined
According to working curve obtained by step (b), selection is located at carbon-coating sheet resistance and reduces rapidly with the increase of carbon layers having thicknesses
Thickness of the thickness as plane carbon-coating；Selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend starts to tend to
Refer to as carbon the thickness of structure sheaf in the thickness of stationary value；
(d) preparation of plane carbon-coating
The determined thickness plane carbon-coating of step (c) is made using method for printing screen, knife coating or spray coating method, and in 350
DEG C sintering 60 minutes, arrive plane carbon-coating；
(6) carbon refers to that structure sheaf makes
The shape and size that design carbon refers to as needed are made step (c) using spray coating method and determine on plane carbon-coating
The carbon of thickness refers to, and is sintered 60 minutes in 350 DEG C, and obtained carbon refers to that the thickness of structure sheaf is generally 30 microns.The carbon refers to
One end of structure sheaf is located at the outside of plane carbon-coating, contacts with conductive substrates, and the other end is located in planar carbon electrode layer surface, with
The contact of planar carbon electrode layer.
(7) absorption of perovskite precursor solution
A certain amount of iodate lead solution is referred to from carbon first and instills and penetrates into structure sheaf in mesoporous layer or insulating layer,
Heating makes solvent volatilize at 70 DEG C, is then immersed in the electrode for adsorbing lead iodide in methylamine iodine solution several minutes, to black shape
Heating in 50 DEG C of thermal station is placed at rear taking-up and removes solvent, forms perovskite battery；The iodate lead solution, dosage
For micro updating；Its solvent is mainly dimethylformamide；Its concentration is 0.5 mol/L.
The solution of the first ammonia iodine, dosage are submergence electrode；Its solvent is mainly isopropanol；Its concentration is general
For 5 mg/mls.
(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 (FF), photoelectric conversion efficiency (η).It is shown in Table 2.
Embodiment 10
(1) conductive substrates are handled
It uses electro-conductive glass for conductive substrates, successively carries out substrate etching, substrate washing and drying treatment；The substrate
Etching is mainly chemical etching；The substrate cleaning is mainly ozone clean, and drying means is heat drying；
(2) compacted zone makes
The conductive substrates surface obtained by step (1) makes nano-oxide compacted zone by spin-coating method；The compacted zone
Thickness is less than 50 nanometers.
The nano-oxide is mainly titanium oxide；The spin-coating method is exactly that nano-oxide spin coating liquid is used to revolve
It applies to prepare under the rotation speed of 8000rpm on instrument and forms ultra-thin oxide membranous layer, and pass through 600 DEG C high temperature sintering 15 minutes
And it obtains.
(3) mesoporous layer production
Suitable nanometer alumina slurry is added on web plate, on the surface using scraper compacted zone obtained by step (2)
5 microns of mesoporous layer is printed and is formed, which forms stable mesoporous layer structure after 600 DEG C of high temperature sinterings.
(4) insulating layer makes
Suitable nanometer alumina slurry is added on web plate, on the surface using scraper mesoporous layer obtained by step (3)
5 microns of insulating layer is printed and is formed, which forms stable insulation aperture layer structure, institute after the sintering of 5 um high temperatures
The thickness of insulating layer stated is 5 microns.
(5) planar carbon electrode layer makes
The surface of insulating layer obtained by step (4) makes plane carbon-coating using the method for following plane carbon-coating；Planar carbon electricity
Pole layer with a thickness of 20 microns.
The preparation of plane carbon-coating:
(a) prepared by low resistance carbon pastes；
Graphite, carbon black, inorganic oxide, organic thickening agent and solvent are mixed, carbon is made using ball milling or three roller methods
Slurry, the weight ratio of the graphite and carbon black are 10:1, and solid content shared by graphite and carbon black is 60wt%, nothing in the carbon slurry
Solid content shared by machine oxide is 10wt%, and solid content shared by organic thickening agent is 10wt%；
The graphite is graphite nodule；The carbon black is nano carbon black；The inorganic oxide is silica；It is described
Organic thickening agent be hydroxypropyl cellulose；The solvent is ethyl alcohol.
(b) working curve between carbon layers having thicknesses and sheet resistance is established
Carbon-coating is made by knife coating in carbon pastes obtained by step (a), is then sintered 10 minutes in 500 DEG C, with four probes
The resistance of resistance meter or ohmmeter measurement carbon-coating, establishes the working curve between carbon layers having thicknesses and sheet resistance；The carbon-coating
Thickness is controlled by blade coating number；
(c) suitable depth of two-layer compound carbon-coating structure is determined
According to working curve obtained by step (b), selection is located at carbon-coating sheet resistance and reduces rapidly with the increase of carbon layers having thicknesses
Thickness of the thickness as plane carbon-coating；Selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend starts to tend to
Refer to as carbon the thickness of structure sheaf in the thickness of stationary value；
(d) preparation of plane carbon-coating
The determined thickness plane carbon-coating of step (c) is made using knife coating, and is sintered 10 minutes in 500 DEG C, planar carbon is arrived
Layer；
(6) carbon refers to that structure sheaf makes
The shape and size that design carbon refers to as needed are made step (c) using knife coating and determine on plane carbon-coating
The carbon of thickness refers to, and is sintered 10 minutes in 500 DEG C, and obtained carbon refers to that the thickness of structure sheaf is generally 100 microns.The carbon refers to
One end of structure sheaf is located at the outside of plane carbon-coating, contacts with conductive substrates, and the other end is located in planar carbon electrode layer surface, with
The contact of planar carbon electrode layer.
(7) absorption of perovskite precursor solution
A certain amount of iodate lead solution is referred to from carbon first and instills and penetrates into structure sheaf in mesoporous layer or insulating layer,
Heating makes solvent volatilize at 70 DEG C, is then immersed in the electrode for adsorbing lead iodide in methylamine iodine solution several minutes, to black shape
Heating in 50 DEG C of thermal station is placed at rear taking-up and removes solvent, forms perovskite battery；The iodate lead solution, dosage
Generally micro updating or milliliter grade, preferably micro updating；Its solvent is mainly dimethylformamide, dimethyl sulfoxide, in fourth
Ester or their mixed solvent；Its concentration is 1.5 mol/Ls.
The solution of the first ammonia iodine, dosage are submergence electrode；Its solvent is mainly ethyl alcohol；Its concentration is generally
15 mg/mls.
(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 (FF), photoelectric conversion efficiency (η).It is shown in Table 2.
Embodiment 11
(1) conductive substrates are handled
It uses electro-conductive glass for conductive substrates, successively carries out substrate etching, substrate washing and drying treatment；The substrate
Etching is mainly laser ablation；The substrate cleaning is that ultralow temperature carbon dioxide cleans, and drying means is heat drying；
(2) compacted zone makes
The conductive substrates surface obtained by step (1) makes nano-oxide compacted zone by spray pyrolysis；The cause
Close layer is with a thickness of 30 nanometers.
The nano-oxide is mainly titanium oxide；
The spray pyrolysis is the conductive base being sprayed on titanium source precursor solution using sprayer in the thermal station of high temperature
On bottom, titanium source presoma is decomposed to form rapidly nano-oxide compacted zone under the action of 400 DEG C of high temperature.The titanium source forerunner
Liquid solution is mainly the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl esters.
(3) mesoporous layer production
Suitable nano-oxide slurry is added on web plate, on the surface using scraper compacted zone obtained by step (2)
The mesoporous layer of 1 micron thickness is printed and is formed, which forms stable mesoporous layer structure after 400 DEG C of high temperature sinterings.
(4) insulating layer makes
Suitable nano-oxide slurry is added on web plate, on the surface using scraper mesoporous layer obtained by step (3)
The insulating layer of 1 micron thickness is printed and is formed, which forms stable insulation aperture layer knot after 400 DEG C of high temperature sinterings
Structure.
The nano-oxide slurry is nano zircite slurry, and partial size is 20 nanometers.
(5) planar carbon electrode layer makes
The surface of insulating layer obtained by step (4) makes plane carbon-coating using the method for following plane carbon-coating；Planar carbon electricity
Pole layer with a thickness of 5 microns.
The preparation of plane carbon-coating:
(a) prepared by low resistance carbon pastes；
Graphite, carbon black, inorganic oxide, organic thickening agent and solvent are mixed, carbon is made using ball milling or three roller methods
Slurry, the weight ratio of the graphite and carbon black are 5:1, and solid content shared by graphite and carbon black is 25wt%, nothing in the carbon slurry
Solid content shared by machine oxide is 2wt%, and solid content shared by organic thickening agent is 2wt%；
The inorganic oxide is silica；The organic thickening agent is hydroxypropyl cellulose；The solvent is
Glycerol.
(b) working curve between carbon layers having thicknesses and sheet resistance is established
Carbon-coating is made by method for printing screen, knife coating or spray coating method in carbon pastes obtained by step (a), then in 350
DEG C sintering 60 minutes, with four probe instruments or ohmmeter measurement carbon-coating resistance, establish between carbon layers having thicknesses and sheet resistance
Working curve；The thickness of the carbon-coating is controlled by the number for printing or scratching or spray；
(c) suitable depth of two-layer compound carbon-coating structure is determined
According to working curve obtained by step (b), selection is located at carbon-coating sheet resistance and reduces rapidly with the increase of carbon layers having thicknesses
Thickness of the thickness as plane carbon-coating；Selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend starts to tend to
In thickness of the thickness as carbon web frame layer of stationary value；
(d) preparation of plane carbon-coating
The determined thickness plane carbon-coating of step (c) is made using method for printing screen, knife coating or spray coating method, and in 350
DEG C sintering 60 minutes；
(6) carbon web frame layer makes
The shape and size of design carbon net as needed, on step (d) gained plane carbon-coating, using method for printing screen
The carbon net of the determined thickness of step (c) is made, and is sintered 60 minutes in 350 DEG C to get low resistance electrode.The carbon web frame
One end of layer is located at the outside of plane carbon-coating, contacts with conductive substrates, the other end is located in planar carbon electrode layer surface, with plane
The contact of carbon electrode layer.
(7) absorption of perovskite precursor solution
A certain amount of methylamine lead iodine precursor solution is instilled from carbon web frame layer and penetrates into mesoporous layer or insulating layer
In, then heating makes solvent volatilize at 100 DEG C, and forms perovskite battery.
The methylamine lead iodine precursor solution, dosage are 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 (FF), photoelectric conversion efficiency (η).It is shown in Table 2.
Embodiment 12
(1) conductive substrates are handled
It uses electro-conductive glass for conductive substrates, successively carries out substrate etching, substrate washing and drying treatment；The substrate
Etching is mainly laser ablation；The substrate cleaning is that ultralow temperature carbon dioxide cleans, and drying means is heat drying；
(2) compacted zone makes
The conductive substrates surface obtained by step (1) makes nano-oxide compacted zone by spray pyrolysis；The cause
Close layer is with a thickness of 50 nanometers.
The nano-oxide is mainly titanium oxide；
The spray pyrolysis is the conductive base being sprayed on titanium source precursor solution using sprayer in the thermal station of high temperature
On bottom, titanium source presoma is decomposed to form rapidly nano-oxide compacted zone under the action of 600 DEG C of high temperature.The titanium source forerunner
Liquid solution is mainly the aqueous isopropanol of two-(acetylacetone,2,4-pentanedione)-metatitanic acid diisopropyl esters.
(3) mesoporous layer production
Suitable nano-oxide slurry is added on web plate, on the surface using scraper compacted zone obtained by step (2)
The mesoporous layer of 3 micron thickness is printed and is formed, which forms stable mesoporous layer structure after 600 DEG C of high temperature sinterings.
(4) insulating layer makes
Suitable nano-oxide slurry is added on web plate, on the surface using scraper mesoporous layer obtained by step (3)
The insulating layer of 3 micron thickness is printed and is formed, which forms stable insulation aperture layer knot after 600 DEG C of high temperature sinterings
Structure.
The nano-oxide slurry is nano zircite slurry, and partial size is 100 nanometers.
(5) planar carbon electrode layer makes
The surface of insulating layer obtained by step (4) makes plane carbon-coating using the method for following plane carbon-coating；Planar carbon electricity
Pole layer with a thickness of 20 microns.
The preparation of plane carbon-coating:
(a) prepared by low resistance carbon pastes；
Graphite, carbon black, inorganic oxide, organic thickening agent and solvent are mixed, carbon is made using ball milling or three roller methods
Slurry, the weight ratio of the graphite and carbon black are 5:1, and solid content shared by graphite and carbon black is 35wt%, nothing in the carbon slurry
Solid content shared by machine oxide is 5wt%, and solid content shared by organic thickening agent is 5wt%；
The inorganic oxide is zirconium oxide；The organic thickening agent is cellulose；The solvent is ethyl alcohol.
(b) working curve between carbon layers having thicknesses and sheet resistance is established
Carbon-coating is made by method for printing screen in carbon pastes obtained by step (a), is then sintered 10 minutes, uses in 500 DEG C
The resistance of four probe instruments or ohmmeter measurement carbon-coating, establishes the working curve between carbon layers having thicknesses and sheet resistance；It is described
The thickness of carbon-coating is controlled by the number for printing or scratching or spray；
(c) suitable depth of two-layer compound carbon-coating structure is determined
According to working curve obtained by step (b), selection is located at carbon-coating sheet resistance and reduces rapidly with the increase of carbon layers having thicknesses
Thickness of the thickness as plane carbon-coating；Selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend starts to tend to
In thickness of the thickness as carbon web frame layer of stationary value；
(d) preparation of plane carbon-coating
The determined thickness plane carbon-coating of step (c) is made using method for printing screen, knife coating or spray coating method, and in 500
DEG C sintering 10 minutes；
(6) carbon web frame layer makes
The shape and size of design carbon net as needed, on step (d) gained plane carbon-coating, using method for printing screen
The carbon net of the determined thickness of step (c) is made, and is sintered 10 minutes in 500 DEG C to get low resistance electrode.The carbon web frame
Layer with a thickness of 50 microns.One end of the carbon web frame layer is located at the outside of plane carbon-coating, contacts with conductive substrates, another
End is located 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 from carbon web frame layer and penetrates into mesoporous layer or insulating layer
In, then heating makes solvent volatilize at 100 DEG C, and forms perovskite battery.
The methylamine lead iodine precursor solution, dosage are milliliter grade；Its solvent be dimethyl sulfoxide, butyrolactone it is mixed
Bonding solvent；Its concentration is 1.5 mol/Ls.
(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 (FF), photoelectric conversion efficiency (η).It is shown in Table 2..
Table 2
Claims (9)
1. a kind of low resistance electrode, which is characterized in that the electrode is to be referred to by plane carbon-coating and carbon or that carbon web frame layer is constituted is double
The compound carbon-coating structure of layer, the plane carbon-coating are planar structure, and the carbon refers to or carbon web frame layer refers to for carbon or carbon net knot
Structure；The carbon refers to or carbon web frame layer is arranged on plane carbon-coating, and coverage rate is no more than 80%；
The 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 and referred to by n carbon
The carbon-coating structure of composition, n >=2, carbon refer to that as the carbon-coating structure of similar finger shape, carbon refers to that one end open, the other end are connected with each other,
Two sides are straight line or curve；The shape that carbon refers to includes that single carbon refers to or more carbon refer to；
The 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 is more grid carbon nets as n >=2, and more grid carbon nets include closing structure or hatch frame, and closing structure is that carbon net is whole
It is made of the grid being closed, hatch frame is that be that the grid that is referred to and be closed by carbon is compound constituted carbon net；It is straight for constituting the line of grid
Line or curve；The shape of carbon net includes single grid carbon net, vertical-shaped more grid carbon nets, the more grid carbon nets of horizontal shape, hands over the more grid carbon of shape
Net and more grid single carbons refer to that composite carbon net and the more carbon of more grids refer to any one of composite carbon net or several.
2. a kind of low resistance electrode according to claim 1, which is characterized in that the carbon layers having thicknesses and carbon-coating of the electrode
It is in inverse ratio between sheet resistance, the thickness selection of plane carbon-coating is located at the thickness that carbon-coating sheet resistance is reduced rapidly with the increase of carbon layers having thicknesses
Degree；Carbon refer to or the thickness of carbon web frame layer selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend starts to tend to
In the thickness of stationary value；The plane carbon-coating with a thickness of 5-20 microns；The carbon refer to or carbon web frame layer with a thickness of
30-100 microns.
3. a kind of low resistance electrode according to claim 2, which is characterized in that the plane carbon-coating it is micro- with a thickness of 10
Rice；The carbon refer to or carbon web frame layer with a thickness of 30-50 microns.
4. a kind of low resistance electrode according to claim 1, which is characterized in that the line width range that the carbon refers to is
0.2mm-2mm, line thickness are greater 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 layer, and carbon refers to
Length b is to be less than or equal to or the length of the carbon-coating greater than Tan Zhi lower layer；
The line width range of the carbon net is 0.5mm-5mm, and line thickness is greater than or equal to 10 microns, and the overall width c of carbon net is small
In or equal to carbon side off the net carbon-coating width, Gridding length d is less than or equal to or the length of the carbon-coating greater than carbon side off the net.
5. a kind of low resistance electrode according to claim 4, which is characterized in that the line width range that the carbon refers to is
0.5-1mm, line is with a thickness of 10-50 microns；The line width range of the carbon net is 1-3mm, and line is with a thickness of 15-50 microns.
6. a kind of preparation method of low resistance electrode according to claim 1, which comprises the following steps:
(1) prepared by low resistance carbon pastes；
Graphite, carbon black, inorganic oxide, organic thickening agent and solvent are mixed, carbon slurry is made using ball milling or three roller methods,
The weight ratio of the graphite and carbon black is 1-10:1, and solid content shared by graphite and carbon black is 10-60wt% in carbon slurry,
Solid content shared by inorganic oxide is 1-10wt%, and solid content shared by organic thickening agent is 1-10wt%；
(2) working curve between carbon layers having thicknesses and sheet resistance is established
Carbon-coating is made by method for printing screen, knife coating or spray coating method in carbon pastes obtained by step (1), then in 350-500
DEG C sintering 10-60 minute, the resistance of carbon-coating is measured with four probe instruments or ohmmeter, establish carbon layers having thicknesses and sheet resistance it
Between working curve；The thickness of the carbon-coating is controlled by the number for printing or scratching or spray；
(3) suitable depth of two-layer compound carbon-coating structure is determined
According to working curve obtained by step (2), selection is located at the thickness that carbon-coating sheet resistance is reduced rapidly with the increase of carbon layers having thicknesses
Spend the thickness as plane carbon-coating；Selection be located at carbon-coating sheet resistance with the increase of carbon layers having thicknesses and decreasing trend start to be intended to it is steady
The thickness of definite value refers to as carbon or the thickness of carbon web frame layer；
(4) preparation of plane carbon-coating
The determined thickness plane carbon-coating of step (3) is made using method for printing screen, knife coating or spray coating method, and in 350-500
DEG C sintering 10-60 minutes；
(5) low resistance carbon refers to or the preparation of carbon web frame layer
Design carbon as needed refers to or the shape and size of carbon net, on the plane carbon-coating obtained by step (4), using silk-screen printing side
The carbon that step (3) determined thickness is made in method, knife coating or spray coating method refers to or carbon net, and in 350-500 DEG C of sintering 10-60 points
Clock is to get low resistance electrode.
7. a kind of preparation method of low resistance electrode according to claim 6, which is characterized in that step (1) the carbon slurry
Solid content shared by middle graphite and carbon black is 25-35wt%, and solid content shared by inorganic oxide is 2-5wt%, organic
Solid content shared by thickener is 2-5wt%；The nanometer particle size of the carbon black is less than 50 nanometers；The graphite is graphite flake
Or graphite nodule；The carbon black is nano carbon black, and nanometer particle size is less than 100 nanometers, preferably less than 50 nanometers；The graphite
Weight ratio with carbon black is 1-5:1；The inorganic oxide is titanium oxide, zirconium oxide, aluminium oxide or silica；Described has
Machine thickener is cellulose or hydroxypropyl cellulose；The solvent is one of water, ethyl alcohol, terpinol, 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 minutes；
The raw material that step (4) makes plane carbon-coating uses carbon pastes obtained by step (1) 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.
8. a kind of preparation method of low resistance electrode according to claim 6, which is characterized in that low electricity obtained by step (5)
Resistance electrode is using four probe instruments or ohmmeter test plane carbon-coating and carbon refers to or the sheet resistance of carbon web frame layer.
9. a kind of application of low resistance electrode according to claim 1, which is characterized in that by low resistance electrode used in no sky
On the carbon-based perovskite solar battery in cave.
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